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WO1990000536A1 - Procede d'obtention de produits de cetone sensiblement exempts d'aldehyde - Google Patents

Procede d'obtention de produits de cetone sensiblement exempts d'aldehyde Download PDF

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Publication number
WO1990000536A1
WO1990000536A1 PCT/US1989/002945 US8902945W WO9000536A1 WO 1990000536 A1 WO1990000536 A1 WO 1990000536A1 US 8902945 W US8902945 W US 8902945W WO 9000536 A1 WO9000536 A1 WO 9000536A1
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Prior art keywords
ketone
group
catalyst
stream
oxidation
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Inventor
Stanley F. Newman
Jacques C. De Deken
Michael L. Cook
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Catalytica Inc
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Catalytica Inc
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Priority claimed from US07/218,693 external-priority patent/US4885399A/en
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Publication of WO1990000536A1 publication Critical patent/WO1990000536A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification

Definitions

  • This invention relates generally to the separation of aldehydes from ketones. More specifically, the present invention is directed to a process in which an aldehyde condensation reaction is used to remove undesirable aldehydic impurities from the desired ketone by the formation of higher boiling ester products. This process has specific application in the manufacture of ketones via olefin oxidation reactions.
  • the removal of aldehydes from ketones is commonly achieved in one of the following two ways: 1) by direct separation, using an appropriate physical unit operation, such as thermal distillation or physical adsorption; or, 2) by converting the aldehyde into a product which is more amenable to separation from the ketone than the parent aldehyde, followed by an appropriate separation of the reaction product.
  • the latter approach typically involves the use of a chemical reaction, such as hydr ⁇ genation, aldol condensation or bisulfite adduction, and is especially preferred, if not required, when the physical properties of the aldehyde impurity and the desired ketone (such as boiling point or molecular size) are too similar to enable an economical direct separation (such as distillation) .
  • a chemical reaction such as hydr ⁇ genation, aldol condensation or bisulfite adduction
  • Examples of the above methods for removing aldehydes from ketones include: physical adsorption of the aldehyde on activated alumina or molecular sieves (Japanese Pat. No. -J45-39083) ; hydrogenation of the aldehyde into the corresponding alcohol followed by distillation (S idt J. and Krekeler H. , 6th World Petroleum Congress, Section IV, Paper 40-PD9, Frankfurt, 1963) ; aldol condensation of the aldehyde into an aldol product followed by, or integrated with, distillation (U.S. Pat. No. 3,198,837; U.S. Pat. No. 3,392,200; Japanese Pat. No.
  • ketone products In commercial application, ketone products often have rigorous odor specifications, which require the elimination of substantially all aldehydic impurities which are odoriferous themselves or are the precursors of readily formed odoriferous compounds. As a result, final, commercial ketone product specifications often require that aldehydic impurities be present in the ketone only at the parts per million level. Economic separation of aldehyde(s) from ketone(s) by one of the above methods to meet these specifications is often very difficult. These methods all rely on a physical or chemical operation which is not specific for the aldehyde, and which thereby affects the ketone. These methods therefore typically result in economically unacceptable losses of the desired ketone.
  • this method may be advantageously applied to purification of keytones produced via olefin oxidation in the presence of precious metal catalysts
  • the selective condensation of aldehydes in the presence of ketones is more generally applied. It finds independent value in ketone production and purification via other reaction routes, such as the direct oxidation of alkanes (e.g., but'ane oxidation to methyl ethyl ketone and acetic acid) .
  • the method of the present invention also applies to aldehyde/ketone streams in which the aldehyde concentration exceeds impurity-level concentrations, for example up to 10 wt.% aldehyde concentration or more.
  • Tischtschenko condensation catalysts require substantially dry crude ketone streams to efficiently condense contained aldehydic components into heavier (and more easily separable) ester products.
  • This limitation is not overly limiting since various methods are available to create a dry, ketone- rich stream from a wet, ketone-rich stream. Among them are thermal distillation, azeotropic distillation, salting out the ketone from water by saturating the system with a salt such as sodium chloride or calcium chloride, as well as combinations of these methods. Adsorption of the water on drying agents such as molecular sieves can be used.
  • extraction of the ketone and aldehydes with an organic solvent has been found to be an efficient "drying" method. Extraction is effective, economic, and easily integrated into a total ketone manufacturing process.
  • Suitable extraction solvents for obtaining dry ketone streams will be those solvents having low miscibility with water and in which the ketone product is highly soluble. Such solvents include alkanes, cycloalkanes, aromatics, and their chlorinated derivatives.
  • this crude ketone product mixture subsequent to the oxidation reaction, consists of an aqueous phase containing a palladium catalyst and all, or part of the ketone product.
  • a ketone-rich organic phase containing unreacted feed components and other oxidation process components (diluents, surfactants, etc.) will form if the ketone concentration exceeds solubility limits in the aqueous phase.
