DE3335639A1 - METHOD FOR PRODUCING A CARBONIC ACID, CARBONIC ACID ANHYDRID OR CARBONIC ACID ESTER - Google Patents

Description

description

The invention relates to the carbonylation of olefins with the formation of carboxylic acids, in particular monocarboxylic acids and above all Nxederalkancarbonsauren, such as propionic acid, the anhydrides of such acids and the esters of such acids, especially the lower alkanecarboxylic acid esters.

Carboxylic acids have been known industrial chemicals for many years, which are used in large quantities to manufacture a wide variety of products. The production of carboxylic acids by the action of carbon monoxide on olefins (carbonylation) is for example in US-PS

2,768,968. These known carbonylation reactions however, olefins require the use of very high pressures. However, there are already carbonylation processes for olefins which can be carried out at lower pressures. So describe the US PS

3,579,551, U.S. Patent 3,579,522 and U.S. Patent 3,816,488, for example, the carbonylation of olefins in the presence of Compounds and complexes of precious metals from Group VIII of the Periodic Table of the Elements, such as iridium and Rhodium, and in the presence of iodide under more moderate pressures than in the US-PS mentioned at the beginning. This low pressure carbonylation process however, have the disadvantage that they require the use of expensive precious metals. In BE-PS 860 557 is the production of carboxylic acids by carbonylation of alcohols in the presence of a nickel catalyst, which is promoted by a trivalent phosphorus compound, and described in the presence of an iodide.

It is also already known to produce acid anhydrides by the action of carbon monoxide on olefins, and For example, reference is made to the US Pat. No. 2,768,968 already mentioned above, according to which very high pressures are required.

must be turned. US Pat. No. 3,852,346 describes the carbonylation of olefins in the presence of compounds of noble metals from Group VIII of the Periodic Table of the Elements, such as iridium and rhodium, and in the presence of an iodide under more moderate pressures than in the process of US Pat. No. 2,768 968 and other so-called Reppe processes. These methods have, in turn, however, the same disadvantages as the patent US, US Patent 3,579,522 and US Patent No. 3,816,488 methods known from the aforementioned 3,579,551 ¹ ^ namely, that also expensive with them, relatively rare metals used Need to become.

The production of carboxylic acid esters by the action of carbon monoxide on olefins by processes in which several Types of catalysts used is also already described in various patents. For example, US Pat. No. 3,168,555-3 shows the implementation of carbon monoxide with an olefinic hydrocarbon in the presence of alcohols using a Transition metal carbonyl catalyst from group VIIIb, the cobalt, ruthenium, rhodium or iridium in complex Contains combination with carbon monoxide and a trialkyl phosphorus. From US-PS 3,040,090 is a conversion of carbon monoxide, an ethylenically unsaturated compound and an alcohol in the presence of a noble metal chelate of Group VIII of the Periodic Table of the Elements. The US-PS 3,917,677 shows a conversion of carbon monoxide, ethylenically unsaturated compounds and alcohols using a catalyst that has a rhodium component and contains a tertiary organophosphorus component. This also includes a discussion of the status of the Technology and the limits of the known processes, namely above all the poor yields that can be achieved with them the known processes generally require the use of relatively high pressures. After the in US Pat. No. 3,917,677 processes described are evidently achieved better yields, but this is only possible with

Twist of a rhodium catalyst.

U.S. Patent 4,335,058, U.S. Patent 4,354,036 and U.S. Patent 4,372,889 describe related processes for carbonylation of olefins using a molybdenum-Nikkei or a tungsten-nickel cocatalyst in the presence a promoter made from an organophosphorus compound or an organonitrogen compound such as a phosphine or a tertiary amine, with the formation of carboxylic acids and carboxylic acid anhydrides or of carboxylic acid esters and Carboxylic acids. These processes using nickel catalysts enable the carbonylation of olefins at moderate pressures with no need to use a noble metal catalyst and are intended for Purpose highly effective, leaving no need in terms of attainable reaction speed and productivity however, there is still room for improvement using organic promoters.

