PROCESS FOR THE PRODUCTION OF METHYL ETHYL KETONE

Abstract: This invention is to the production of methyl ethyl ketone (MEK) from mixed normal butenes using polyoxoanion oxidants in an aqueous solution, catalyzed by palladium and preferably containing minor amounts of dissolved chloride ion. An intermediate MEK stream is hydrogenated to remove trace amounts of butyraldehyde from the product MEK stream.

Description: PROCESS FOR THE PRODUCTION OF METHYL ETHYL KETONE RELATED APPLICATIONS This is a continuation-in-part of U.S. Ser. No.07/489,806 "OLEFIN OXIDATION SYSTEM" (PA-0015), filed March 5, 1990, the entirety of which is incorporated by reference. FIELD OF THE INVENTION This invention is to the production of methyl ethyl ketone (MEK) from mixed normal butenes using polyoxoanion oxidants in an aqueous solution, catalyzed by palladium and preferably containing minor amounts of dissolved chloride ion. An intermediate MEK stream is hydrogenated to remove trace amounts of butyraldehyde from the product MEK stream. BACKGROUND OF THE INVENTION Our disclosed catalyst solutions and processes are useful for the production of aldehydes, ketones, and carboxylic acids, which are chemicals of commerce and/or feedstocks for the production of chemicals and materials of commerce. For example, acetone, MEK and methyl isobutyl ketone are used as solvents. Acetaldehyde is used in the production of acetic acid, polyols, and pyridines. Acetic acid is used in the production of vinyl acetate, cellulose acetate, and various alkyl acetate esters which are used as solvents. Acetone is used in the production of methylmethacrylate for poly-methylmethacrylate. Cyclohexanone is used in the production of caprolactam for nylon-6 and adipic acid for nylon-6,6. Other cyclic ketones can be used for the production of other nylon-type polymers. Acetaldehyde is industrially produced by the Wacker oxidation of ethylene by dioxygen, which uses an aqueous catalyst system of palladium chloride, copper chloride, and hydrochloric acid to accomplish the following net conversion: C 2 H 4 + _0 2 > CH 3 CHO(1) Reviews of the Wacker process chemistry and manufacturing processes for the direct oxidation of ethylene to acetaldehyde can be found in "The Oxidation of Olefins with Palladium Chloride Catalysts", Angew. Chem. internat. Edit., Vol. 1 (1962), pp. 80-88, and in Chapter 8 of Ethylene and its Industrial Derivatives, S.A. Miller ed., Ernest Benn Ltd., London, 1969, each of which is incorporated by reference entirely. Aspects of Wacker technology are also disclosed in United States Patents Nos. 3,122,586, 3,119,875, and 3,154,586, each incorporated by reference entirely. In the Wacker process chemistry, ethylene is oxidized by cupric chloride in aqueous solution, catalyzed by palladium: Pd"CI 4 C 2 H 4 + 2 Cu"CI 2 + H 2 0 > CH 3 CHO + 2 Cu'C! 2 - + 2 H " (2) In a typical manufacturing operation, copper is present in the aqueous solution at concentrations of about 1 mole per liter, total chloride is present at concentrations of about 2 moles per liter, and the palladium catalyst is present at concentrations of about 0.01 moles per liter. Under these conditions, palladium(ll) exists predominantly as the tetrachloropalladate ion. Cuprous chloride resulting from the oxidation of ethylene is solubilized in the aqueous solution by the co-produced hydrochloric acid, as the dichlorocuprate ion. In a subsequent Wacker chemistry step, this reduced copper is reoxidized by reaction with dioxygen: 2 Cu'cr 2 + 2 H + + _ 0 2 > 2 Cu CI 2 + H 2 0(3) (Reactions (2) and (3) combined give overall reaction (1)) Two acetaldehyde manufacturing processes, a two-stage process and a one-stage process, have been developed and operated using the Wacker system chemistry. In the two-stage process, ethylene oxidation by cupric chloride, reaction (2), and reoxidation of cuprous chloride by air, reaction (3), are conducted separately, with intermediate removal of the acetaldehyde product from the aqueous solution. The reoxidized aqueous solution is recycled to the ethylene oxidation stage. The reactions are conducted at temperatures of about 100 to 120" C in reactors which, by providing very efficient gas-liquid mixing, result in high diffusion (mass transfer) rates of the reacting gas into the aqueous solution. Under these conditions, about 0.24 moles ethylene per liter of solution can be reacted within about 1 minute in the ethylene reactor, corresponding to an average ethylene reaction rate of about 4 (millimoles/liter) /second. With a typical palladium concentration of about 0.01 moles per liter, this corresponds to a palladium turnover frequency (a measure of catalyst activity) of about 0.4 (moles C 2 H 4 /mole Pd)/second. In the air reactor, about 0.12 moles dioxygen per liter of solution can be reacted within about 1 minute, corresponding to an average dioxygen reaction rate of about 2 (millimoles/ liter)/second. In the one-stage process, ethylene and dioxygen are simultaneously reacted with the aqueous solution, from which acetaldehyde is continuously removed. Palladium catalyzes the oxidation of ethylene by cupric chloride (reaction (2)) by oxidizing ethylene (reaction (4)) and then reducing cupric chloride (reaction (5)): C 2 H 4 + PdCI 4 = + H 2 0 > CH 3 CHO + Pd° + 2 H + + 4CP(4) Pd° + 4CI ' + 2 Cu"CI 2 > PdCI 4 = + 2 Cu'C ;(5) Functionally, the copper chlorides mediate the indirect reoxidation of the reduced palladium (0) by dioxygen via reaction (5) plus reaction (3). Direct oxidation of palladium (0) by dioxygen is thermodynamically possible but is far too slow for practical application. The overall rate of oxidation of ethylene by the Wacker system is limited by the rate of oxidation of ethylene by the tetrachloropalladate (reaction (4)). The reaction rate is inversely dependent on both the hydrogen ion concentration and the square of the chloride ion concentration, having the following concentration dependencies: reaction rate= f[PdCI 4 ][C 2 H 4 ]/[H + ][Cr] 2 (6) Two chloride ions must be dissociated from tetrachloropalladate before palladium(ll) productively binds both the substrates of reaction (4), ethylene and water. Said another way, chloride competes with the two substrates for the third and fourth coordination sites on palladium(ll). This occurs by the following equilibria: PdCI 4 = + C 2 H 4 = = = = = PdCI 3 (C 2 H 4 )- + Cf(7) PdCI 3 (C 2 H 4 V + H 2 0 = = = = = PdCI 2 (C 2 H 4 )(H 2 0) + CP(8) Not only does chloride ion competitively inhibit the binding of substrates, but the remaining bound chlorides in intermediate complexes diminish the electrophilicity (positive charge density) at the palladium(II) center, which electrophilicity drives the overall reaction to palladium(0). The subsequent reaction steps, hydrogen ion dissociation (reaction (9)) and collapse of the resulting intermediate to products (reaction (10)), are less favored for these chloride-bound intermediate complexes, relative to their aquated counterparts with fewer or no bound chlorides. PdCI 2 (C 2 H 4 ) (H 2 0) = = = = = PdC! 2 (C 2 H 4 ) (OHV + H + (9) PdCI 2 (C 2 H 4 )(OH)- .. > .. > .. > CH 3 CHO + Pd° + H + + 2Cr(10) A step in reaction (10) is turnover rate-limiting for reaction (4) in the Wacker system (reactions (7), (8), (9), and (10) give reaction (4)), so that the disfavoring influences of chloride ion on reaction (10) and on the preceding equilibria (7), (8), and (9) are manifested in the obtained palladium catalyst activity. However, the Wacker system requires a high total chloride concentration to function effectively. The chloride to copper ratio must be greater than 1:1 for the copper(ll) to be soluble CuCI 2 rather than insufficiently soluble copper hydroxide chlorides, and for copper(l) to be soluble CuCI 2 " rather than insoluble CuCI. Moreover, in the absence of chloride, aquated copper(ll) is thermodynamically impotent for oxidizing palladium (0) metal to aquated palladium(ll). Chloride complexation raises the copper(ll)/copper(l) oxidation potential and lowers the palladium (11)/ palladium (0) oxidation potential, so that at high chloride ion concentrations the forward reaction (5) becomes thermodynamically favored. The Wacker system has several undesirable characteristics in the manufacture of acetaldehyde. These undesirable characteristics result from the high cupric chloride concentration. The aqueous cupric chloride solution is extremely corrosive; manufacturing process equipment is constructed of expensive corrosion resistant materials, usually titanium. The manufacturing processes typically convert a percent or more of the ethylene feed to chlorinated organic by-products. These chlorinated organic by-products are hygienically and environmentally objectionable. Their adequate separation from the acetaldehyde product and from other gas and liquid streams which exit the process and their proper destruction or disposal add to the operating costs of the manufacturing processes. These chlorinated organic by-products have a number of mechanistic origins. Some result from direct additions of hydrochloric acid to ethylene, giving ethylchloride, and to olefinic by-products. Others result from palladium centered oxychlorination, for example, 2-chloroethanol from ethylene. The predominant origin of chlorinated organic by-products is oxychlorination by cupric chloride; most arise from copper centered oxychlorination of acetaldehyde, giving chloroacetaldehydes, and further reactions of the chloroacetaldehydes. Accordingly, we determined that most of the objectionable chlorinated organic by-product yield results not simply from the presence of chloride, but from the combination of chloride and copper. Aqueous palladium(ll) salts also oxidize higher olefins to carbonyl compounds according to equation (11), where R, R', and R" are hydrocarbyl substituent groups and/or hydrogen (R = R' = R" = H for ethylene): O RR'C=CHR" + Pd" + H 2 0 > RR'CH-CR" + Pd° + 2 H + (11) As examples, aqueous palladium(ll) salts oxidize propylene to acetone (and some propionaldehyde), butenes to MEK (and some butyraldehyde), and cyclohexene to cyclohexanone. Higher olefins can be oxidized by dioxygen using the Wacker system, but serious problems encountered in using the Wacker system to oxidize higher olefins have effectively prohibited any other significant application to manufacturing carbonyl compounds. The rate of oxidation of the olefinic double bond by aqueous palladium(ll) salts generally decreases as the number and/or size of hydrocarbyl substituents increases. This decrease in rate is particularly severe with PdCI 4 = in the Wacker system, due to the competition of chloride with the more weakly binding higher olefins for palladium(ll) complexation and due to the lowered electrophilicity of multiply chloride-bound olefin-palladium(ll) intermediates. Consequently, much higher palladium concentrations (with its concomitant palladium investment) are necessary to obtain volumetric production rates of higher carbonyl compounds comparable to acetaldehyde production rates. An even more prohibitive disadvantage of the Wacker system for manufacturing carbonyl compounds from higher olefins is the substantially increased production of chlorinated organic by-products. Higher olefins are more susceptible to palladium centered oxychlorination, which chlorinates not only at olefinic carbon atoms but also at allylic carbon atoms. Higher aldehydes and ketones having methylene groups adjacent to the carbonyl group are also more susceptible to cupric chloride mediated oxychlorination than is acetaldehyde. As a result, the productivity of the Wacker system for producing chlorinated organic by-products increases rapidly both with increasing number and size of hydrocarbyl substituents in the olefin. Other, multistep manufacturing processes are typically used instead of the Wacker process to convert higher olefins into corresponding carbonyl compounds. For example, the manufacture of MEK (2-butanone) involves the reaction of n-butenes with concentrated sulfuric acid to produce sec-butyl hydrogen sulfate and hydrolysis of sec-butyl hydrogen sulfate to obtain 2- butanol and diluted sulfuric acid. The alcohol, 2-butanol, is catalytically dehydrogenated to produce MEK. The diluted sulfuric acid must be reconcentrated for recycle. Other carbonyl compounds are instead manufactured from starting materials more expensive than the corresponding higher olefin. For example, cyclopentanone is manufactured from adipic acid instead of from cyclopentene. An effective method for the direct oxidation of higher olefins to carbonyl compounds by dioxygen has been long sought in order to enable more economical manufacturing of carbonyl compounds. Yet, in 30 years since the development of the Wacker system, no alternate palladium-based system for the oxidation of olefins by dioxygen which avoids the disadvantages and limitations of the Wacker system has been successfully applied in commercial manufacturing operation. Systems have been proposed which use polyoxoanions, instead of cupric chloride, in combination with palladium to