  • the crude ketone product will generally contain as impurities: water, an aldehyde of the same molecular weight as the ketone, organic acids, and other olefin oxidation products.
  • ketone is obtained via olefin oxidation in an aqueous medium, such as in the Wacker process, it is necessary to recover the desired ketone from the crude oxidation reaction mass, including the dissolved catalyst components. Further, efficient and economic recovery and purification of the ketone product made via such aqueous phase olefin oxidation may be complicated by formation of ketone/water azeotropes, making application of simple thermal distillation techniques impractical to separate the desired ketone, the aqueous phase and other organic oxidation reaction byproducts. Important olefin oxidation process economics factors affect the separation of the desired ketone products from the crude ketone product.
  • the desired ketone When the desired ketone is sufficiently volatile, it may be separated from the crude olefin oxidation reaction mass by flashing. However, ketone recovered by this flashing technique will still be wet, containing water that flashes over along with the desired ketone. When the desired ketone is less volatile than water, the ketone must be recovered from the crude oxidation reaction mass by means other than flashing. Even if the ketone forms a second liquid phase in the crude reaction mass, there will be much ketone left in the aqueous phase. Thus, adequate recovery of ketone from the aqueous phase is a requirement of any economic process.
  • the present invention provides a method by which substantially all of the aldehydes are removed from a dry crude ketone-rich stream by use of the Tischtschenko condensation reaction.
  • the present invention also provides a method for obtaining a dry crude ketone-rich substrate suitable for the removal of aldehydic impurities via Tischtschenko condensation.
  • the present invention provides an integrated olefin-to-ketone process which satisfies the aforementioned process economic concerns.
  • an extraction step which when coupled with thermal distillations to make pure ketone product, creates a dry substrate suitable for treatment by Tischtschenko condensation. This extraction step also serves to separate the precious metal oxidation catalyst from the desired ketone products and oxidation byproducts without detrimental loss of precious metal catalyst components.
  • aldehydes are removed ifrom aldehyde-containing ketone mixtures by Tischtschenko condensation of the aldehyde into an ester, followed by overhead distillation of the ketone.
  • An extraction step provides substantially dry, crude ketone to the Tischtschenko condensation step.
  • the desired ketone product and oxidation byproducts are extracted to form an organic extractant phase while the precious metal catalyst remains in a second, aqueous raffinate phase, suitable for recycle to the olefin and/or catalyst oxidation step without further treatment.
  • the extraction step advantageously creates a substantially dry ketone-rich stream, thereby eliminating the need to "break" any ketone-water azeotrope in order to obtain essentially dry pure ketone product.
  • Subsequent distillations to recover the extraction solvent for recycle and to reject other non-aldehydic impurities from the desired ketone product will easily create the substantially dry ketone-rich stream suitable for Tischtschenko condensation of the aldehyde.
  • the desired ketone product is suitably more volatile than water so that it can be economically recovered from the ketone crude by distillation, .the extraction step can be advantageously applied to the flash-recovered wet crude ketone stream. This procedure, in combination with the normal distillations required for solvent and product recovery, will provide the substantially dry ketone-rich stream for subsequent treatment by Tischtschenko condensation.
  • the present invention provides a process for obtaining a substantially aldehyde-free ketone product, without regard to the source of the ketone crude.
  • a crude ketone stream containing a desired ketone product and an aldehyde contaminant is contacted with a Tischtschenko catalyst selected from the group consisting of multivalent metal alkoxides of the form [M(OR) n ], where M is a Group IIIA, Group IIB, or Group IVB metal, R an alkyl group and n the valence state of metal M.
  • a chloride promoter is provided of the form M'Clm, where M' is Group II or Group IIIA metal and m the valence state of metal M 1 .
  • the aldehyde components are condensed into ester products whose boiling points are substantially different than that of the desired ketone. These esters may then be easily separated by conventional thermal distillation.
  • the present invention further provides a process for obtaining a dry crude ketone stream, suitable for subsequent treatment by Tischtschenko condensation. Such a dry stream is necessary, because the Tischtschenko catalyst activity is adversely affected by water.
  • the present invention also provides an integrated process for obtaining high purity ketone products from aqueous phase catalyzed olefin oxidation.
  • An olefin feed stream, and an aqueous phase catalyst stream, are provided to an oxidation reactor.
  • the olefin feed stream is combined with said catalyst phase in the presence of oxygen, to thereby obtain a ketone crude.
  • the ketone crude contains desired ketone products, oxidation byproducts, and unreacted olefin feed components, all dissolved in, or mixed with the aqueous catalyst phase.
  • this ketone crude stream is contacted with an extraction solvent to form two liquid phases: a first substantially catalyst-free organic extractant phase which contains the desired ketone products, oxidation byproducts and the extraction solvent and a second, catalyst-containing aqueous raffinate phase.
  • the aqueous raffinate phase is directly recycled to said olefin oxidation reactor.