As a result of the disadvantages of the known methods set out above, the invention is now based on the object of improved Process for the preparation of carboxylic acids, in particular lower alkanecarboxylic acids such as propionic acid, the To provide anhydrides of such acids and their esters, in which neither high pressures nor noble metals from the Group VIII of the Periodic Table of the Elements is needed and which involves the manufacture of carboxylic acids, carboxylic acid anhydrides and carboxylic acid esters in high yield with short reaction times with no need for use enable organic promoters.

This object is now achieved according to the invention by carbonylating an olefin using a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium-nickel-alkali metal cocatalyst in the presence of a halide, preferably an iodide, a bromide and / or a ¹ chloride, especially one

Iodide, and in the presence of a coreactant in which it is can be water, a carboxylic acid or an alcohol. Therefore, if you want to produce a carboxylic acid, then this carbonylation is carried out in the presence of water. If you want to produce a carboxylic acid anhydride, then the carbonylation is carried out under practically anhydrous conditions in the presence of a carboxylic acid. To produce an ester, this carbonylation is carried out in the presence of an alcohol. It was

¹ ^ after surprisingly found that this cocatalyst system in an environment of the specified type enables the carbonylation of olefins not only at relatively low pressures, but that after this, carboxylic acids, carboxylic acids are also rapidly and in high yield

¹ ^ reanhydrides and carboxylic acid esters can be produced.

The particular effectiveness of the catalyst system of the process according to the invention is above all taken into account of the test data surprisingly given in EP-OS 0 035 458, in which the carbonylation of methanol under Formation of acetic acid is described. In the experiments it contains using nickel in combination with molybdenum, tungsten or chromium there is absolutely no reaction even after 2 hours. It is also observed that with the usual use of nickel-based catalysts in carbonylation reactions there is a tendency for the nickel components to be volatilized and then dissipated together with the reaction resulting vapors escape. In contrast, it has now surprisingly been found that the catalyst system according to the invention greatly reduces the volatility of nickel and results in a highly stable catalyst combination, in particular in the case of the molybdenum-containing cocatalyst, which is the cocatalyst preferred according to the invention is.

The method according to the invention therefore consists in a

Reaction of carbon monoxide with an olefin, such as a lower one Alkene, in the presence of a halide, for example a hydrocarbon halide, especially one Lower alkyl halide, such as ethyl iodide, in the presence and in the presence of a cocatalyst of the type defined above of water, a carboxylic acid (under anhydrous conditions) or an alcohol. Propionic acid, propionic anhydride or a propionic acid ester can be efficiently prepared hereafter, for example, by ethylene a Carbonylation in the presence of the appropriate co-reactant and in the presence of the catalyst system according to the invention undergoes. In the case of the production of propionic anhydride, propionic acid is used as a coreactant.

In a similar way, other alkanecarboxylic acids, Like butyric acid or valeric acid, their anhydrides and their esters can be prepared by adding the appropriate Alkene, such as propylene, butene-1, butene-2, the hexenes, the octenes and the like, are carbonylated. Similar can be also other alkanecarboxylic acids, such as capric acid, caprylic acid or lauric acid and corresponding higher carboxylic acids, prepare their anhydrides and their esters by subjecting the respective olefin to a "carbonylation" process.

The olefin required as a reactant can be any an ethylenically unsaturated hydrocarbon, generally of 2 to about 25 carbon atoms and preferably contains 2 to about 15 carbon atoms. The ethylenically unsaturated compound has the following

QQ general formula

wherein R ,, R ", R_ and R. for hydrogen or the same or various alkyl, cycloalkyl, aryl, alkaryl, or aralkyl or in which one of the substituents R, and R "and one of the substituents R ^ and R together each one

form a single alkylene group of 2 to about 8 carbon atoms. The substituents R ,, R ₃₇ R ₃ and R may be branched and may be substituted by substituents which are inert in the inventive reactions.