effect the oxidation of olefins. United States Patent No. 3,485,877, assigned to Eastman Kodak Company (hereafter, "Eastman patent") discloses a system for converting olefins to carbonyl compounds by contacting with an agent comprising two components, one of which is palladium or platinum, and the other is molybdenum trioxide or a heteropolyacid or salt thereof. This patent discloses that the so-called "contact agent" may be in an aqueous solution for a liquid phase process, but that it is advantageous and preferred to support the agent on a solid carrier for a vapor phase process in which gaseous olefin is contacted with the solid phase agent. The patent compares the oxidation of propyiene with a liquid phase contact agent (in Example 16), to give acetone substantially free of by-products with the oxidation of propyiene in the vapor phase with a corresponding solid contact agent (in Example 10), to give acrolein. Apparently, the behavior of an olefin's liquid phase reaction with the disclosed aqueous contact agent solution cannot be predicted from the behavior of the olefin's vapor phase reaction with the analogous solid contact agent. The Eastman patent discloses that, when operating in the liquid phase, heteropolyacids or their salts, and particularly phosphomolybdic acid or silicomolybdic acid in water are preferred. Among the heteropolyacids disclosed, only phosphomolybdic acid and silicomolybdic acid are demonstrated by working example. No salts of heteropolyacids are so demonstrated. Phosphomolybdovanadic acid or salts thereof are nowhere mentioned in this patent. Eastman patent also discloses the reaction in the presence of oxygen or oxygen containing gas. It also discloses periodic regeneration of the contact agent with air. However, the use of oxygen or air is demonstrated by working examples only for reactions of olefins in the vapor phase with solid phase contact agents. We have found that oxygen reacts too slowly with reduced phosphomolybdic acid or silicomolybdic acid in aqueous solutions for such solutions to be practically useful in the industrial conversion of olefins to carbonyl compounds using oxygen or air as oxidant. In contrast, our reduced polyoxoanions comprising vanadium in aqueous solution of the present invention can react rapidly with oxygen or air. In addition, Eastman patent discloses palladium chlorides among various preferred palladium or platinum components for the contact agent. Palladous chloride is predominantly used among the working examples. Eastman patent also discloses that it is possible to improve the action of the contact agent by incorporating small amounts of hydrochloric acid or ferric chloride. However, the only demonstration by working example adds ferric chloride in a solid phase contact agent for a vapor phase reaction (Example 19) to obtain higher reaction rates (conversion and space time yield). No such demonstration, nor result, is given for addition of hydrochloric acid to either a solid or a liquid phase contact agent, nor for addition of either hydrochloric acid or ferric chloride to a liquid phase contact agent. Belgian Patent No. 828,603 and corresponding United Kingdom Patent No. 1,508,331 (hereafter "Matveev patents") disclose a system for the liquid phase oxidation of olefins employing an aqueous solution combining: a) a palladium compound; b) a reversible oxidant which has a redox potential in excess of 0.5 volt and which is a mixed isopolyacid or heteropolyacid containing both molybdenum and vanadium, or a salt of said polyacid; and, c) an organic or mineral acid other than said mixed isopolyacid or heteropolyacid, which organic or mineral acid is free of halide ions and is unreactive (or at most weakly reactive) with the palladium compound. The disclosed system differs from that of Eastman patent by simultaneously employing only certain heteropolyacids and mixed isopolyacids and adding certain other acids to the solution. Those certain polyacids employed contain both molybdenum and vanadium. Those certain other acids added are not the polyacid and are free of halide ions. The Matveev patents disclose that only the certain polyacids, containing both molybdenum and vanadium, function satisfactorily in the system as reversiblv acting oxidants, wherein the reduced form of the oxidant is reacted with dioxygen to regenerate the oxidant. The patent further discloses that the polyacid used contains from 1 to 8 vanadium atoms, more preferably 6 atoms, in a molecule with molybdenum. According to the disclosure, as the number of vanadium atoms increases from 1 to 6 the principal characteristics of the catalyst, such as its activity, stability, and olefin capacity, increase. The Matveev patents disclose typical heteropolyacids of a formula H n [PMo p V q O 40 ], in which n=3+q, p = 12-q, q = 1 to 10. The Matveev patents disclose that the catalyst is prepared, in part, by dissolving in water, oxides, salts, and/or acids of the elements forming the polyacid and then adding to the solution, the specified other organic or mineral acid. A preferred catalyst is said to be prepared by dissolving in water Na 3 P0 4 (or Na 2 HP0 4 , or NaH 2 P0 4 , or H 3 P0 4 , or P 2 0 5 ), Mo0 3 (or Na 2 Mo0 4 , or H 2 Mo0 4 ), V 2 0 5 (or NaV0 3 ), and Na 2 C0 3 (or NaOH) to form a solution, adding PdCI 2 to the solution of molybdovanadophosphoric acid, and then adding the other acid. (Sulfuric acid is the only such acid demonstrated by working example.) It is said to be best if the total number of Na atoms per atom of P is not less than 6. Heteropolyacids in the series designated are said to be obtained, and are said to be used in most of the working examples. (We have found that such solutions prepared according to the methods disclosed in Matveev patents are not actually solutions of free heteropolyacids, as designated by formulas of the type H n [PMo p V q O 40 ]. Instead, they are solutions of sodium salts of partially or completely neutralized heteropolyacids; that is, solutions of sodium polyoxoanion salts.) According to the Matveev patents, the activity and stability of the catalyst is increased by the presence of certain other mineral or organic acids which do not react (or react only feebly) with palladium and contain no halide ions(e.g. H 2 S0 4 , HN0 3 , H 3 P0 4 , or CH 3 COOH),. The most preferable of the above acids is sulfuric acid, which is said to increase the activity and stability of the catalyst while not seriously increasing the corrosivity of the solution. Sulfuric acid is the only acid which appears in the working examples. The Matveev patents prescribe that the amount of acid is enough to maintain the pH of the solution at not more than 3, preferably at 1.0. The working examples predominantly demonstrate pH 1. The Matveev patents indicate that with "higher pH values", the catalyst is not sufficiently stable with respect to hydrolysis and palladium precipitation, and is of low activity in the olefinic reaction. They further indicate that with "lower pH values", the rate of the oxygen reaction is appreciably diminished. However, the Matveev patents do not disclose any method for determining the pH of the disclosed solutions, nor do they specify anywhere how much sulfuric acid was added to achieve the stated pH value. The disclosure in the Matveev patents is generally directed towards providing a catalyst system having a reversibly acting oxidant (wherein the reduced form of the oxidant can be reacted with dioxygen to regenerate the oxidant) and having an absence of chloride ions. Mineral acids which contain halide ions are specifically excluded from the certain other acids added in the disclosed system. PdCI 2 is among the palladium compounds used in the working examples; it is the only source of added chloride disclosed and is added only coincidental to the selection of the palladium source. PdCI 2 and PdS0 4 are generally disclosed to be equivalent palladium sources. The Matveev patents' preferred palladium concentration in the catalyst is said to be 0.002 g-atom/liter (2 millimolar). This is the concentration demonstrated in most of the working examples. In Example 9 of both Belgian and British patents, a catalyst containing a very high concentration of heteropolyacid, 1.0 g-mole/liter, and a very high concentration of PdCI 2 , 0.5 g- atom/liter, is disclosed. This would mean that 1.0 g-atom/liter chloride is added as part of the palladium source. The stated conclusion from this example is that the high viscosity and specific gravity of such concentrated solutions adversely affect the mass transfer conditions and make the process diffusion controlled and impractical. The result reported for this test with 0.5 g- atom/liter PdCI 2 is so poor, especially in terms of palladium activity (see Table 1), as to lead one away from attempting to use the example. The results of selected working examples reported in Matveev patents are presented in Table 1. The examples selected are those said to use a phosphomolybdovanadic heteropolyacid in the oxidation of ethylene for which quantitative results are reported. Data and results to the left of the vertical bar in Table 1 are taken directly from the patent. Results to the right of the vertical bar are calculated from the reported results. The Example numbers are those used in Belgian 828,603. Most working examples in the Matveev patents report tests conducted in a shaking glass reactor. Typical reaction conditions in this reactor were 90 °C with 4.4 psi of ethylene, and separately with 4.4 psi of oxygen. Among the examples collected in Table 1, those using the shaking glass reactor with the preferred concentrations of heteropolyacid and palladium (Examples 1-6) gave ethylene and oxygen rates of 0.089-0.156 and 0.037-0.086 (millimoles/liter) /second, respectively (see Table 1). Example 9, with 0.5 g- atom/ liter PdCI 2 , is said to be diffusion controlled; ethylene and oxygen reaction rates were 0.223 and 0.156 (millimoles/ liter)/second, respectively. We have found that shaking reactors are generally poor devices for mixing such gaseous reactants and liquid aqueous phases and diffusion (mass transfer) of gaseous reactants into an aqueous catalyst solution for reaction is prohibitively slow. Additionally, 4.4 psi of ethylene is relatively too low a pressure for rapid diffusion of ethylene into a aqueous catalyst solution. One test in Example 6 is reported for another reactor, a stainless steel reactor, with 88.2 psi of ethylene and with 51.4 psi of oxygen, each at 110°C. The method of mixing the gas and liquid phases in this reactor is not specified. Example 6 also reports results with the same catalyst system in the shaking glass reactor. The ethylene reaction rates were 0.141 (millimoles/liter) /second in the shaking glass reactor and 0.670 (millimoles/liter)/second in the stainless steel reactor. The oxygen reaction rates were 0.045 (millimoles/liter)/second in the shaking glass reactor and 0.335 (millimoles/ liter)/second in the stainless steel reactor. Thus, the reaction rates did not increase proportionally with the pressure increases. It is well known that the diffusion rate of a reacting gas into a liquid, as well as the gas molecule concentration in the liquid phase at saturation, is proportional to the partial pressure of the gas in the gas phase, all other factors being constant. Accordingly, the stainless steel reactor used for the higher pressure test of Example 6 appears to be a poorer device for the mixing of gas and liquid phases than the shaking glass reactor used for the other tests in the Matveev patents. Typical apparent palladium turnover frequencies calculated from ethylene reaction rates and palladium concentrations reported in the Matveev patents' working examples using a shaking glass reactor are all less than 0.2 (millimoles C 2 H 4 /mg-atom Pd) /second. The higher pressure test at 110°C in a stainless steel reactor in Example 6 gave the highest apparent palladium turnover frequency of 0.335 (millimoles C 2 H 4 /mg-atom Pd)/second. Although the Matveev patents state that the disclosed catalysts are up to 30 to 100 times more active in olefin oxidation than the Wacker catalyst, the apparent activity of the palladium catalyst in the best example is no higher than the activity of a typical Wacker palladium catalyst in typical process operation at comparable temperatures. This result is obtained even though the disclosed catalyst solution is substantially free of the chloride ion concentration which inhibits the palladium activity in the Wacker catalyst. The present invention demonstrabiy provides palladium catalyst activities substantially exceeding the activity of a Wacker palladium catalyst in typical process operation. From the Matveev patents' ethylene reaction capacities and the palladium concentrations, the number of palladium turnovers per ethylene reaction capacity can be calculated (see Table 1, TON). The highest number of turnovers obtained was 400 with the heteropolyacid containing 8 vanadium atoms (and with 35% excess vanadium present), Example 2. The ethylene reaction capacities