  • the organic extraction solvent is then recovered from said organic extractant phase and thereafter recycled to the extraction- contacting step.
  • Substantially pure, anhydrous ketone product is recovered from the organic extractant phase by thermal distillation.
  • the exact configuration of the thermal distillation of the extractant phase depends upon the relative boiling points of the extraction solvent and the desired ketone product.
  • An anhydrous ' ketone-rich stream is.contacted with a Tischtschenko catalyst, to condense aldehydic impurities in the anhydrous ketone-rich stream product into ester products of boiling points different than the desired ketone. Thereafter the Tischtschenko catalyst, optional promoter, and ester products are separated from the anhydrous ketone-rich stream products to obtain a high purity ketone product.
  • the recovered ketone-free catalyst system from the extraction step now partially or totally in a reduced state, is reoxidized with an oxygen-containing gas before being recycled to the olefin oxidation reactor.
  • the ketone crude is depressurized (or flashed) after the olefin oxidation reaction to remove volatile and unreacted olefin feed components from the ketone crude.
  • this crude depressurization step may also be used to recover the desired ketone, and optionally the co-produced impurities, by causing these components to flash into a vapor stream which is then condensed into a liquid phase which is then subjected to extraction.
  • the ketone recovery may be enhanced by distillation of the ketone crude.
  • a dry ketone-rich stream containing aldehydic impurities is subjected to Tischtschenko condensation to form higher boiling esters of these aldehydes, which are thereafter more easily separated from the desired ketone products by thermal distillation.
  • the olefin feed stream is butene
  • the desired ketone product is methyl ethyl ketone
  • the extraction solvent is butane
  • Figure l is a graph which shows the ratio of the first order reaction rate coefficients for both the aldehyde and ketone in a batch or plug flow reactor to achieve a desired residual aldehyde concentration at specified ketone loss.
  • Figure 2 is a graph which shows the ratio of the first order reaction rate coefficients for both the aldehyde and ketone in a backmixed reactor to achieve a desired residual aldehyde concentration at specified ketone loss.
  • Figure 3 is a flow diagram describing a generalized process according to the present invention.
  • Figure 4 is a process flow diagram which shows the process equipment used to obtain ketone products from olefins wherein oxygen is co-fed to the olefin oxidation reactor and wherein an extraction solvent is used which has a boiling point lower than the desired ketone.
  • Figure 5 is a process flow diagram which shows modifications to the process schematic shown in Figure 4 when an extraction solvent is used which has a ' boiling point higher than the desired ketone product.
  • Figure 6 is a ternary phase diagram for the butane, methyl ethyl ketone and water system at 18°C.
  • Figure 7 illustrates equilibrium curves for butane developed from the ternary diagram of Figure 6, and equilibrium curves for hexane and heptane as solvents at 25°C obtained form the open literature, R.E. Treybal, O.J. Vondrak, Industrial & Chemical Engineering, Vol. 41, No. 8, pp. 1761-63 (August 1949).
  • Figure 8 illustrates the number of theoretical countercurrent stages required to recover methyl ethyl ketone from a water solution containing 15% methyl ethyl ketone, as a function of the butane to water feed ratio.
  • Olefin oxidation processes have been developed to convert olefins to ketones in the presence of palladium and free oxygen.
  • a water soluble palladium catalyst is introduced in the aqueous phase to insure generation of palladium cations.
  • processes based upon co-feeding oxygen to the olefin oxidation reactor are described. It will be understood, however, that processes such as the Wacker process, in which the palladium catalyst solution is reoxidized in a separate reactor, are equally well suited to the present invention.
  • the ketone crude which hereinafter refers to the olefin oxidation reactor effluent stream, can comprise two liquid phases.
  • the first phase is an aqueous phase comprising wholly or partially soluble palladium catalyst and co-catalyst components, the desired ketone product, oxidation byproducts, dissolved unreacted olefin components, and optional pH controlling components, including, but not limited to sulfuric acid.
  • a second organic phase rich in ketone will form in equilibrium with the aqueous phase.
  • This second organic phase for purposes of the present invention, is subsumed within the definition of ketone crude as used hereinafter. It is intended that processes employing aqueous phase catalyst systems other than palladium, useful in olefin oxidation to ketone products, are within the scope of the instant invention. Regardless of the specific precious metal catalyst used, the same overriding economic constraints govern process design, as efficient and complete precious metal catalyst recovery is a precondition to any economical process. In investigating the separation of the precious metal catalyst from the desired ketone product, it was found experimentally that the presence of unreacted olefin feed components in the ketone crude led to palladium complexation which hindered the complete separation of the precious metal catalyst from the organic components.