Examples of ethylenically unsaturated hydrocarbons useful in the process of the invention include ethylene, propylene, butene-1, butene-2, 2-methylbutene-1, cyclobutene, hexene-1, hexene-2, cyclohexene, 3-ethylhexene-1, isobutylene, octene -1, 2-Methylhexen-1, Ethyleyelohexen, Decen-1, Cyclohepten, Cycloocten, Cyclononen, 3,3-DimethyI-nonen-1, Dodecen-1, Undecen-3, 6-Propyldecen-1, Tetrad- u cen- 2,3-Amyldecene-1 and the like, hexadecene-1, 4-ethyltridecene-1, octadecene-1, 5,5-dipropyldodecene-1, vinylcyclohexane, allylcyclohexane, styrene, p-methylstyrene, (X-methylstyrene, p-vinylcumene , β-vinylnaphthalene, 1,1-diphenylbutene-1, 3-benzylheptene-1, divinylbenzene, 1-allyl-3-vinylbenzene, etc. Of the olefins listed above, the cx-hydrocarbon olefins and the olefins having 2 to about 10 carbon atoms preferred, such as ethylene, propylene, butene-1, hexene-1, heptene-1, octene-1 and the like, namely those olefins of the above formula in which R 1, R 1, R and R _{4 are} hydrogen or Are alkyl groups with a total of 1 to 8 carbon atoms, the lower alkenes being preferred, namely the alkenes with 2 to 6 carbon atoms, and here in particular ethylene.

In the case of the production of an acid anhydride as a coreactant The carboxylic acid required can generally be any carboxylic acid having 1 to about 25 carbon atoms and have the following formula

RCOOH,

wherein R is hydrogen, alkyl, cycloalkyl or aryl. R preferably contains 1 to about 18 carbon atoms and is in particular alkyl having 1 to about 12 carbon atoms,

especially with 1 to 6 carbon atoms, such as methyl, Ethyl, propyl, isobutyl, hexyl, nonyl and the like or aryl of 6 to about 9 carbon atoms such as phenyl, tolyl, and the like.

Examples of suitable acids include acetic acid, propionic acid, η-butyric acid, isobutyric acid, pivalic acid, n-valeric acid, n-caproic acid, stearic acid, benzoic acid, Phthalic acid, terephthalic acid, toluic acid, 3-phenylhexanecarboxylic acid, 2-xylyl palmitic acid or 4-phenyl-5-isobutyl stearic acid. The preferred acids are the fatty acids or alkanecarboxylic acids having 2 to about 12 carbon atoms, such as acetic acid, propionic acid, η-butyric acid, isobutyric acid, Pivalic acid, caproic acid, undecylic acid and the like. The lower alkanecarboxylic acids are particularly preferred, namely the acids of the above formula in which R is an alkyl group with 1 to 6 carbon atoms, especially propionic acid. R can be branched or substituted by substituents be substituted, which are inert in the reactions according to the invention.

The reactants are preferably chosen so that the anhydride obtained is a symmetrical acid anhydride, viz an acid anhydride with two identical acyl groups. 25th

The alcohol required as a coreactant can generally be any alcohol of the formula ROH, where R is alkyl, cycloalkyl, Aryl, alkaryl or aralkyl, or a mixture thereof. R preferably contains 1 to about 18 carbon atoms and is in particular alkyl having 1 to about 12 carbon atoms, such as methyl, ethyl, propyl, butyl, isobutyl, Pentyl, hexyl, nonyl and the like, or means aralkyl with 7 to about 14 carbon atoms, such as benzyl, Phenethyl and the like.

Examples of suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, t-butanol, penta-

nol, hexanol, 2-ethylhexanol, octanol, decanol, 6-pentadecanol, Cyclopentanol, methylcyclopentanol, cyclohexanol, Benzyl alcohol, O ^ Qc-dimethylbenzyl alcohol, ex, α-diethy! .Benzyl alcohol, CX ethyl phenethyl alcohol, naphthyl carbinol, xylyl carbinol, tolyl carbinol, and the like.