of the catalyst solutions of Matveev's working examples appear generally to follow the vanadium content of the solutions (see Table 1). For the tests with the preferred concentrations of heteropolyacid and palladium and at the preferred pH 1 (Examples 1-6), the reported ethylene reaction capacities are calculated to correspond to 40% to 53% of the oxidizing capacity of the vanadium (V) content of the solution, assuming two vanadium(V) centers are reduced to vanadium(IV) for each ethylene oxidized to acetaldehyde. Example 12 of Matveev's Belgian patent reports a test with no addition of sulfuric acid. (This result was omitted from the UK patent.) The heteropolyacid is designated H 5 [PMo 10 V 2 O 40 ] and is used at 0.1 molar concentration with palladium sulfate at 0.1 mg-atom/liter concentration. A pH for this solution is not reported. The reaction is conducted at 50 °C. On cycling between ethylene and oxygen reactions, the rate of the ethylene reaction is said to diminish constantly due to hydrolysis of the Pd salt. (Typical examples with sulfuric acid added, such as examples 1-6, were reported stable to 10 or more cycles.) This result corresponds to Matveev's disclosure that the stability of the catalyst is increased by sulfuric acid, that the amount of acid is such as to maintain the pH at not more than 3, and that with higher pH values the catalyst is not sufficiently stable against hydrolysis and palladium precipitation. This result reported with no addition of sulfuric acid is so poor as to lead one away from attempting to use the example. The Matveev patents also report working examples for the oxidation of propyiene to acetone, n-butenes to MEK, and 1-hexene to methyl butyl ketone using the disclosed catalyst system. For reaction of mixtures of n-butenes, 4.4 psi, at 90 β C in the shaking glass reactor (Example 19 in Belgian 828,603; Example 16 in UK 1,508,331), the reported reaction rate is 50 [(ml butenes at 750 mm Hg, 23°C)/liter]/minute (corresponding to 0.037 (millimoles butenes/liter)/second) an the capacity of the reaction solution is 0.25 moles butenes/liter. The palladium concentration in the example is 2 mg-atom/liter: the palladium turnover frequency is calculated 0.019 (millimoles butenes/mg- atom Pd)/second; the number of Pd turnovers per butene reaction capacity is calculated 125. The fraction of the vanadium(V) concentration of the solution reduced by the butene capacity is calculated 51%. In contrast to the teachings of the Matveev patents, we have found the following: 1) Although the patent teaches that sulfuric acid increases the activity and stability of the catalyst, we have discovered that substantially increased activity (olefin and oxygen reaction rates) and stability can be obtained by avoiding the presence of sulfuric acid, and of sulfate species generally; 2) Although the patent teaches that the rate of the oxygen reaction is appreciably diminished at pH values lower than 1 , we have discovered oxygen reaction rates which are orders of magnitude higher than those reported in the patent and which are substantially undiminished in solutions substantially more acidic than pH 1 , can be obtained; 3) Although the patent teaches that the activity and stability of the catalyst are increased on increasing the number of vanadium atoms in the polyacid, for example from 1 to 6, we have discovered that, at least in the production of acetaldehyde, the activity (olefin and dioxygen reaction rates) is typically invariable with the vanadium content of the polyacid and the stability is decreased on increasing the vanadium content of the polyacid towards 6; 4) Although the patent teaches that the total number of Na atoms per atom of P be not less than 6, we have found that in the preferred polyoxoanion-comprising catalyst solutions of the present invention, which optionally contain Na + countercations, by preferably keeping the number of Na atoms per atom of P is less than 6, the desired acidity can be obtained while avoiding sulfuric acid. Additional results from some of the inventors of the Matveev patents are reported in Kinetika i Kataliz, vol. 18 (1977), pp. 380-386 (English translation edition pp. 320-326, hereafter "Kinet. Katal. 18-1"). Reaction kinetic experiments are reported for the ethylene oxidation reaction with phosphomolybdicvanadic heteropolyacids in the presence of Pd(ll) sulfate using a shaking reactor with circulation of the gas phase. The absolute values of the observed reaction rates are said to be quite small, and not complicated by mass-transfer processes. Most of the reported experiments are conducted at about 20 β C, and this low temperature appears to be the principal reason the observed reaction rates are so small as to be slower than the mass-transfer limitations of the shaking reactor. Typical reaction rates reported are about 1 to 12 x 10 "4 (moles/liter)/minute, which corresponds to about 0.002 to 0.020 (millimoles/liter)/second; compare to ethylene reaction rates of about 0.1-0.2 (millimoles/liter)/second calculated from the results reported for experiments at 90°C in Matveev patents (see Table 1). Ethylene pressures for these reactions are not reported; the ethylene concentrations are instead given, but no method of determining the ethylene concentration or of relating it to the partial pressure is given. Kinet. Katal. 18-1 states that solutions of phosphomolybdicvanadic heteropolyacids were synthesized by a procedure described in Zh. Neorg. Khim., vol. 18 (1973), p. 413 (English translation edition pp. 216-219). This reference describes making solutions from Na 2 HP0 4 , Na 2 Mo0 4 »2H 2 0, and NaV0 3 »2H 2 0 at pH 2; the method of acidification of the solutions of these basic salts, when stated, is with sulfuric acid. (This reference further mentions the isolation of crystalline vanadomolybdophosphoric acids via ether extraction of their ether addition compounds from sulfuric acid-acidified solutions. These methods of preparing solution vanadomolybdophosphoric acids with sulfuric acid and crystalline products by ether extraction are also described in earlier papers cited by this reference; for example, Inorg. Chem., 7 (1968), p. 137.) The reaction solutions of Kinet. Katal. 18-1 are said to be prepared from the solutions of phosphomolybdicvanadic heteropolyacids by addition palladium sulfate, dilution, and adjustment of the pH by the addition of H 2 S0 4 or NaOH. However, this reference does not disclose the composition of the test solutions, in terms of the amounts of H 2 S0 4 or NaOH added, nor any method for determining the pH of the disclosed solutions. Kinet. Katal. 18-1 reports the dependence of the ethylene reaction rate on the solution pH over the stated range 0.8 to 2.2, under the disclosed conditions with the heteropolyacid designated H 6 [PMo 9 V 3 O 40 ] at 0.05 mole/liter, palladium at 3 x 10 '3 g-atom/liter, ethylene at 1 x 10 " mole/liter, and 21 °C. As the pH is increased towards 2, the rate of the ethylene reaction is shown to decrease. From evaluation of graphic figures in the reference, the maximum rate of ethylene reaction was achieved over a pH range of 0.8 to 1.6, and corresponded to 0.023 (millimole C 2 H 4 /liter)/second and a palladium turnover frequency of 0.078 (mole C 2 H 4 /mole palladium)/second. Matveev reviews his studies on the oxidation of ethylene to acetaldehyde in Kinetika i Kataliz, vol. 18 (1977), pp. 862-877 (English translation edition pp. 716-727; "Kinet. Katal. 18-2" ). The author states (English translation edition p. 722): "The chloride-free catalyst was an aqueous solution of one of the HPA-n, acidified with H 2 S0 4 to pH 1, in which a nonhalide palladium salt (sulfate, acetate, etc.) was dissolved." (HPA-n are defined as phosphomolybdenumvanadium heteropolyacids.) Reference is then made to the studies reported in Kinet. Katal. 18-1. Reaction Kinetics and Catalysis Letters, vol 16 (1981), pp. 383-386 reports oxidation of 1 -octene to 2-octanone using a catalytic system of PdS0 4 and heteropolyacid designated H 9 PMo 6 V 6 O 40 in a shaking glass reactor with 1 atm. oxygen. The heteropolyacid is said to be synthesized as in UK 1,508,331, and used as an acidic sodium salt Na 7 H 2 PMo 6 V 6 O 40 . The catalyst solution is said to have a pH equal to 0.5-1.0, which was attained by the addition of H 2 S0 4 . However, no results are identified with a specific pH value. Palladium is used in concentrations of -4-6 millimolar and PdS0 4 is said to give a more active catalyst than PdCI 2 . The catalyst is said to have limited stability above 80 °C, apparently due to precipitation of palladium. Ropa Uhlie 28, pp. 297-302 (1986) (Chem Abstr. 107(1):6740r) reports oxidation of 1-octene to 2-octanone using a solution of 0.075 M heteropolyacid designated H 3+n PMo 12.n V_O 40 , n= 6 or 8, and containing PdS0 4 . The heteropolyacid solution was prepared from NaH 2 P0 4 , Mo0 3 , and V 2 0 5 in water by addition of NaOH, then H 2 S0 4 , with adjustment of the stated pH to 1. J. Organomet. Chem. 327 (1987) pp. C9-C14 reports oxidation of 1- octene to 2-octanone by oxygen using an aqueous solution of 0.12 mole/liter heteropolyacid designated HNa 6 PMo 8 V 4 O 40 , with 0.01 mole/liter PdS0 4 , with various co-solvents, at 20 °C, in one-stage mode. The heteropolyacid is said to be prepared by the method described in UK 1 ,508,331 ; the pH of the catalyst solution is not specifically disclosed. For the reaction, 1 -octene and oxygen are contacted simultaneously with the catalyst solution. The heteropolyacid cocatalyst is said to be regenerated by treating the aqueous solution with 1 atm. 0 2 at 75 β C. Reaction Kinetics and Catalysis Letters, vol 3 (1975), pp. 305-310 reports the oxidation of vanadium (IV) in aqueous solutions of vanadyl sulfate (V lv OS0 4 ), 0.05-0.25 mole/liter, in the pH region 2.5-4.5, in the presence of small amounts of sodium molybdate in a shaker reactor, at 30 °C with 730 mmHg oxygen pressure. At pH values below 3.0 the reaction rate is reported to decrease sharply. A heteropolyacid complex of molybdenum and vanadium was isolated from a reaction solution. Koordinatsionnaya Khimiya, vol. 3 (1977), pp. 51-58 (English translation edition pp. 39-44) reports the oxidation of reduced phosphomolybdovanadium heteropolyacids containing vanadium(IV), in aqueous solution at pH's . 1, at 60°C by oxygen. Heteropolyacids designated H 3+n [PMo 12 . n V n 0 40 ], n = 1-3, were said to be synthesized by the method of Zh. Neorg. Khim., vol. 18 (1973), p. 413 (see above), and a solution of the sodium salt of the heteropolyacid designated n=6 was said to be prepared by dissolving stoichiometric amounts of sodium phosphate, molybdate, and vanadate in water, boiling the solution, and acidifying it to pH 1. Different pH values for the solutions of the reduced forms of these heteropolyacids were said to be obtained by altering the initial pH values of the heteropolyacid solutions, monitored by a pH meter. The acid used for acidification and for altering the initial pH values are not disclosed. Oxygen reaction rates for the reduced forms of the heteropolyacids designated n= 2, 3, and 6 show maxima at about pH 3 (at about 34 x 10 '3 (mole/ liter)/minute; or, 0.57 (millimole/liter)/second), and decline precipitously as the pH is lowered; it becomes almost negligible for n=2 at pH 1. Koordinatsionnaya Khimiya, vol. 5 (1979), pp. 78-85 (English translation edition pp. 60-66) reports the oxidation of vanadium (IV) in aqueous solutions of vanadyl sulfate, 0.1-0.4 mole/liter, in the pH region 2.5-4.5, in the presence of smaller amounts of molybdovanadophosphoric heteropolyacid designated H 9 PMo 6 V 6 O 40 , in an agitated reactor, at 0-30 "C, by oxygen . A weak dependence of the rate on pH is reported, with the rate decreasing with decreasing pH below about pH 3.5. The addition of Na 2 S0 4 is said to have no influence on the rate of the reaction. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1981, pp. 2428- 2435 (English translation edition pp. 2001-2007) reports studies of the oxidation of reduced forms ("blues") of molybdovanadophosphate heteropolyacids designated H 3+ -[PMo 12 . n V n O 40 ], n = 1-4,6, containing vanadium(IV), in aqueous solution at pH 3.0, in a glass flask with magnetically-coupled stirring of the liquid phase, at 25 β C with 2-10 kPa (0.3-1.5 psi) oxygen. Reaction rates are extremely slow under these low temperature, low pressure conditions in this reaction mixing vessel. (From the data, reaction rates in the region < 0.0001 (millimoles/liter)/ second are calculated.) The oxygen reaction rates of a reduced form of the molybdovanadophosphate n=3 were measured at pH's 2.0, 3.0, and 4.0. A maximum was observed at pH 3.0. Aqueous solutions of Na salts of the heteropolyacids and the corresponding blues for the experiments were said to be obtained as in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, 1980, pp. 1469. This reference discloses that aqueous solutions of heteropolyanions were obtained by reacting stoichiometric amounts of H 3 P0 4 , Mo0 3 , and NaV0 3 «2H 2 0 with heating in the presence of Na 2 C0 3 . (Neither the amount of Na 2 C0 3 added, the concentration of heteropolyanion, the resulting pH's, nor the complete compositions of the solutions are disclosed.) This reference further discloses the addition of vanadium(IV) in the form of VOS0 4 »2H 2 0 to produce the heteropoly blues. The experimental solutions in this reference are said to comprise heteropolyanion and vanadyl at pH 1.60-2.98, buffer solution of NaHS0 4 and Na 2 S0 4 ; neither the concentration of the buffering sulfate ions nor an accounting of their origin is disclosed. Reaction Kinetics and Catalysis Letters, vol 17 (1981), pp. 401-406 reports the oxidation of vanadium (IV) in aqueous solutions of vanadyl sulfate , 0.02-0.4 mole/liter, in the pH region 2.5-4.5, in the presence of smaller amounts of molybdovanadophosphoric heteropolyacid designated H 6 PMo 9 V 3 O 40 , by the methods of Koordinatsionnaya Khimiya, vol. 5 (1979), pp. 78-85. At pH values below 3.0 the reaction rate is reported to decrease sharply. J. Chem. Soc. Dalton Trans., 1984, pp. 1223-1228 reports studies of the palladium sulfate-cataiyzed oxidation of 1 -butene to MEK with phosphomolybdovanadic acids both in the absence and in the presence of oxygen. These studies are reported in greater detail in Palladium and Heteropolyacid Catalyzed Oxidation of Butene to Butanone, S.F. Davison, Ph.D. Thesis, University of Sheffield, 1981. These references report, as do others loc. cit.. that phosphomolybdovanadic acids are extremely complex mixtures of anions of the type [PMo 12 . x V x O 40 ] (3+x)" . Crystalline phosphomolybdovanadic acids, designated H 3+n [PMo 12 . n V n O 40 ], n = 1-3, prepared by the ether extraction method of Inorg. Chem., 7 (1968), p. 137 were observed to be mixtures which disproportionated still further in the acidic media used for catalysis. Accordingly, solutions prepared by the method of UK 1,508,8,331 were chosen as appropriate for the catalytic reactions (see Davison Thesis, pp. 63 and 77), except that stoichiometric amounts of V 2 0 5 (not excess) were used. The solutions were prepared from V 2 0 5 , Mo0 3 , Na 3 P0 4 »12H 2 0, and Na 2 C0 3 , at 0.2 M P, and acidified to pH 1 by addition of concentrated sulfuric acid The reactions of J. Chem. Soc. Dalton Trans., 1984, pp. 1223-1228 and Davison Thesis in the absence of oxygen were conducted at 20 °C and 1 atm 1 -butene in a mechanically shaken round-bottomed flask. Reactions using 5 mM PdS0 4 and 0.05 M vanadium(V) in aqueous sulfuric acid (0.03-0.2 mole/liter, depending on n) are reported to give similar initial reaction rates for n = 1-7. The reactions required ca. 30 minutes for completion and gave 5 turnovers on Pd (stoichiometric for two vanadium(V) reduced to vanadium(IV) per 1 -butene oxidized to MEK.). A stated intention of the work was to minimize chloride content; PdCI 2 is said to have similar reactivity to PdS0 4 . The reactions of J. Chem. Soc. Dalton Trans., 1984, pp. 1223-1228 and Davison Thesis in the presence of oxygen were conducted at 20 °C and 1 atm of 1:1 1-butene:oxygen in a round-bottomed flask with magnetically coupled stirring. Results are reported for the solutions used in reactions in the absence of oxygen; up to about 40 turnovers on Pd were obtained in about 120 minutes with the heteropolyacid designated PMo 6 V 6 (H 9 [PMo 6 V 6 O 40 ] in the journal account). An experiment is also reported using this heteropolyacid in 0.87 M sulfuric acid (in the journal account it is cited as 1 M sulfuric acid and the pH is stated to be ca. -0.3.) . The extra acid is said to be slightly detrimental: up to about 32 turnovers on Pd were obtained in about 120 minutes. The various P- Mo-V co-catalysts are said to be longer lasting in the pH range 1-2. United States Patents Nos. 4,434,082; 4,448,892; 4,507,506; 4,507,507; 4,532,362; and 4,550,212, assigned to Phillips Petroleum Company, disclose systems for oxidizing olefins to carbonyl compounds comprising a palladium component, a heteropolyacid component, and additional components. U.S. 4,434,082 and 4,507,507 both add a surfactant and a diluent of two liquid phases, one of which is an aqueous phase, and one of which is an organic phase. U.S. 4,448,892 and 4,532,362 also both add a surfactant and a fluorocarbon. U.S. 4,507,506 adds cyclic sulfones (e.g. sulfolane). U.S. 4,550,212 adds boric acid and optionally a surfactant. The disclosure of heteropolyacids in each of these patents is the same as in Matveev patents, and the heteropolyacids demonstrated by working examples are prepared by the same method as in Matveev patents, including acidification to pH 1.00 with sulfuric acid. PdCI 2 is among the palladium components exemplified. Among the disclosed surfactants are quaternary ammonium salts and alkyl pyridinium salts, including chloride salts. However, cetyltrimethylammonium bromide is the only surfactant demonstrated by working example. The working examples for olefin oxidation among the above patents predominantly demonstrate the one-stage oxidation of individual n-butenes to MEK in the presence of oxygen. U.S. 4,434,082 and 4,507,507 demonstrate oxidation of 3,3-dimethyH -butene and 3-methyl-1 -butene. U.S. 4,448,892 and 4,532,362 demonstrate the oxidation of 1-dodecene. U.S. 4,507,506 is concerned with the one-stage oxidation of long-chain alpha-olefins and demonstrates oxidations of 1-decene and 1-dodecene. United States Patents Nos. 4,720,474 and 4,723,041 , assigned to Catalytica Associates, disclose systems for oxidizing olefins to carbonyl products comprising a palladium component, a polyoxoanion component, and additionally a redox active metal component (certain copper, iron, and manganese salts are disclosed) and/or a nitrile ligand. The disclosures emphasize the elimination of chloride from the system; the catalyst systems do not contain chloride ions except sometimes as eventual trace contaminants introduced during polyoxoanion synthesis. The patents disclose that pH or acidity can be adjusted by various proton sources, such as an acid form of a polyoxoanion or certain inorganic acids; sulfuric acid is said to be a preferred acid and is the only acid so described. The pH of the liquid phase is said to be preferably maintained between 1 and 3 by the addition of appropriate amounts of H 2 S0 4 . The working examples for olefin oxidation all add H 2 S0 4 to the reaction solution, either to obtain 0.1 N concentration or to obtain pH 1.5 or 1.6. U.S. 4,720,474 and 4,723,041 demonstrate by working example the oxidation of various olefins to carbonyl products: predominantly 1-hexene, as well as ethylene, 1- and 2-butenes, 4-methy!-1-pentene, cyclohexene, 1 -octene, and 2-octene, all in the presence of oxygen. Example XL gives initial olefin reaction rates using a catalyst solution including Pd(N0 3 ) 2 , K 5 H 4 PMo 6 V 6 O 40 , and Cu(N0 3 ) 2 , with H 2 S0 4 added to pH 1.5, at 85 °C and 100 psig total pressure with oxygen in a stirred reactor without baffles. The reported ethylene reaction rate is 8.58 x 10 "7 moles C 2 H 4 /sec ml (0.858 (millimoles/liter)/second). This corresponds to a palladium turnover frequency of 0.17 (millimoles C 2 H 4 /millimole Pd)/ second. A slightly lower rate is reported for 1 -butene. SUMMARY OF INVENTION This invention is a process for the production of MEK from mixed normal butenes using a catalyst system comprising a palladium catalyst and a polyoxoacid or polyoxoanion oxidant comprising vanadium. The process includes steps for the separation of product MEK from byproducts or the conversion of the byproducts to a nonharmful form. In this process, a stream containing mixed normal butenes is mixed with an aqueous stream containing the catalyst system. The catalyst system comprises a vanadium-containing polyoxoanion of the formula: (3+x-y)- [H y PMo (12 . x) V x O 40 ] where 0<x<12 and 0<y< (3+x), or mixtures thereof, along with palladium, and chloride ion. Preferred materials include those having cations of Group IA or IIA metals or ammonium, but preferably H, Li, Na, K, or NH 4 . The most preferred polyoxo-material is that in which y=6 and x=3. The aqueous catalyst solution comprises chloride ions at a concentration effective for maintaining the activity and stability of the palladium catalyst for continued process operation, potentially at a concentration greater than twice the concentration of palladium, but generally no more than six times the palladium content. The catalyst is removed from the crude MEK stream leaving the MEK reactor (along with a major portion of the extra water) in a catalyst stripper. The catalyst is regenerated using an oxygen-containing gas and recycled to the MEK reactor. The catalyst stripper is operated to recover a very large proportion of the product MEK so to prevent the over-oxidation of any residual MEK left in the aqueous catalyst stream to various oxidized products such as acetic acid and acetaldehyde in the catalyst oxidizer. In any event, the MEK stream from the catalyst stripper is very wet and made up mainly of MEK and water. It may be fed to a distillation step in which organic acids, principally acetic acid, are largely separated from the MEK stream. The MEK stream is them stripped of butanes and butenes which may be further purified for recycle or other use. The MEK stream is further treated to remove light ends, heavy ends, and any residual chlorinated hydrocarbons. The largely purified stream desirably is mildly hydrogenated to remove any butyraldehyde byproducts. The hydrogenation step desirably utilizes a fixed bed of a supported Group VIII metal, preferably Fe, Co, Ni, Ru, Pd, Pt or alloys or mixtures of those metals on Al 2 0 3 or Si0 2 or some other oxide support. The MEK product may be distilled in a finishing column to remove products of the hydrogenation and excess hydrogen as well as any heavy end byproducts. The MEK product typically is substantially pure, e.g., 99.5-99.95+ %, by weight. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram of an MEK process made according to the invention. DETAILED DESCRIPTION OF THE INVENTION The invention is discussed below in the following order: I. the general technological background relating to the olefin oxidation catalyst is provided, II. the general process conditions for the olefin oxidation step are provided, III. a description of a specific desirable embodiment of the invention is provided, which embodiment includes an inventive butyraldehyde hydrogenation step, and IV. examples of the invention. I. Empirical and Theoretical Discussion on the Olefin Oxidation Catalyst We have found after extensive investigations that certain catalyst solutions and processes discussed in the background references are wholly impractical or practically unworkable for economically practicable commercial manufacture of carbonyl products by the oxidation of olefins. Characteristic problems we found for background catalyst solutions and processes using palladium and polyoxoanions include insufficient olefin oxidation reaction rates, insufficient palladium catalyst activity, insufficient catalyst stability for continued process operation, and insufficient dioxygen reaction rates. The following discussion outlines the results of our investigations towards solving these problems and our understanding of why our solutions to these problems are successful. We do not intend to be bound by the following theoretical explanations since they are offered only as our best beliefs in furthering this art. In the oxidation of olefins to carbonyl compounds by palladium catalysts and polyoxoanion oxidants comprising vanadium, palladium appears to catalyze the oxidation of olefins by vanadium (V) in the polyoxoanion oxidant (illustrated in reaction (12) for ethylene oxidation to acetaldehyde), where [V v ] and [V lv ] represent a single vanadium (V) atom and single vanadium (IV) atom in an aqueous solution of polyoxoanion oxidant, respectively: Pd" C 2 H 4 + 2 [V ] + H 2 0 > CH 3 CHO + 2 [V l ] + 2 H(12) In a subsequent step, conducted either simultaneously (one-stage process) or sequentially (two-stage process) to the above, vanadium (IV) in the polyoxoanion solution can be oxidized by dioxygen to regenerate vanadium (V) for the oxidation of additional olefin: 2 [V lv ] + 2 H + + ^0 2 > 2 [V v ] + H 2 0(13) (Reactions (12) and (13), when combined, give the overall reaction (1) for oxidation of ethylene to acetaldehyde by dioxygen.) Palladium appears to catalyze the oxidation of olefins by vanadium(V) in the polyoxoanion oxidant (reaction (12)) by oxidizing the olefin (reaction (14), illustrated for ethylene), and then reducing vanadium (V) (reaction (15)): C 2 H 4 + Pd" + H 2 0 > CH 3 CHO + Pd° + 2 H + (14 ) Pd° + 2 [V v ] > Pd" + 2 [V v ](15 ) Functionally, the vanadium in the polyoxoanion solution mediates the indirect oxidation of the reduced Pd° by dioxygen (reaction (15) plus reaction (13)), and functions in a manner similar to copper chloride in the Wacker process. We have determined that, in preferred processes of the present invention, under mixing conditions sufficient for the olefin oxidation rate to