  • one method of avoiding complex formation takes advantage of the fact that the vapor pressure of olefin feed components is typically higher than the vapor pressure of water and ketone products. This vapor pressure difference makes it possible to simply depressurize (or, flash) the ketone crude to remove unreacted olefin feed components. This flashing causes decomposition of the palladium-olefin complexes which may have fo-cmed in the olefin oxidation step or immediately subsequent to the oxidation step.
  • Another related method for eliminating precious metal complexation and for improving precious metal catalyst recovery is to react the remaining olefin feed components virtually to extinction in a post-olefin-oxidation reaction step. While this precious metal catalyst complex formation phenomenon is described here with reference to palladium, it is predicted that, for example, rhodium would also tend to form the same complexes with the unreacted olefin feed components.
  • the ketone crude is contacted with an extraction solvent to obtain two liquid phases.
  • an organic extractant phase contains the desired ketone products and the oxidation byproducts such as e.g. aldehydes.
  • the second aqueous raffinate phase contains the water- soluble olefin oxidation catalyst which can thereafter be recycled to the olefin oxidation step. Any oxidation byproducts which could deleteriously accumulate in the aqueous raffinate phase, and thereby adversely affect olefin oxidation reaction kinetics are conveniently extracted into the extraction solvent where they can be more easily separated from the desired ketone product.
  • the use of the extraction solvent to separate the desired ketone from the aqueous-soluble precious metal catalyst also results in the recovery of the desired ketone product in an organic phase that is substantially free of water, eliminating problems attendant to azeotrope formation, which is characteristic of many ketone-water mixtures.
  • the extraction solvent must be carefully selected with the following considerations in mind. The solvent must not form complexes with the olefin oxidation catalyst present in the ketone crude. The extraction solvent must also be capable of selectively extracting the desired ketone products, as well as the olefin oxidation reaction byproducts which would otherwise accumulate in the olefin oxidation catalyst recycle. The extraction solvent should be selected to eliminate the formation of any ketone-water azeotropes.
  • the extraction solvent should also be chosen so as to be adaptable to a variety of olefin oxidation catalyst systems. Further, the extraction solvent should be chosen to simplify the separation of the extraction solvent from the desired ketone product, as both components must ultimately be obtained in substantially pure form, the ketone as product and the extraction solvent for recycle to the extraction step.
  • the extraction solvent should be easily separated from all of the olefin oxidation reaction byproducts, preferably by simple thermal distillation.
  • the preferred class of solvents which addresses the above noted criteria is alkane compounds, including linear, branched and cyclic alkanes. Substituted alkanes, e.g., chloroalkanes, alcohols and others, can also be useful provided that these solvents meet the other criteria set forth above. Petroleum ether can also be used.
  • part of the process of the instant invention involves depressurizing the ketone crude to remove unreacted olefin feed components which tend to co plex with the precious metal olefin oxidation catalyst.
  • the extraction solvent must be free of carbon-carbon double bonds, and substantially free of unsaturated impurities.
  • a particularly preferred group of extraction solvents comprises butane, pentane, hexane, heptane, octane, nonane and decane. It is possible to select an extraction solvent which corresponds to the olefin substrate. The extraction solvent can then often be directly obtained in sufficient quantities from the olefin feed stream.
  • Another process design consideration encountered in separating the desired ketone product from the olefin oxidation reaction mass involves the separation of the desired ketone product from its aldehyde analog, unavoidably formed during olefin oxidation.
  • the difficulty in separating the ketones and aldehydes derives from the molecular weight and boiling point similarities between a ketone and its aldehyde analog which makes thermal distillation an impractical method of separation.
  • the solvent phase is distilled to remove the remaining water overhead along with other volatile impurities made in the oxidation reaction.
  • aldol condensation differs from Tischtschenko condensation in terms of the specific reaction conditions and catalyst systems that are used. For instance, whereas aldol condensation typically uses alkali or alkaline earth hydroxides or oxides at relatively elevated temperatures, Tischtschenko condensation typically requires multivalent metal alkoxides and is favored at lower temperatures.
  • the activity of Tischtschenko catalysts is said to be adversely affected by small amounts of water (see, for instance, W.C. Child and H.
  • the metal alkoxides are generally represented by the formula [M(OR) n ], where M is a Group IIIA, Group IIB, or Group IVB metal, R an alkyl group and n the valence state of metal M.
  • Particularly preferred catalysts include aluminum isopropoxides, aluminum butoxides, aluminum ethoxide and titanium ethoxide.
  • any catalyst that is useful for Tischtschenko condensation of aldehydes can be applied within the frame of the present invention.
  • Tischtschenko catalysts can optionally be used in combination with a chloride promoter of the form M*Cl m , wherein M' is Group II or Group IIIA metal and m is equal to the valence state of metal M 1 .
  • Preferred promoters include ZnCl2, HgCl2, CaCl2 and AICI 3 . While the true function of the chloride pro otor is not known, it is believed that its promoting effect is due, at least in part, to the scavenging of contaminant water molecules. Hence, any promotor that is also a water scavenger, would be expected to have a beneficial effect on the condensation reaction.