In the most preferred embodiments of the invention, carbon monoxide is used with ethylene and water, propionic acid or methanol in the presence of the cocatalyst-halide system of the type described above, resulting in propionic acid, propionic anhydride or methyl propionate got. The formula for these conversions is as follows:

C ₀ H. + CO + H ₀ O > C _o H _c C00H

2 4 2. Zd

C ₀ H + C ₀ H + CO COOH> C _{0 0} H H COOCOC

C ₂ H ₄ + CO + CH ₃ OH> C ₂ H ₅ COOCH ₃

Carbon monoxide is combined with unreacted in the vapor phase Olefin removed when the olefin is normally gaseous, as is the case with ethylene, and it can be return if desired. Usually liquid and relatively volatile components, such as alkyl halide, usually liquid unreacted olefin and the co-reactant (water, carboxylic acid, or alcohol) and any By-products that are present in the resulting reaction mixture can be easily removed and separated from each other are separated, for example by distillation, so that they can then be recycled, and in such a way In this case, the net product yield consists practically exclusively of the desired carboxylic acid, the desired one Acid anhydride or the desired ester. In the case of the preferred liquid phase reaction, they can be organized Compounds readily, for example, by distillation separate from the metal-containing components. The reaction is expediently carried out in a reaction

zone carried out in which the carbon monoxide, the olefin, the co-reactants, the halide and the cocatalyst feeds. If you want an acid anhydride as the desired product, then no water is formed and the reaction, as mentioned above, carried out under practically anhydrous conditions. In the case of making a Esters, the liquid phase reaction is preferably carried out under boiling conditions, all of which are volatile Components are removed in the vapor phase, so that the catalyst remains in the reactor.

As the above equations show, requires a carbonylation reaction of the type described, which is selective to a carboxylic acid, a carboxylic acid anhydride or a carboxylic acid ester leads, at least 1 mole of carbon monoxide and 1 mole of the co-reactant (water, carboxylic acid or alcohol) per Mol (equivalent) of converted ethylenically unsaturated. Binding. The olefin serving as the feed is therefore normally introduced with equimolar amounts of the co-reactant, although in a larger amount of the co-reactant can be worked.

The inventive method can be performed over a wide temperature range, for example, generally at temperatures of 25 to 35O ⁰ C. is preferably carried out at temperatures of 100 to 250 ⁰ C, and especially at temperatures of 125 to 225 ° C. Lower temperatures can also be used, but this tends to result in slower reaction rates. It is also possible to work at higher temperatures, but this is no longer of any particular advantage. The reaction time is also not a parameter of the process according to the invention and depends largely on the temperature used. For example, residence times of 0.1 to 20 hours can generally be used. The reaction is carried out under superatmospheric pressure. Excessively high pressures,

which would make the use of special high-pressure systems necessary, but are not necessary- In general, the reaction is carried out at carbon monoxide partial pressures of preferably at least 1 to less than 140 bar, in particular at carbon monoxide partial pressures of 1 to 70 bar, and especially at carbon monoxide partial pressures of 2 up to 14 bar. In general, however, carbon monoxide partial pressures of 0.07 to 350 bar or even up to 700 bar can be used. By adjusting the carbon monoxide partial pressure to one of these values, sufficient quantities of this reactant are always present. The total pressure is of course the pressure which provides the desired carbon monoxide partial pressure, and it preferably represents the pressure which one needs to maintain a liquid phase, and in such a case the reaction is conveniently carried out in an autoclave or similar apparatus. At the end of the residence time desired in each case, the reaction mixture is separated into its individual components, ^{which is} best done by distillation. The reaction product is preferably introduced into a distillation zone, which can be a Fraktionierdestillatxonskolonne or a series of columns through which the volatile constituents can be separated from the anhydride or ester desired as the product and through which the product can also be separated from the less can separate volatile constituents of the catalyst from the reaction mixture. The boiling points of the volatile constituents are so far apart that their separation by conventional distillation does not cause any particular problem. In a similar way, the higher-boiling organic constituents can easily be separated from the metal catalyst components by distillation. The cocatalyst obtained in this way can then be combined with fresh amounts of olefin, carbon monoxide and coreactant, including the halide component, and reacted again, producing further amounts of carboxylic acid, anhydride or ester

are formed. If the reaction is carried out under boiling conditions, the reaction effluent is complete in the vapor phase, so that the components separate from one another after condensation in the manner described let separate.