be determined by chemical kinetics, the volumetric rate of olefin oxidation by aqueous polyoxoanion comprising vanadium (V) (reaction (12)) is first-order dependent on the concentration of palladium(ll), and is substantially independent of the concentration vanadium(V). Accordingly, the oxidation of the Pd° product of reaction (14) by vanadium(V) (reaction (15)) is rapid relative to the rate of olefin oxidation by palladium(ll) (reaction (14)). We discovered that the catalyst systems of the background references discussed above become deactivated with agglomeration of Pd° to colloidal palladium or even to precipitated solid palladium metal. Such agglomeration and precipitation competes with the oxidation of Pd° by vanadium (V) to regenerate the olefin-active Pd" form (reaction (15)). Accordingly, what would have been an originally active palladium inventory would progressively accumulate into an inactive form. For olefin oxidation in the absence of dioxygen (as in equation (12)), essentially complete palladium catalyst deactivation would often occur in these referenced processes before effective utilization of the oxidizing capacity of the vanadium (V) content of the solution. Even when most of the palladium would remain active through the olefin reaction in two-stage operation with subsequent dioxygen reaction, multiple olefin/oxygen reaction cycles resulted in a cumulative loss of the active palladium catalyst concentration. The aqueous catalyst solutions of this invention have increased stability towards deactivation because of palladium colloid or solid metal formation. Apparently, our processes more rapidly oxidize Pd° with vanadium (V) (reaction (15)) in competition with agglomeration of Pd° into colloids or solid palladium metal, and/or they aggressively oxidize already agglomerated palladium (0) forms with vanadium(V), with the result that the concentration of olefin-active Pd" is maintained. Among features of the inventive solutions and related processes which may contribute to the increased stability are the following: 1) hydrogen ion concentrations greater than 0.10 mole/liter, 2) presence of chloride ions above a level coincidental to using PdCI 2 as the palladium source, 3) concentrations of dissolved olefin which are effective for sustaining the palladium activity, and 4) essential absence of sulfate ions. The favorable influences of hydrogen ion and chloride ion concentrations on catalyst stability are thought to be related, in part, to decreasing palladium O/ll oxidation potentials, favoring oxidation of all forms of reduced palladium to active Pd". We have also discovered that chloride ion at centimolar concentrations appears to catalyze the rapid corrosive oxidation of even solid palladium metal to soluble Pd" catalyst by polyoxoanions comprising vanadium (V). Accordingly, chloride ions can function to disfavor net accumulation of inactive colloidal and solid metallic palladium by catalyzing rapid regeneration of all forms of reduced palladium to active Pd" catalyst. A theoretical explanation for the favorable influence of dissolved olefin concentration on palladium catalyst stability is that dissolved olefin is able to bind to the Pd° product of olefin oxidation, stabilizing it in solution and thereby slowing its rate of agglomeration into colloidal or metallic forms. The oft-used sulfate salts may decrease ("salt-out") olefin solubility in the aqueous solution, thereby decreasing its ability to stabilize the palladium catalyst. In any event, we have found that, when the concentration of chloride ions in the solution is insufficient to otherwise maintain palladium activity, when ethylene concentration in solution is reduced (due to low ethylene pressure in the gas phase and/or due to insufficient mixing of the gas and liquid phases for the ethylene oxidation rate to be determined by chemical kinetics), initial palladium activity declines precipitously. We have determined that such conditions are typical of the examples disclosed in Matveev patents, and contribute to their low apparent palladium catalyst activities relative to the present invention; a significant fraction of the loaded palladium appears to reside in inactive forms. Effective concentrations of dissolved olefin for sustaining the palladium activity may be achieved when the olefin is contacted with the aqueous catalyst solution in mixing conditions sufficient for the olefin oxidation rate to be determined by chemical kinetics, and are further enhanced by raising the concentration of olefin in the olefinic phase (as in raising the partial pressure of gaseous olefins). Mixing conditions sufficient for the olefin oxidation rate to be determined by chemical kinetics are established when the reaction rate is determined by chemical characteristics of the catalyst solution, such as palladium concentration, and independent of moderate variations in the phase mixing efficiency. When mixing conditions are insufficient, the olefin concentration in the bulk catalyst solution is depleted by reaction, and the olefin oxidation rate becomes determined by the rate of diffusion (mass transfer) of the olefin into the catalyst solution. When mixing conditions are sufficient, the olefin concentration in the catalyst solution approaches the phase partitioning limit and this limit is increased in proportion to the olefin concentration in the olefinic phase. For each combination of olefin, olefin concentration in the olefinic phase, precise catalyst solution composition, and reaction temperature, sufficient mixing requirements in a given reactor device can be established by observing rates determined by chemical kinetics. In comparison to the inventive catalyst solutions and processes, the catalyst systems and processes of background references using catalysts comprising palladium and polyoxoanion components have generally poor palladium catalyst activity. The background references typically utilize much higher high palladium catalyst loadings to compensate for low palladium activity, and even then do not report acceptable volumetric olefin oxidation rates. A higher palladium concentration results in a lesser number of palladium turnovers (moles olefin reacted/mole palladium present) to react an amount of olefin. Accordingly, the palladium in the systems of the background references is used relatively inefficiently; that is, more palladium is used for the production of a given amount of carbonyl product. Since palladium is a very costly catalyst solution component, this places an economic burden on commercial utilization of the background reference processes. A convenient measure of palladium catalyst activity is the palladium turnover frequency, (moles olefin reacted/mole palladium)/unit time. Similarly, improved palladium catalyst activities are also obtained for olefins other than ethylene. Each olefin will have its own intrinsic rate of reaction with the Pd" in a given aqueous catalyst solution, and these rates are influenced by the conditions of the olefin oxidation process using the solution. However, the relative reaction rates of different olefins with various palladium catalyst solutions under various reaction conditions generally follow the same qualitative order. The poor palladium catalyst activity of the catalyst systems of the background references can be attributed in part to the extent of deactivation of the active palladium catalyst into inactive forms; a fraction of the palladium load resides in colloidal or solid metallic forms with little or no activity. To that extent, the features of the catalyst solutions and related processes of the present invention which contribute to improved palladium catalyst stability, as recited above, also contribute to better apparent palladium catalyst activity. Aqueous catalyst solutions and related processes of the present invention were also discovered to provide higher intrinsic palladium(ll) activity than the catalyst systems and processes of background references. (Intrinsic palladium (I I) activity can be determined by observing initial reaction rates under conditions when all the palladium loaded is initially present as olefin-active palladium(ll); that is, in the absence of any accumulation of inactive forms.) Among the features of the inventive solutions and related processes which contribut- Ό increased intrinsic palladium(ll) activity are: 1) hydrogen ion concentrations greater than 0.10 mole/liter, 2) mixing conditions sufficient for the olefin oxidation rate to be determined by chemical kinetics, 3) concentrations of dissolved olefin effective for oxidizing the olefin at a rate which is independent of the dissolved olefin concentration, and 4) essential absence of sulfate ions. Surprisingly, the presence of chloride ions may contribute to higher palladium activity, depending on the chloride concentration and the hydrogen ion concentration. Particularly, at hydrogen ion concentrations less than about 0.10 moles/liter, the presence of an effective concentration of chloride ions can increase palladium activity over the level with no chloride present. In acidic aqueous solutions comprising palladium(ll) (containing no coordinating ligands or anions other than water), Pd" exists in aqueous solution predominantly as its hydrolytic forms: tetraaquopalladium dication, Pd(H 2 0) 4 2+ , aquated palladium hydroxide, Pd(OH) 2 (H 2 0) 2 and solid phase palladium oxide which may be hydrated. These forms are interconverted by the following equilibria: Pd"(H 2 0) 4 2+ = = = Pd"(OH) 2 (H 2 0) 2 + 2 H + (16) Pd"(OH) 2 (H 2 0) 2 = = = Pd"0.nH 2 0 + (3-n) H 2 0 (17) The two-step-wise acid dissociation constants of reaction 16 have not been resolved (Pd"(OH)(H 2 0) 3 + has not been detected), and the pK_ of reaction 16, as written, is reported to be 2 in water, at or near zero ionic strength. We have found that, contrary to the teaching of Matveev patents, the activity of the catalyst solution, specifically its volumetric olefin oxidation reaction rate, is independent of the vanadium content of phosphomolybdovanadate heteropolyacids, when tested at the same hydrogen ion concentration greater than 0.10 mole/liter, in the absence of mineral acid anions other than the heteropolyanion (in the absence of sulfate and chloride), under mixing conditions sufficient for the rate to be determined by chemical kinetics. Since the chemical kinetics are first-order dependent on the concentration of the Pd", these findings indicate that under these conditions, the olefin-active Pd" is not coordinated by phosphomolybdovanadate heteropolyanions (since its reactivity does not depend on the identity of heteropoly anions). Accordingly, it appears that under these conditions, the olefin-active Pd" exists in solution as tetraaquopalladium, Pd(H 2 0) 4 2+ . We further discovered that (in the effective absence of chloride ion) the rate of palladium catalyzed olefin oxidation in the polyoxoanion solution is highest with solutions having hydrogen ion concentrations greater than 0.1 mole/liter, and rates decrease substantially as the hydrogen ion concentration of the solution is decreased to 0.1 mole/liter and less. This indicates that the dicationic tetraaquopalladium, Pd(H 2 0) 4 2+ is the most active form of palladium(ll) under these conditions, and that as the hydrogen ion concentration of the solution is decreased to 0.1 mole/liter and less, an increasing fraction of the palladium(ll) present as Pd(H 2 0) 4 2+ is converted to less active (lower positively charged and less electrophilic) hydroxo- and/or oxo-forms by deprotonation of coordinated water, via equilibria such as reactions (16) and (17). These hydrolytic forms are apparently less active due to their lower positive charge and decreased electrophilicity at Pd". Therefore, it is quite desirable to utilize polyoxoanion solutions having hydrogen ion concentrations greater than 0.10 mole/liter. Background references for the oxidation of olefins with systems using palladium and vanadium-containing polyoxoacids generally teach that PdCI 2 and PdS0 4 are equivalent palladium catalysts. PdS0 4 completely ionically dissociates in water to sulfate ions and one or more hydrolytic forms of Pd", as governed by hydrogen ion concentration. Accordingly, one would be led to conclude that when PdCI 2 is added in the systems of the background references, chloride is similarly dissociated to give the same hydrolytic form(s) of Pd". However, the background references do not report the addition of chloride ions at a concentrations in excess of that coincidental to providing PdCI 2 . Indeed, the background references generally promote that chloride-free systems are most desirable. The inventive aqueous catalyst solutions and related processes, by having an effective concentration of chloride ions, give substantially improved catalyst stability with no inhibition or only a moderate inhibition of the intrinsic Pd" activity. Moreover, since a greater fraction of loaded palladium can be maintained in the active Pd" form, greater productivity can be obtained from the total palladium load in