  • catalyst and promotor required depend on the particular feedstock composition, but typically vary from 0.001 to 0.1 moles of alkoxide catalyst per mole of aldehyde in the feedstock, and 0.00001 to 0.1 moles of promotor per mole of aldehyde in the feedstock, respectively.
  • liquid state e.g., aluminum secondary butoxide
  • solid state e.g., aluminum isopropoxide 5 catalysts
  • Some organic solvents which meet this design criterion are carbontetrachloride, heptane, xylene, petroleum ether, benzene and chloroform.
  • the Tischtschenko reaction is preferably conducted between 0°C and 100°C, more preferably between 20°C and 70°C.
  • the optimum temperature will, however, have to be determined for each specific feedstock and catalyst/pro otor system.
  • the undesired aldehydic impurity is butyraldehyde which is the aldehydic analog of methyl ethyl ketone.
  • Butyraldehyde is condensed to butyl butyrate upon Tischtschenko condensation.
  • the process design may include a solid-liquid separation means, e.g., a centrifuge or filter plus a means for returning the solid catalyst mass to the olefin oxidation reactor.
  • the major process components include an olefin oxidation reactor 1, a flash separator 2, a contactor 3 and a separation set 4.
  • separation set 4 is generically represented in this figure since the order of the separation scheme is dependent upon the boiling points of the extraction solvent and the desired ketone product relative to each other.
  • the olefin oxidation reaction which occurs in oxidation reactor 1, and the depressurization of the ketone crude 5 in the flash separator 2 to obtain unreacted olefin components 6 and a flashed ketone crude 7, have been previously described.
  • the depressured 5 ketone crude 7 is next fed countercurrent to an extraction solvent stream 12 in a multistage contactor 3.
  • An extraction solvent make up stream 8 is provided as necessary.
  • the extract 10 is a substantially water- free organic phase which comprises the extraction 1.0.
  • the raffinate is an aqueous phase containing the precious metal oxidation catalyst which is recycled to 15 the olefin oxidation reactor 1 through catalyst recycle stream 9.
  • the raffinate phase is substantially reduced in its content of oxidation byproducts which could deleteriously accumulate in the olefin oxidation 20 reactor 1, and thereby reduce olefin oxidation reaction rates and selectivities to the desired ketone products.
  • the organic extractant phase 10 is then further separated to obtain a substantially pure, anhydrous ketone product 11, the organic extraction solvent 12 for 25 recycle to contactor 3, and a waste stream 13 containing unwanted oxidation byproducts.
  • separation set 4 The details of separation set 4 are more fully described below with reference to Figures 4 and 5.
  • One step of the instant invention which is 30 included in separation step 4 but is not specifically illustrated in the generalized process flow diagram of Figure 3, is the Tischtschenko condensation of the aldehydic impurities contained in the organic extractant phase 10 from the contactor 3. Since organic extractant 35 phase 10 is bound to contain some residual water, it is not advisable to subject organic extractant phase 10 to the Tischtschenko reaction without first rendering the ketone-containing stream substantially anhydrous by distillation.
  • the configuration of separation step 4 to generate a substantially anhydrous ketone-containing stream is a function of the boiling point relationship between the extraction solvent and the desired ketone product.
  • the Tischtschenko reaction may be effected downstream of separation set 4.
  • the present invention is intended to be applicable to catalytic olefin oxidation as that term is broadly used.
  • olefin oxidation substrates any hydrocarbon containing at least one carbon-carbon double bond, or mixtures of such hydrocarbons.
  • the olefinic hydrocarbon which contains at least two carbon atoms per molecule, can be either substituted (e.g., 4-methyl, 1-pentene) or unsubstituted (e.g., 1-pentene) , and either cyclic (e.g., cyclohexene) or acyclic (e.g., 2- hexene) .
  • the carbon-carbon double bond can be either terminal (so- called alpha-olefins) or non-terminal (so-called internal olefins) .
  • the olefinic hydrocarbon contains more than one carbon-carbon double bond, the double bonds can be conjugated or unconjugated.
  • the olefin feed stream is a mixed butene stream
  • the desired ketone product is methyl ethyl ketone ("MEK”)
  • the extraction solvent is chosen to be butane.
  • the organic extractant phase 10 is subsequently neutralized to reduce residual organic acid byproduct acidity to obtain an organic extractant stream which is not corrosive to the downstream process equipment, enabling the use of carbon steel as a material of construction. Removal of the organic acids also assures that their presence will not interfere with the subsequent treatment with Tischtschenko catalyst.
  • any number of liquid-liquid contact media e.g., saddles, rings, etc., or mechanical means can be chosen to facilitate two liquid phase contact and component separation.
  • the nu ber of theoretical stages which are required to effect the necessary separation of the desired ketone from the aqueous phase is a function of many parameters including the extraction solvent selection, the flashed ketone crude 7 composition, the temperature of the various feed streams, and the extraction solvent/crude ketone feed ratio.