The method according to the invention can also be carried out in the presence an organic solvent or diluent can be carried out, but this is not absolutely necessary is. The presence of a higher boiling solvent or diluent, preferably the product itself,

:. such as propionic acid, propionic anhydride or a propionic acid ester in the case of the carbonylation of ethylene, allows the use of more moderate total pressures. Optionally can the solvent or diluent can also be any organic solvent present in the vicinity of the present Process is inert, for example a hydrocarbon such as octane, benzene, toluene, xylene or tetralin, or a carboxylic acid. If a carboxylic acid is used, this should preferably be the one to be produced Carboxylic acid correspond, since the solvent used should preferably be native, so that in the case of a Carbonylation of ethylene for example propionic acid should be used. Instead, however, can also use other carboxylic acids, such as acetic acid. If it is not the product itself, then it is advisable a solvent or diluent is selected which is sufficient in terms of its boiling point from the desired Product differs in the reaction mixture so that it can be separated off without further ado. Of course you can mixtures of solvents or diluents can also be used.

The carbon monoxide is preferably used in a practically pure and as commercially available form, if desired however also contain inert diluents, such as carbon dioxide, nitrogen, methane or noble gases. The presence inert diluent affects the car-

Bonylierungsreaktion not, but makes an increase in System pressure required to achieve the desired carbon monoxide partial pressure can be maintained. Hydrogen can be present and even stabilize the Contribute to the catalyst. Carbon monoxide feed can be used to achieve lower carbon monoxide partial pressures therefore even dilute with hydrogen or some other inert gas of the kind mentioned above. That as a diluent serving gas can be used in amounts up to 95%.

The cocatalyst components can be used in any suitable form, for example in the zero valent state or in any superior form. So you can, for example, the nickel and the molybdenum, or tungsten Use chromium in metallic and finely divided form or in the form of a compound, both an organic one as well as an inorganic compound through which the cocatalyst components effectively enter the reaction system let introduce. Corresponding carbonates, oxides, Hydroxides, bromides, iodides, chlorides, oxyhalides, hydrides, lower alkoxides (methoxides), phenoxides or carboxylates, the carboxylation of which is derived from an alkanecarboxylic acid with 1 to 20 carbon atoms, such as acetates, butyrates, decanoates, Laurates, benzoates and the like, of molybdenum, tungsten, chromium or nickel can be used. In a similar way Complexes of the cocatalyst components can also be used, for example carbonyls, metal alkyls, Chelates, association compounds or enol salts. Examples of other complexes include bis (tripheny! Phosphine ) nickeldicarbony1, tricyclopentadieny1trinickeldicarbonyl, Tetrakisitriphenylphosphit) nickel and the corresponding complexes of the other components, such as molybdenum

gg hexacarbonyl or tungsten hexacarbonyl.

The elemental forms, compounds which are halides, in particular

dere iodides, and organic salts, such as the salts of the monocarboxylic acid, which corresponds to the carboxylic acid residue of the product to be manufactured.

The alkali metal component, for example a metal from Group IA of the periodic table, such as lithium, potassium, sodium or cesium is conveniently used as a compound, especially as a salt, and especially as a halide, such as Iodide, used. The preferred alkali metal is lithium. However, the alkali metal component can also be used as a hydroxide, Carboxylate, alkoxide or in the form of other suitable compounds can be used, as described above in connection with the other cocatalyst components have been mentioned, and typical alkali metal components are therefore exemplary- ■ * ■ " wise sodium iodide, potassium iodide, cesium iodide, lithium iodide, lithium bromide, lithium chloride, lithium acetate and lithium hydroxide .