continuous operation by the addition of an effective concentration of chloride ions. In tested embodiments with hydrogen ion concentrations less that 0.1 mole/liter, the presence of chloride ion at 5 millimoles/liter does not inhibit of Pd" activities. With chloride ion at 25 millimoles/liter, Pd" activities were within 40-60% of those in the absence of chloride ions, and still about 100 times greater than for a typical Wacker catalyst system under comparable conditions. Even more surprisingly discovered, as the hydrogen ion concentration is decreased below 0.1 moles/liter, a region where Pd" activity in the absence of chloride ions decreases substantially, Pd" activity in the presence of an effective concentration of chloride ions can be substantially maintained. Said another way, intrinsic Pd" activity in the presence of chloride can exceed Pd" activity in the absence of chloride. In tested embodiments with hydrogen ion concentrations about 0.01 mole/liter, Pd" activity in the presence of 25 millimoles/liter chloride ion were about 5 times greater than those without chloride. When chloride ions are added to solutions of acidic solutions of Pd" in water, a series of aquated chloride complexes are formed as the chloride ion concentration is increased. Where the acidity is such to provide Pd(H 2 0) 4 2+ as the hydrolytic form, the series is as follows (in each of the following equilibria a chloride ion is added and a water is lost, to the right as written): Pd(H 2 0) 4 2+ = PdCI(H 2 0) 3 + = PdCI 2 (H 2 0) 2 = PdCI 3 (H 2 0)- = PdCI 4 = (18) As the acidity of a solution is decreased, each of the complexes containing coordinated water can dissociate a hydrogen ion to leave a complex of coordinated hydroxide. With the successive replacement of coordinated water in Pd(H 2 0) 4 2+ by chloride ions (equation (18)), the positive charge on the palladium complex is decreased and the pK a for deprotonation of remaining coordinated water is increased. This increase in pK a by chloride coordination appears sufficient so that the chloro-aquo species formed in the presence of moderate amounts of chloride, are not significantly deprotonated to chloro- hydroxo species as the hydrogen ion concentration is decreased to at least 0.01 millimoles/liter. Thereby, the Pd" catalyst activity of these chloride-bound catalysts at hydrogen ion concentrations greater than 0.1 mole/liter can be substantially maintained on decreasing the hydrogen ion concentration to at least 0.01 millimoles/liter. Further, the chloro-aquo species appear substantially more active for olefin oxidation than hydroxo-aquo species (such as Pd"(OH) 2 (H 2 0) 2 ) formed when Pd(H 2 0) 4 2+ is deprotonated as the hydrogen ion concentration is decreased towards 0.01 millimoles/liter. We have also discovered that in using the chloride-comprising catalyst solutions for the oxidation of olefins, chlorinated organic by-products are not formed in amounts significant relative to the amounts formed with other catalyst systems. The polyoxoanion in the solutions and processes of the present invention appears to provide two functions which are not provided with vanadium alone in aqueous solution. First, the polyoxoanion solution provides an environment for dissolution of suitably high concentrations of vanadium. In acidic aqueous solutions with hydrogen ion concentrations comparable to preferred solutions of the present invention, vanadium (V) alone exists predominantly as the pervanadyl ion, V0 2 + aq , whose solubility is limited; at saturation, it deposits solid V 2 0 5 . Likewise, vanadium(IV) alone exists predominantly as the vanadyl ion, V0 2+ aq , which saturates with respect to insoluble reduced vanadium oxides. In contrast, polyoxoanions comprising vanadium can provide vanadium solubilities to much higher concentrations, such as the decimolar to molar level concentrations of vanadium utilized in preferred solutions and processes of the present inventions. Second, the polyoxoanion solution appears to enable suitably rapid reaction of vanadium(IV) with oxygen, to regenerate vanadium(V) (reaction (13)). Although pervanadyl ion is capable of palladium-catalyzed oxidation of olefins, in a reaction similar to reaction (12), vanadyl ion alone reacts only very slowly with dioxygen to regenerate pervanadyl. In contrast, in our preferred polyoxoanion solutions, polyoxoanions comprising vanadium(IV) react very rapidly with dioxygen, thereby providing preferred processes of the present invention. Moreover, when vanadyl(IV) ion is present in the polyoxoanion solution, it too can react rapidly with dioxygen. Preferred polyoxoanions comprising vanadium, which enable particularly rapid oxidation of vanadium(IV) to vanadium (V), further comprise phosphorus or molybdenum. Particularly preferred polyoxoanions further comprise both phosphorus and molybdenum. The regeneration step which includes reaction of preferred polyoxoanion solutions comprising vanadium(IV) with dioxygen, can proceed with volumetric dioxygen reaction rates many-fold greater than rates in background references. Improved volumetric dioxygen reaction rates can be achieved, in part, by operating the vanadium(IV)-dioxygen reaction process under more efficient gas-liquid chloride in polyoxoanion solutions prepared from them. It is desirable to use aqueous catalyst systems comprising chloride at concentrations greater than coincidental to using PdCI 2 as the palladium source; that is greater than twice the palladium molar concentration. Preferably, the chloride concentration is greater than four times the palladium concentration. There is no particular upper limit on the chloride concentration, but is preferably less than a concentration at which the palladium catalyst activity becomes inversely dependent on the square of the chloride concentration. Typically, the chloride is present in these solutions at a molar ratio of 10/1 to 10,000/1 relative to palladium. In terms of absolute concentrations, chloride is typically present at a concentration of 0.001 to 1.0 moles/liter, preferably 0.005 to 0.50 moles per liter, and most preferably 0.010 to 0.100 moles per liter. When chloride is present in the catalyst solutions of this invention, the solution is preferably essentially free of copper ions. "Essentially free of copper ions" means the olefin oxidation process with the solution does not produce higher amounts of chlorinated organic by-products than a corresponding solution which is free of copper ions. II. General Process Conditions Broadly, olefin oxidation processes of the present invention are conducted under oxidative conditions sufficient to oxidize the olefin to a carbonyl product. Likewise, in processes involving reaction of dioxygen, the dioxygen reaction is conducted under oxidative conditions sufficient to utilize dioxygen to oxidize the olefin, or intermediately, to regenerate the polyoxoanion oxidant in its oxidized state. The preferred temperature range for processes of the present invention varies with the identity of the olefin and is interdependent with such factors as the olefin concentration of olefin in aqueous solution, chloride ion concentration, palladium concentration, and other factors which determine reaction rates. Increasing temperature generally provides increased reaction rates, although these increases are slight for reactions which are limited by diffusion. In some cases, lower temperatures may be preferred to avoid troublesome side-reactions. In two-stage operation, temperatures for the olefin reaction and the dioxygen reaction can be set independently. Generally, temperatures utilized in processes of the present invention may range from about 20 to about 200 °C, usually in the range 60 to 160°C. For gaseous olefins, such as ethylene, propyiene, and butenes, the temperature is preferably in the range 80 to 130 β C. Pressures for the processes of the present invention depend strongly on the nature of the olefin, whether gaseous or liquid under the reaction conditions, whether dioxygen reaction is conducted simultaneously or separately with the olefin oxidation reaction, whether oxygen is added as oxygen or air, and reaction temperatures. For example, at reaction temperatures less than 100°C, the atmospheric boiling point of water, with olefins which are liquid under the reaction conditions, in the absence of dioxygen, the olefin oxidation process may be conveniently conducted at atmospheric pressure. For temperatures near or above 100°C and above, water vapor contributes significantly to the total pressure in the reactor device. For gaseous olefins, elevated partial pressure is usually utilized to increase the concentration of olefin in the gas phase in contact with the liquid phase, to increase reaction rates and decrease reactor volumes. Generally, gaseous olefins are reacted at partial pressures of 1 atmosphere to 100 atmospheres, typically in the range 4 atmospheres (about 60 psi) to 20 atmospheres (about 300 psi). In two-stage mode, gaseous olefins are preferably reacted at partial pressures in the range of 8 atmospheres (about 120 psi) to 12 atmospheres (about 180 psi). In certain solutions and processes of the present invention, olefin is dissolved in solution at concentrations such that its rate of oxidation becomes independent of the olefin concentration (olefin saturation kinetics). Reaction conditions which meet this criteria can be established by routine experimentation. For gaseous olefins such as ethylene, propyiene, and butenes, this criteria is met in reactions conducted at olefin partial pressures greater than about 120 psi. For the dioxygen reaction, elevated partial pressure is usually utilized to increase the concentration of oxygen in the gas phase in contact with the liquid phase, to increase reaction rates and decrease reactor volumes. Generally, oxygen is reacted at partial pressures of 0.2 atmosphere (1 atmosphere air) to 100 atmospheres, typically in the range 0.2 atmospheres to 20 atmospheres, and preferably in the range 1 atmosphere (about 15 psi) to 15 atmosphere (about 225 psi). For oxidation of gaseous olefins by dioxygen in two stage mode, the total pressures in the olefin reactor and the dioxygen reactor are typically similar, but may be varied independently. In two stage mode, compressed air is typically used, but oxygen could be used as well. For oxidation of gaseous olefins by dioxygen in one-stage mode, oxygen is typically used and olefin and oxygen are typically fed in near stoichiometric ratios, about 2:1. Liquid olefins can be reacted neat or in combination with substantially inert diluents. Generally, the concentration of the liquid olefin in a second liquid olefinic phase is increased to increase reaction rates and decrease reactor volumes. However, in some applications, it may be advantageous to use a diluent. Such diluent may improve mixing and mass transfer of the olefin into the aqueous catalyst solution, or provide improved recovery of the carbonyl product by improved liquid-liquid phase distribution, and/or improved phase separation. In other applications, the olefinic feed may be obtained in combination with substantially inert diluents which are more easily or economically separated from the carbonyl product than from the olefin. For example, butenes may be obtained in combination with butane, cyclohexene may be obtained in combination with cyclohexane and/or benzene. In other applications, it may be desirable to use a cosolvent diluent which miscibilizes the olefinic and aqueous solution components. Suitable reactors for the processes of the invention provide for efficient mixing of olefinic and aqueous catalyst phases. Efficient mixing in the olefin reaction is established when the rate of the reaction is determined by chemical kinetics, and is not limited by diffusion of the olefin into the aqueous phase. Once that condition is established, preferably the olefin concentration in the aqueous solution is effective for the olefin oxidation rate to be independent of the olefin concentration in the aqueous solution (olefin saturation kinetics). Olefin concentration in the aqueous solution can be increased by increasing the olefin concentration in the olefinic phase. Efficient mixing in the dioxygen reaction is established when the diffusion-limited dioxygen reaction rate proceeds rapidly enough for convenient and economical utilization in the intended application. Reactors and associated equipment in contact with the aqueous catalyst solution should withstand the oxidizing nature of the solution and processes without corrosion. For solutions and processes in the absence of chloride, stainless steel, Hastelloy C, glass, and titanium provide suitable equipment surfaces. For solutions and processes in the presence of chloride, titanium and/or glass is preferred. Solutions and Processes wherein the hvdroαen ion concentration is greater than 0.1 mole/liter: Solutions and related processes of the present invention wherein the hydrogen ion concentration is greater than 0.1 mole/liter need not be essentially free of sulfate, not further comprise