  • a series of mixers and settlers may be used instead of contactor column 3.
  • Liquid-liquid extraction is a common unit operation. Choosing precise design and operating criteria such as the type of contactor best suited for the application, feed locations and volume rates is within the capability of one skilled in this art.
  • aqueous phase 23 which may form in the separator drum by condensation of stream 22 is discarded.
  • the stripping column bottom product 24 is then distilled in a light ends column 30 to reject low boiling impurities 32 made in the olefin oxidation step.
  • This light ends distillation provides further assurance that any trace water in stream 24, perhaps as the result of a temporary upset in solvent stripping column 20, will be rejected overhead to yield an anhydrous ketone product 34 as the bottoms of this thermal distillation.
  • Stream 34 is treated in condensation reactor 33 to remove aldehydic impurities by use of the Tischtschenko condensation reaction described above, to form higher boiling ester products which are more easily separated from the desired ketone product than the aldehyde analog.
  • the treated ketone bottoms product 34 is distilled in ketone column 36 to obtain high purity ketone product overhead 11 and heavy ends 29. If they are soluble and were not removed prior to distillation in ketone column 36, the Tischtschenko catalyst and promoters or their residues will be part of heavy ends stream 29. Stream 29 is joined with the non-aqueous low boiling impurities 27 to become organic waste stream 13 which is thereafter properly and safely disposed of, for example, by incineration.
  • the light ends column 30 and the ketone column 36 comprise standard thermal distillation apparatus. The design parameters for these distillation columns are a function of the feed stream composition, product capacity, final product specifications and the desired energy efficiency.
  • these columns will be useful in the production of several ketone products, from a variety of ketone crude compositions.
  • the interchangeability of all of the process equipment may be a contributing factor to enhanced process economics.
  • the ability to calculate the number of theoretical stages required in the thermal distillations, and the product through-put requirements is within the skill of an ordinary worker in this art.
  • the extraction solvent has a boiling point which is higher than the boiling point of desired ketone product.
  • a somewhat different process scheme must be utilized to separate the desired ketone from the extraction solvent.
  • depressurized ketone crude 7 is fed countercurrent to the extraction solvent 56 in the contactor 3.
  • Make-up extraction solvent 8 is added as needed.
  • the denser, aqueous raffinate phase 9, containing the oxidation catalyst, is withdrawn from the bottom of column 3.
  • the lighter, organic extractant phase 10 is taken overhead.
  • the organic extractant phase 10 is subsequently neutralized to reduce residual organic acid byproduct acidity to obtain an organic extractant stream which is not corrosive to the downstream process equipment, enabling the use of carbon steel as a material of construction.
  • the organic extractant phase 10 is fed to a light ends column 40 to take low boilers and water overhead in stream 42, which is eventually incinerated.
  • the bottoms product 43 from column 40 contains the desired ketone product and the extraction solvent.
  • the substantially anhydrous bottoms product 43 is treated via Tischtschenko condensation of the unwanted aldehydic impurities in condensation reactor 33. This treated stream 43 is then fed to a ketone column 44.
  • The. desired ketone product is taken overhead as stream 11.
  • the higher boiling extraction solvent remains as bottom product stream 48 which is thereafter fed to a heavy ends column 52 in which substantially pure extraction solvent is taken as a bottoms product 56 and recycled to the contactor 3. If they have not been previously removed, Tischtschenko catalyst and promoter or their residues may be removed from this recycle solvent stream 56 by any conventional means.
  • the heavy ends stream 54 is joined with light ends stream 42 to become waste stream 13, which may be sent to incineration.
  • Figure 6 shows a ternary diagram for the butane, methyl ethyl ketone and water system at 18°C.
  • the binodal curve A'B' was determine-. by turbidity
  • a mixture as shown in Column II of Table 2 was prepared at room temperature in a well-stirred vessel. To this mixture was added 1.6366 grams of homogeneous palladium olefin oxidation catalyst, containing 0.011 grams of palladium. Specifically, the oxidation catalyst added comprised 1.3574 grams of 0.2545 grams of CuS0 4 • 5H 2 0 and 0.0247 grams PdS0 4 • 2H2O. The solution was then allowed to react with 0.2976 grams 1-butene at 30°C. After one hour reaction time, and cooling to room temperature, 17.3640 grams butane solvent was added to extract the oxidation reaction products. The butane-rich phase was analyzed by plasma photo emission spectrometry.
  • EXAMPLE 6 0.2298 grams of 99.999% pure solid aluminum isopropoxide and 0.0398 grams of zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. The zinc chloride had previously been dried at 200°C for hours, to remove any residual moisture. After closing the flask with a sealed septum cap, a solution consisting of 1.6108 grams of n-butyraldehyde, 33.7829 grams of n-heptane solvent and 1.8219 grams of n-hexane internal standard was introduced by syringe. The flask was then placed in an oil bath at 25"C and the contents of the flask were immediately stirred at about 350 rpm.