The above-mentioned compounds and complexes are a matter of course are merely examples of suitable forms for several cocatalyst components and are therefore not limiting to grasp.

The cocatalyst components mentioned and to be used can also contain impurities, as they normally do Commercially available metals or metal compounds are present and they do not need to be cleaned any further will.

The amount of each cocatalyst component is in no way critical and does not constitute a parameter of the invention Procedure and can vary over a wide range. Of course, with an amount of catalyst worked, which ensures the desired suitable and appropriate reaction rate, since the reaction rate is influenced by the amount of catalyst. However, virtually any amount of catalyst results in one

Facilitates the basic reaction and can therefore be regarded as a catalytically effective amount. The amount of each Catalyst component is generally 1 mmol to 1 mol per liter of reaction mixture, preferably 15 to 500 mmol per liter of reaction mixture, and in particular 15 to 150 mmol per liter of reaction mixture.

The ratio of nickel to molybdenum, tungsten or chromium cocatalyst components can vary. In general this ratio is 1 mole of the Niekel component to 0.01 to 100 moles of the second cocatalyst component, namely the molybdenum, tungsten or chromium component. Preferably the nickel component is in an amount of 1 mol to 0.1 to 20 mol of the second cocatalyst component

¹ ^ te, and especially in an amount of 1 mole to 1 to 10 moles of the second cocatalyst component, applied. The ratio of nickel to alkali metal component can fluctuate in a similar way. The amount of nickel can be, for example, 1 mole per 1 to 1000 moles of the alkali metal component. It is preferably 1 mole of nickel to 10 to 100 moles of the alkali metal component, and in particular makes 1 mole of nickel to 20 to 50 moles of the alkali metal component.

The "amount of the halide component can also be within fluctuate across broad boundaries. The halide component should preferably be in an amount of at least 0.1 mol (in terms of as elemental halogen) per mole of nickel. Usually with an amount of halide from 1 to 100 moles per mole of nickel, and in particular with an amount of halide of 2 to 50 moles per mole of nickel, worked. Normally no more than 20 0 moles of halide per mole of nickel are used. The halide component must be part of the system of course, it cannot be added as a hydrocarbon halide, but can also be added as another organic one Halide, as hydrogen halide or as other inorganic halide, such as a salt, for example

as an alkali metal salt or other metal salt, or even as elemental halogen, such as iodine or bromine, are supplied.

The catalyst system according to the invention exists, as already mentioned, from a halide component, in particular an iodide component, and a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium-nickel-alkali metal cocatalyst component. The invented

¹ ^ proper catalyst system allows the formation of carboxylic acids, ⁽ carboxylic acid anhydrides and carboxylic acid esters in
high yield with short reaction times, without the need to use noble metals from group VIII, and the presence of the alkali metal component together

¹ ^ men with the molybdenum, tungsten or chromium component allows good results with relatively low
Amounts of cocatalyst components and lower amounts
. of nickel in comparison to the known processes in which nickel-containing catalysts have to be used.

A particular embodiment of the catalyst from
The molybdenum-nickel-alkali metal, tungsten-nickel-alkali metal or chromium-nickel-alkali metal cocatalyst component and the halide component can be represented by the following formula:

X: T: Z: Q,

where X stands for molybdenum, tungsten or chromium, T nickel
is, X and T in either zero-valued. State or in the form of a halide, oxide, carboxylate with 1 to 20 carbon atoms, carbonyls or hydride, Z is a halide source which is hydrogen halide,
Halogen, an alkyl halide having 1 to 20 carbon atoms in the alkyl group, or an alkali metal halide, and Q is the alkali metal component. According to the above, the preferred alkali metal is lithium

in the form of an iodide, bromide, chloride or carboxylate as defined for X and T, wherein the molar ratio of X: T ranges from 0.1 to 10: 1, the molar ratio of X + T: Q also ranges from 0.1 to 10: 1 and the molar ratio of Z: X + T ranges from 0.01 to 0.1: 1.