chloride ions, nor further comprise dissolved olefin at concentrations effective for olefin saturation kinetics or for stabilization of the palladium catalyst. However, preferred embodiments of such solutions and processes may use one or more of these features. Solutions and Processes essentially free of sulfate: Processes of the this invention which are essentially free of sulfate ions need not also comprise a hydrogen ion concentration is greater than 0.1 mole/liter, nor further comprise chloride ions, nor further comprise dissolved olefin at concentrations effective for olefin saturation kinetics or for stabilization of the palladium catalyst. However, preferred embodiments of such solutions and processes may use one or more of these features. In particular, it is preferred that the hydrogen ion concentration of the solution be at least greater than 10 *3 moles/liter. Solutions and Processes comprising Chloride: Solutions and related processes of the present invention using those solutions which comprise effective concentrations of chloride ions need not also comprise a hydrogen ion concentration is greater than 0.1 mole/liter, nor also be essentially free of sulfate, nor further comprise dissolved olefin at concentrations effective for olefin saturation kinetics or for stabilization of the palladium catalyst. However, preferred embodiments of such solutions and processes may use one or more of these features. In particular, it is preferred that the hydrogen ion concentration of the solution be at least greater than 10 "3 moles/liter. It is especially preferred that solutions and processes which do not provide effective concentrations of dissolved olefin, do comprise effective concentrations of chloride ions. Solutions and Processes comprising dissolved olefin at effective concentrations: Solutions and related processes of the present invention which comprise effective concentrations olefin dissolved in the aqueous catalyst solution, and processes which comprise mixing conditions sufficient for the olefin oxidation rate to be determined by chemical kinetics need not also comprise a hydrogen ion concentration greater than 0.1 mole/liter, nor be essentially free of sulfate, nor further comprise chloride ions. However, preferred embodiments of such solutions and processes provide one or more of these features. In particular, it is preferred that the hydrogen ion concentration of the solution be at least greater than 10 "3 moles/liter. III. An Embodiment of the Invention This embodiment of the invention is shown in Figure 1. A mixed linear butene stream may be used as the feedstock to this process. The feedstream may contain other diluents, as was noted above. Because these streams would typically be from such sources as a fluid catalytic cracking unit, the feed would contain a number of normal and branched butanes. It is highly desirable that the stream contain less than about 2000ppm of butadiene, little if any sulfur-bearing compounds, and only a minimum of isobutene content. Isobutene can be tolerated in the process but is converted to t-butyl alcohol and may run afoul of certain product quality specifications. In any event, the butene feedstock is fed via line (102) to the butene oxidation reactor (104) along with the catalyst solution system found in the catalyst recycle line (106). As we noted above, the catalyst system is an aqueous mixture comprising a vanadium-containing polyoxoanion of the formula: [H y PMo (12 . x) V x O 40 ] (3+x-y)- where 0<x<12 and 0<y< (3+x), or mixtures thereof, along with palladium, and chloride ion. Preferred materials include those having cations of Group lA or IIA metals or ammonium, but preferably Li, Na, K, or NH 4 . The most preferred polyoxo-material is that in which y=6 and x=3. The aqueous catalyst solution comprises chloride ions at a concentration effective for maintaining the activity and stability of the palladium catalyst for continued process operation, potentially at a concentration greater than twice the concentration of palladium. The stream (108) leaving the butene oxidation reactor (104) may be as much as 99% by mole of water with the remainder of the stream comprising the desired MEK (-0.25% by mole) and a variety of other excess feed materials and oxidized olefins. The stream is sent to a catalyst stripper (110) where the majority of the hydrocarbonaceous materials are stripped from the aqueous catalyst system and sent to an azeotrope column (112). The catalyst stripper (110) is operated to maintain a very high MEK recovery so to minimize the recycle of MEK into the catalyst oxidizer (118) where it could be "over oxidized" to produce such products as acetic acid and acetaldehyde. The bottoms stream (114) from the catalyst stripper is mixed with a compressed oxygen- containing stream (116) and sent to a catalyst oxidizer (118). The oxygen- containing gas may be air or an oxygen-enhanced stream. The major difference in results amongst the various oxygen-containing gas streams is that the residence time of the catalyst oxidizer (118) must be larger for the same reaction end-point if a more dilute oxygen stream is used. The off-gas from the oxidize is separated in separator (122). The de-gassed but oxidized catalyst stream is then returned to the butene oxidation reactor via stream (106). The overhead stream from catalyst stripper is sent to azeotrope column (112) where it distilled into two streams: a bottoms stream (124) containing the majority of the organic acids produced in the butene oxidation reactor (104) and an overhead stream (126) containing an azeotrope of water and MEK as well as a minor amount of other materials. At this point, the overhead stream may contain 40-45% of MEK and 30-35% (molar) of water. The azeotrope column (112) bottoms stream (124) may be sent to a acetic acid extractor (128) where MEK is used as an extractant to remove acetic acid from the water. The extracted water (130) is recycled to the butene oxidation reactor (104) after a second stage of stripping in a water stripper (132). The acetic acid extractor (128) overhead stream (134) contains acetic acid and MEK. It is fed to a MEK solvent stripper (136) where the liquid is heated and the acetic acid stream (138) is taken off the bottom as a product stream. The overhead stream (140) is fairly clean of acetic acid and is recycled back to the acetic acid extractor (128). Returning to the overhead stream (126) from the azeotrope column (112); that stream is separated in an MEK stripper (142) into two streams: one overhead stream (144) containing a majority of the unreacted butenes and the unreactable butanes and another bottoms stream containing the desired MEK (146). The MEK stripper (142) is operated in such a way so to minimize the eventual production of ethanol in the in the butyraldehyde hydrogenator (182) from acetaldehyde byproducts found in the stream and to prevent their accumulation in the MEK extractor (158) and C 4 solvent stripper (166). The MEK stripper (142) overhead stream (144) is separated into a light ends stream (148) containing acetaldehyde in a first C 4 recovery column (150) and into a mixed normal C 4 /C 4 = stream (152) and a heavy ends stream (154) of mixed C 4 -dimers in the second C 4 recovery column (156). The MEK stripper (142) bottoms stream (146) is sent to a MEK extractor column (158) where a nominally isobutane and n-butane stream (160) is used to extract MEK from the water remaining to form a stream containing mostly water (162) for recycle to the azeotrope column (112). The butanes in the overhead stream (164) and the residual water are recovered for recycle in the C 4 solvent stripper (166). The C 4 solvent stripper (166) bottoms stream (168) is sent to light ends column (170) to remove a minor amount of light ends, again primarily isobutane with a minor amount of acetone and propionaldehyde, in stream (172). heavy materials are separated from the bottoms stream (174) in heavy ends column (176). Again, the heavy ends in stream (178) are primarily C 4 dimers and a small amount of chlorinated hydrocarbons. These chlorinated materials must be removed at this stage lest they deactivate the hydrogenation catalyst in the butyraldehyde hydrogenator (182). The overhead stream (180) from the heavy ends column (176) is now substantially dry. It is cooled to help with the selectivity of the hydrogenation reaction, mixed with hydrogen from stream (181), and introduced into butyraldehyde hydrogenator (182). The stream may be chilled so to improve the selectivity of the butyraldehyde hydrogenation reaction even further but that has the allied problem of slowing the reaction and mandating a larger bed of catalyst. As we mentioned above, the catalyst used in this reactor is a preferably a supported Group VIII hydrogenation catalyst. The preferred Group VIII metals are Fe, Co, Ni, Ru, Pt, Pd, and alloys or mixtures of those metals; and the most preferred is Ni. Most oxidic catalyst supports, including ceria, silica, zirconia, alumina, tungsten oxide, boria, silica-alumina, zeolites, various porous clays, kieselguhr, and the like, are suitable for use in this service but silica and alumina to be most suitable, and alumina is preferred. The butyraldehyde hydrogenator (182) may be operated in the temperature range between 20 and 200 β C, preferably between 20 and 90 β C. The temperature selected depends upon the catalyst selected and the composition of the stream entering the butyraldehyde hydrogenator (182). As we noted above, the effectiveness of the reactor in eliminating butyraldehyde and not hydrogenating MEK improves as the temperature is lowered. The amount of hydrogen added to the reactor should be slightly in excess of that needed to react all of the butyraldehyde in the feed to the reactor. The pressure of the reactor should be maintained between 1 and 25 atm. This MEK process produces a small amount (<1%) of butyraldehyde, which is very difficult to separate from MEK by distillation. The MEK product specifications often allow less than 50 ppm of butyraldehyde because of the severe odor of butyric acid formed by contact of air with butyraldehyde. We have shown that at 50 ppm the average human nose cannot detect the presence of butyraldehyde or butyric acid. This hydrogenation step is capable of reducing the butyraldehyde content to less than about 50 ppm and even less than 25 ppm. In doing so less than about 2.5 % of the MEK and, with some conditions and catalysts, notably the Ni/Al 2 0 3 catalyst, no more than about 1.0% or 0.5% of the MEK fed to the hydrogenation step is converted to another product. We consider a neat MEK feed with a butyraldehyde contaminant concentration of only ~ 1 % was the most economic feed for the hydrogenation step. The butyraldehyde hydrogenator (182) selectively hydrogenates the butyraldehyde to 1-butanol. The 1-butanol product is easily separated from MEK in the MEK finishing column (186). The effluent stream (184) from the butyraldehyde hydrogenator (182) may then be treated in the MEK finishing column (186) to remove light ends, mainly H 2 , (188) and heavy ends, mostly isobutane, (190) and finally to result in a MEK stream (192) having an MEK content of greater than 99.5%. IV. Examples One skilled in the art could, using the preceding description, utilize the present invention to its fullest extent. The following specific examples are intended to illustrate and not to limit the invention in any way. Polyoxoanion solutions were prepared according to the examples below in 3 neck Morton flasks, or 5.0 liter and 12.0 liter capacity, each equipped with an electric heating mantle, an efficient reflux condenser/demister, a powder addition funnel and a high torque overhead mechanical stirrer. Example 1 This Example shows the long term use of the inventive process in producing MEK from a mixed ' normal butene/butane stream. The continuous unit is a small pilot plant facility having a butene oxidation reactor similar to (104) in Figure 1 , a catalyst oxidizer (analogous to (118)), a product flash vessel for separating hydrocarbons and products from the butene oxidation reactor effluent (analogous to catalyst stripper (110)), and a gas-liquid separator on the outlet of the catalyst oxidizer. The two reactors are multistage, continuously stirred reactors of appropriate construction materials. Product and feed sample points are situated at various points throughout the reaction system. The system is equipped for continuous operation. A mixed C 4 feed of 23.0 % (by mole) of 1 -butene, 45% mixed 2- butenes, and 32 % of iso- and n-butanes was introduced into the butene oxidation reactor. The feed also contained trace amounts of C 3 's, C 5 's, and butadiene. Also introduced into the reactor was a catalyst system containing 0.3 M H 6 PMo 9 V 3 O 40 as the heteropolyacid, 35 mmolar Cl " , 3.6 mmolar palladium. The chloride was added by a solution of 1 N HCI and the palladium was added by sodium tetrachloropalladate(ll). The butene oxidation reactor was operated at 250 psig and at 115°C. The catalyst oxidation reactor was operated