  • Example 6 was repeated with methyl ethyl ketone instead of butyraldehyde, to ascertain the specificity of the condensation reaction. In this experiment,
  • Example 6 was repeated using both butyraldehyde and methyl ethyl ketone in the reaction solution, to ascertain that no cross condensation between butyraldehyde and methyl ethyl ketone would occur.
  • 0.2496 grams of aluminum isopropoxide and 0.0347 grams of dried zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar.
  • Relative concentrations are defined as the ratio of the concentration in solution at time t and the concentration in solution at time zero.
  • the percentage butyraldehyde conversion at time t is given by 100 minus 100 times the relative butyraldehyde concentration at time t.
  • Example 8 was repeated in the absence of n-heptane co-solvent and using an excess amount of methyl ethyl ketone.
  • 0.2610 grams of aluminum isopropoxide and 0.0510 grams of dry zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.4998 grams of n-butyraldehyde, 41.4848 grams of methyl ethyl ke'tone and 0.6302 grams of n-hexane internal standard was introduced by syringe.
  • Example 9 In order to verify the conclusion arrived at in Example 9, the procedure of Example 9 was repeated, but this time using methyl ethyl ketone that had been purified by fractional distillation in order to reduce its water content.
  • 0.2980 grams of aluminum isopropoxide and 0.0393 grams of dried zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.4667 grams of n- butyraldehyde, 37.2653 grams of purified methyl ethyl ketone and 0.3060 grams of n-hexane internal standard was introduced by syringe.
  • Example 10 was repeated at 50°C instead of 25°C, again using distilled methyl ethyl ketone.
  • 0.2250 grams of aluminum isopropoxide and 0.0455 grams of dried zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.3418 grams of n-butyraldehyde, 26.2086 grams of methyl ethyl ketone and 0.1742 grams of n-hexane internal standard was introduced by syringe.
  • Example 10 was repeated at 100°C instead of 25°C, again using distilled methyl ethyl ketone.
  • 0.2600 grams of aluminum isopropoxide and 0.0400 grams of dried zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.5895 grams of n-butyraldehyde, 42.3720 grams of methyl ethyl ketone and 0.2305 grams of n-hexane internal standard was introduced by syringe.
  • Example 12 was repeated, this time however allowing the alkoxide catalyst and zinc chloride promotor to soak for 1 hour in distilled methyl ethyl ketone at 100°C, prior to introduction of the n-butyraldehyde and n- hexane standard.
  • the procedure of this experiment was as follows. 0--2701 grams of aluminum isopropoxide, 0.0398 grams o- dried zinc chloride and 43.8838 grams of methyl ethyl ketone were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar.
  • Example 11 was repeated using aluminum tertiary butoxide instead of aluminum isopropoxide as a catalyst, again using distilled methyl ethyl ketone.
  • 0.2341 grams of aluminum tertiary butoxide and 0.0464 grams of dried zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.7832 grams of butyraldehyde, 39.7766 grams of methyl ethyl ketone and 0.3936 grams of n-hexane internal standard was introduced by syringe.
  • Example 11 was repeated using liquid zinc isopropoxide instead of aluminum isopropoxide as a catalyst, and in the absence of zinc chloride.
  • 0.4068 grams of zinc isopropoxide was placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar. After closing the flask with a sealed septum cap, a solution consisting of 1.6942 grams of n-butyraldehyde, 37.4425 grams of methyl ethyl ketone and 0.2289 grams of n-hexane internal standard was introduced by syringe. The flask was then placed in an oil bath at 50°C and the contents of the flask were immediately stirred at about 350 rpm. Samples of the reaction solution were analyzed at periodic time intervals, as indicated in Table 9. The conversion of butyraldehyde amounted to 53.1% after 100 minutes of reaction time.
  • Methyl ethyl ketone was purified by slow fractional distillation, followed by storage over activated molecular sieve 3A for 24 hrs, in an attempt to further improve the dryness of the methyl ethyl ketone used. Prior to use, the molecular sieve had been activated at 300°C for 48 hours. The methyl ethyl ketone was then used in the following experiment, with substantially the same procedure of Example 11. 0.2378 grams of aluminum isopropoxide and 0.0573 grams of dry zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar.
  • Example 16 was repeated, but this time in the absence of zinc chloride promotor.
  • 0.2728 grams of aluminum isopropoxide was placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar.
  • a solution consisting of 1.5178 grams of n- butyraldehyde, 34.7936 grams of methyl ethyl ketone and 0.5273 grams of n-hexane internal standard was introduced by syringe.
  • the flask was then placed in an oil bath at 50°C and the contents of the flask were stirred at about 350 rpm. After 40 minutes reaction time, the butyraldehyde conversion only amounted to 41.4%, as opposed to 78.0% under the conditions of Example 16.
  • Example 16 was repeated using the same purifieid methyl ethyl ketone feed source, but at the following different loadings.
  • 0.2589 grams of aluminum isopropoxide and 0.0326 grams of dry zinc chloride were placed under nitrogen in a 60 ml glass flask containing a teflon coated magnetic stir bar.
  • a solution consisting of 0.5112 grams of n-butyraldehyde, 37.5153 grams of methyl ethyl ketone and 0.4353 grams of n-hexane internal standard was introduced by syringe.
  • the flask was then placed in an oil bath at 50°C and the contents of the flask were stirred at about 350 rpm.
  • the conversion of butyraldehyde amounted to 96.7% after 70 minutes reaction time.
  • Example 16 was repeated using liquid aluminum secondary butoxide instead of aluminum isopropoxide as a catalyst, with the same purified methyl ethyl ketone feed source. In this experiment,

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Abstract

La condensation de Tischtschenko d'aldéhydes est utilisée pour éliminer les aldéhydes de courants contenant une cétone sèche. La condenstion de Tischtschenko est utilisée pour condenser les aldéhydes en esters dont les points d'ébullition sont sensiblement différents de ceux des cétones, simplifiant considérablement la séparation des esters des cétones. Une étape d'extraction organique est utilisée pour obtenir un courant contenant une cétone sensiblement sèche. Une classe particulièrement préférée de solvants d'extraction est sélectionnée dans le groupe incluant le butane, le pentane, l'hexane, l'heptane, l'octane, le nonane, le décane et leurs mélanges. Dans des modes préférentiels de réalisation, la réaction de Tischtschenko est utilisée dans le contexte d'oxydation catalysée en phase aqueuse d'oléfines en cétones. La condensation d'aldéhydes en esters permet une élimination aisée et efficace des analogues d'aldéhydes des cétones désirées.
PCT/US1989/002945 1988-07-13 1989-07-06 Procede d'obtention de produits de cetone sensiblement exempts d'aldehyde Ceased WO1990000536A1 (fr)

Applications Claiming Priority (2)

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US218,693 1988-07-13
US07/218,693 US4885399A (en) 1986-11-26 1988-07-13 Process for obtaining substantially aldehyde-free ketone products

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1785166A (en) * 1925-07-14 1930-12-16 Carbide & Carbon Chem Corp Manufacture of esters from aldehydes
US3047618A (en) * 1960-05-18 1962-07-31 Gulf Research Development Co Process for condensing aldehydes to esters
US4507507A (en) * 1982-04-12 1985-03-26 Phillips Petroleum Company Catalysts
US4550212A (en) * 1982-03-09 1985-10-29 Phillips Petroleum Company Catalysts
US4620038A (en) * 1984-02-29 1986-10-28 Babcock-Hitachi Kabushiki Kaisha Process for producing methyl ethyl ketone
US4723041A (en) * 1985-09-24 1988-02-02 Catalytica Associates Olefin oxidation catalyst system
US4738943A (en) * 1986-02-04 1988-04-19 Catalytica Associates Palladium-nitrile ligand catalyst system and oxidation process
US4847421A (en) * 1986-02-04 1989-07-11 Catalytica, Associates Palladium-nitrile ligand catalyst system and oxidation processes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1785166A (en) * 1925-07-14 1930-12-16 Carbide & Carbon Chem Corp Manufacture of esters from aldehydes
US3047618A (en) * 1960-05-18 1962-07-31 Gulf Research Development Co Process for condensing aldehydes to esters
US4550212A (en) * 1982-03-09 1985-10-29 Phillips Petroleum Company Catalysts
US4507507A (en) * 1982-04-12 1985-03-26 Phillips Petroleum Company Catalysts
US4620038A (en) * 1984-02-29 1986-10-28 Babcock-Hitachi Kabushiki Kaisha Process for producing methyl ethyl ketone
US4723041A (en) * 1985-09-24 1988-02-02 Catalytica Associates Olefin oxidation catalyst system
US4738943A (en) * 1986-02-04 1988-04-19 Catalytica Associates Palladium-nitrile ligand catalyst system and oxidation process
US4847421A (en) * 1986-02-04 1989-07-11 Catalytica, Associates Palladium-nitrile ligand catalyst system and oxidation processes

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 45, December 1923, W.C. CHILD, "The Condensation of Aldehydes to Esters by Aluminum Ethoxide", pages 3013-3023. *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 47, March 1925, W.C. CHILD, "The Condensation of Aldehydes to Esters by Alcoxides", pages 798-807. *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 68, August 1946, FRANK J. VILLANI, "Glycol Esters from Aldehydes", pages 1674-1675. *
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 74, 20 October 1952, I. LIN, "A Study of the Mixed Tischtschenko Reaction", pages 5133-5134. *

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