at 250 psig and 115°C. The continuous run was terminated after 420 hours of operation. Although catalyst leaks occurred twice during the run and required the introduction of small amounts of additional catalyst to account for those losses, the catalyst system operated without substantial deactivation during that period of time. The average selectivity of C 4 = to MEK during the run was about 93.44 %. The major byproduct (acetic acid) selectivity averaged about 2.86 %. Minor amounts of chlorinated organics were detected; the ratio of organic chloride to MEK produced was 1:650. Both oxygen and air were utilized during the run as the catalyst oxidizing gas. The oxygen performed much better apparently due to the fact that the catalyst oxidation reactor was limited in size. Example 2 This example shows selective hydrogenation of butyraldehyde to 1-butanol in the presence of a large excess of MEK with very low MEK loss. The hydrogenation step was carried out in a fixed bed reactor employing a Ni on alumina catalyst in a trickle bed configuration. Hydrogen was fed to the reactor through a mass flow controller, while liquid MEK was fed with a HPLC pump. The MEK feed was preheated to operating temperature before reaching the reactor. The reactor and feed tubes were heated and well insulated. After leaving the reactor, the product was depressurized and cooled before reaching the liquid product reservoir from which the vapor phase was vented. Liquid samples were drawn just before the liquid product reservoir. The MEK feed was kept under nitrogen cover to avoid air oxidation of butyraldehyde to butyric acid. Since the temperature dependence of the reaction was found to be quite significant, the reactor system was equipped with several thermocouples to control the operating temperature. The initial testing covered use of two commercial catalysts; Ni on Al 2 0 3 from Calsicat and Ni on Kieselguhr from United Catalyst Inc. These catalysts were activated according to the manufacturer's recommendations and tested at different reaction temperatures and pressures. The Table gives an overview of the test conditions and a brief summary of the experiment. Table 1 Catalyst TfC) Pressure fpsia) Comments 55% Ni/Kieselguhr 60 200 90 hr test 58% Ni/Al 2 0 3 75 200 a.) 100 hr test, b.) organic contaminants test The principle objective was to lower the butyraldehyde levels in the feed to less than 50 ppm while having the lowest possible MEK loss. Ideally the MEK loss would be 1% or less. Ni/Kieselouhr Catalyst Results: We observed that the freshly activated Ni/Kieselguhr catalyst initially showed very high activity (hyper-activity) which is rapidly lost, after which the activity reaches a steady level. The activity of the catalyst in the experiments reaches a steady level after about 5 hours of operation. This catalyst showed very stable activity up to 92 hours. The steady level of activity observed for the Ni on Kieselguhr catalyst under these operating conditions was not high enough to reduce the butyraldehyde level to less than 50 ppm. However, by increasing the operating temperature by about 10 °C a high enough activity could be obtained to reach the desired conversion. The corresponding MEK loss was about 2 to 2.5 %, somewhat higher than the goal of about 1% or less. The Ni on Kieselguhr catalyst (after it reached a stable activity level) was then tested at different temperatures (22 to 76 °C). The tests showed that the butyraldehyde hydrogenation reaction is strongly dependent on operating temperature. The Ni on Kieselguhr catalyst (after it reached a stable activity level) was also tested at different hydrogen pressures (total pressure - 45 to 300 psia). The experiment did not show a clear effect of hydrogen pressure on butyraldehyde reaction rate or selectivity as the Table indicates: Table Pressure fpsial fbutvrald.] (ppm " ) MEK loss(%ϊ Residence timefmin) 45 632 0.9 1.4 105 519 1.1 1.6 200 475 1.2 1.8 290 465 1.4 1.9 @ 60-70 «c catalyst bed temperature 6250 ppm butyraldehyde in feed Ni on Kieselguhr catalyst Since the MEK loss was above 1% at 50 ppm butyraldehyde a different catalyst was examined. Ni/A O- catalyst results: The preliminary tests performed with the Ni/Kieselguhr catalysts were repeated with the Ni/Al 2 0 3 catalysts (40-60 mesh) but at a temperature of 75° C. These experiments showed that the MEK loss observed at a given butyraldehyde conversion was about half of that observed with Ni on Kieselguhr. At 50 ppm butyraldehyde the MEK loss was 1.0 %. We then ran a life test (76 "C and 210 psia H 2 ) using both a synthetic feed containing of 6250 ppm butyraldehyde in MEK and one approximating an actual plant feedstock: Table Component Concentration (vΛ%) MEK 97.4 Butyraldehyde 0.62 Tetradecane 1 1.24 Acetaldehyde 0.0058 Propionaldehyde 0.50 2-Pentanone 0.079 2-Butanol 0.14 1-Butanol 0.0093 1 Tetradecane was used as an internal standard The initial feed was run for 114 hours and the latter feed was run for 40 hours with no diminution in activity. At no time did the butyraldehyde concentration in the product stream reach the level of detectability (25 ppm). The Ni on Al 2 0 3 catalyst was clearly superior to the Ni on Kieselguhr from a process economics point of view although either would be acceptable if high MEK losses were tolerable. This invention has been shown both by description and by example. The examples are however only examples; they should not be used in any fashion to limit the scope of the invention otherwise described here. Additionally, it should be clear that one having ordinary skill in this art would envision equivalents to the processes found in the claims that follow and that these equivalents would be within the scope and spirit of the claimed invention.

Claims: WE CLAIM AS OUR INVENTION: 1. A process for converting normal butenes into methyl ethyl ketone comprising the steps of: a. contacting a feed stream comprising normal butenes with an aqueous solution comprising a polyoxoanion oxidant comprising vanadium, a palladium catalyst, and chloride under conditions suitable for oxidizing the stream comprising normal butenes to a reactor product stream comprising methyl ethyl ketone, water, and butyraldehyde, b. separating the reactor product stream into a stream containing methyl ethyl ketone and butyraldehyde and an aqueous stream containing a substantial portion of the polyoxoanion oxidant comprising vanadium, a palladium catalyst, and chloride, c. contacting at least a portion of the stream containing methyl ethyl ketone and butyraldehyde with hydrogen and a hydrogenation catalyst to hydrogenate at least a portion of the butyraldehyde, and d. recovering the methyl ethyl ketone. 2. The process of Claim 1 where the aqueous stream containing a substantial portion of the polyoxoanion oxidant comprising vanadium, a palladium catalyst, and chloride is contacted with an oxygen-containing gas to oxidize that stream and the stream is recycled to contact the butene feed stream. 3. The process of Claim 2 where the oxygen-containing gas is oxygen. 4. The process of Claim 2 where the oxygen-containing gas is air. The process of Claim 1 where the stream containing methyl ethyl ketone and butyraldehyde further contains acetic acid and where a stream containing acetic acid is separated from the methyl eth ketone and butyraldehyde and is extracted with methyl ethyl ketone to recover acetic acid and stripped prior to recycling to the butene feed stream. 6. The process of Claim 1 where the feed stream comprising norm butenes also contains butanes and where the process additionall comprises the steps of stripping those butanes and unreacted butenes from the stream containing methyl ethyl ketone and butyraldehyde. 7. The process of Claim 1 where the vanadium-containing polyoxoanion oxidant is of the formula: [H y PMo (12 . x) V x O 40 ] (3+ ^ " where 0<x<12 and 0<y<(3+x), or mixtures thereof. 8. The process of Claim 7 where in the vanadium-containing polyoxoanion oxidant, y=6 and x=3. 9. The process of Claim 1 where the molar chloride concentration i more than twice that of the palladium. 10. The process of Claim 1 where hydrogenation catalyst comprises a Group VIII metal on an oxidic support. 11. The process of Claim 1 where the hydrogenation catalyst comprises Fe, Co, Ni, Ru, Pd, Pt, or mixtures on a support of ceria, silica, zirconia, alumina, tungsten oxide, boria, silica- alumina, zeolite, or kieselguhr. 12. The process of Claim 11 where the hydrogenation catalyst comprises Ni on a support of alumina. 13. A process for converting normal butenes into methyl ethyl ketone comprising the steps of: a. contacting a feed stream comprising normal butenes with an aqueous solution comprising vanadium- containing polyoxoanion oxidant is of the formula: (3+ χ -y)- [H y PMo (12 . x) V x O 40 ] where 0<x<12 and 0<y<(3+x), or mixtures thereof; a palladium catalyst; and chloride under conditions suitable for oxidizing the stream comprising normal butenes to a reactor product stream comprising methyl ethyl ketone and water, b. separating the reactor product stream into a stream containing methyl ethyl ketone and an aqueous stream containing a substantial portion of the polyoxoanion oxidant comprising vanadium, a palladium catalyst, and chloride, and c. recovering the methyl ethyl ketone. 14. The process of Claim 13 where the aqueous stream containing a substantial portion of the polyoxoanion oxidant comprising vanadium, a palladium catalyst, and chloride is contacted with an oxygen-containing gas to oxidize that stream and the stream is recycled to contact the butene feed stream. 15. The process of Claim 14 where the oxygen-containing gas is oxygen. 16. The process of Claim 14 where the oxygen-containing gas is air. 17. The process of Claim 13 where the cation associated with the polyoxoanion is selected from Group IA metals, Group IIA metals, or ammonium. 18. The process of Claim 13 where the polyoxoanion is of the formula H 6 PMo 9 V 3 O 40 . 19. The process of Claim 13 where the stream containing methyl ethyl ketone and butyraldehyde further contains acetic acid and where a stream containing acetic acid is separated from the methyl ethyl ketone and butyraldehyde and is extracted with methyl ethyl ketone to recover acetic acid and stripped prior to recycling to the butene feed stream. 20. The process of Claim 13 where the feed stream comprising normal butenes also contains butanes and where the process additionally comprises the steps of stripping those butanes and unreacted butenes from the stream containing methyl ethyl ketone and butyraldehyde. 21. The process of Claim 13 where the stream containing methyl ethyl ketone further comprises butyraldehyde and the process additionally comprises contacting at least a portion of the stream containing methyl ethyl ketone and butyraldehyde with hydrogen and a hydrogenation catalyst to hydrogenate at least a portion of the butyraldehyde. 22. The process of Claim 21 where hydrogenation catalyst comprises a Group VIII metal on an oxidic support. 23. The process of Claim 21 where the hydrogenation catalyst comprises Fe, Co, Pt, Pd, Ru, or Ni or mixtures or alloys of those metals on a support of ceria, silica, zirconia, alumina, tungsten oxide, boria, silica-alumina, zeolite, or kieselguhr. 24. The process of Claim 23 where the hydrogenation catalyst comprises Ni on a support of alumina. 25. A process for the hydrogenation of a minor amount of butyraldehyde in a stream containing a major amount of methyl ethyl ketone comprising the steps of contacting hydrogen and the stream with a hydrogenation catalyst comprising a Group VIII metal on an oxidic support. 26. The process of Claim 25 where the hydrogenation catalyst comprises Fe, Co, Ni, Pd, Ru, Pt or mixtures or alloys of those metals on a support of ceria, silica, zirconia, alumina, tungsten oxide, boria, silica-alumina, zeolite, or kieselguhr. 27. The process of Claim 26 where the hydrogenation catalyst comprises Ni on a support of alumina. 28. The process of Claim 25 where the contacting step is carried out at a temperature between 20 and 200 °C. 29. The process of Claim 28 where the contacting step is carried out at a temperature between 20 and 90 °C. 30. The process of Claim 27 where the stream, after contacting the hydrogenation catalyst contains less than about 50 ppm of butyraldehyde. 31. The process of Claim 25 where no more than about 1 % of the methyl ethyl ketone is hydrogenated. 32. . The process of Claim 30 where no more than about 1 % of the methyl ethyl ketone is hydrogenated.

Inventors: COOK MICHAEL L, FELLMANN JERE D, GRATE JOHN H, HAMM DAVID R, KLINGMAN KENNETH A, MAHAJAN SURESH, MURAOKA MARK T, ROSTRUP-NIELSEN THOMAS, SAXTON ROBERT J, SMITH ARNOLD R, COOK, MICHAEL, L., FELLMANN, JERE, D., GRATE, JOHN, H., HAMM, DAVID, R., KLINGMAN, KENNETH, A., MAHAJAN, SURESH, MURAOKA, MARK, T., ROSTRUP-NIELSEN, THOMAS, SAXTON, ROBERT, J., SMITH, ARNOLD, R.
Applicants: CATALYTICA INC, CATALYTICA, INC.
Application year: 1991
Main classification: C07C45
IPC codes: B01J23, B01J27, B01J31, C07B61, C07C29, C07C45, C07C47, C07C49