The reaction described above lends itself to a continuous one Process in which the reactants and the catalyst are continuously fed into the respective reaction zone feeds and the reaction mixture for separation the volatile organic matter is continuously distilled, resulting in a net product of practically the carboxylic acid, the carboxylic acid anhydride or the ester, with the other organic components recycled and, in the case of a liquid phase reaction, also recirculates a fraction containing residual catalyst.

The catalytic which takes place in the process according to the invention Reaction can of course, if desired be carried out in the vapor phase by adjusting the total pressure in a suitable manner so as a function of the Temperature controls that the reactants are in vapor form when in contact with the catalyst. In the case a vapor phase process and also in the case of a liquid phase process If desired, supported catalysts can be used, namely catalysts whose catalytically active ingredients are dispersed on a support of conventional type, such as on alumina, silica, Silicon carbide, zirconia, carbon, bauxite, attapulgite clay and the like. The catalyst components can can be applied to the carrier in a conventional manner, for example by impregnating the respective carrier with a solution of the catalyst component. The concentrations of the catalyst components on the carrier can fluctuate within wide limits. For example, they can make up 0.01 to 10% by weight or more. Ty-

european working conditions for a vapor phase method are temperatures of generally from 100 to 350 ⁰ C, preferably 150 to 275 ° C, and especially 175-255 ° C, pressures of generally from 0.07 to 350 bar, preferably 4 to 105 bar, and in particular 10.5 to 35 bar, and space velocities of generally 50 to 10,000 hours, preferably 200 to 6000 hours, and in particular 500 to 4000 hours (STP). If a supported catalyst is used, the iodide component is contained in the reactants and is not arranged on the support.

The invention is further illustrated below with the aid of examples. Unless otherwise stated, are in it all partial information is to be understood as weight information.

Example 1

A glass-lined pressure vessel stirred with a magnetic stirrer is used in this example.

The reaction vessel is charged with 12 parts of water, 11.9 parts of ethyl iodide, 0.76 parts of nickel iodide (NiI-), 1.4 parts of molybdenum hexacarbonyl, 14.3 parts of lithium iodide and 60 parts of ethyl acetate as a solvent. The vessel is flushed with argon, whereupon hydrogen is added up to an overpressure of 6.9 bar and then carbon monoxide up to a pressure of 34.5 bar. The vessel is then heated ^{to 180 ° C. with stirring.} The pressure is then brought to 52 bar with ethylene. The pressure is increased by adding a 1; 1 mixture of ethylene and carbon as required.

2Q monoxide at 52 bar maintained, and the temperature is maintained at 180 ⁰ C. After one hour of reaction shows a gas chromatographic analysis of the reaction mixture, the formation of propionic acid at a rate of 4.38 moles per liter per hour, where the entire unreacted olefin i ⁿ Propionic acid has been converted.

"- 20 -

example

The pressure vessel used in Example 1 is charged with 12 parts of water, 12 parts of ethyl iodide, 0.74 parts of nickel iodide (Nil “), 1.4 parts of molybdenum hexacarbonyl, 14.4 parts of lithium iodide and 60 parts of tetrahydrofuran as solvent. The vessel is flushed with argon, whereupon hydrogen is added up to an overpressure of 6.9 bar and then carbon monoxide up to a pressure of 34.5 bar. The vessel is then heated ^{to 180 ° C. with stirring.} The pressure is then brought to 55 bar with ethylene. The pressure is kept at 55 bar by adding a 1: 1 mixture of ethylene and carbon monoxide as required, and the temperature is kept at 180 ^° C. After one hour of reaction, gas chromatographic analysis of the reaction mixture shows the formation of propionic acid at a rate of 2 .97 moles per liter per hour with all of the olefin converted having been converted to propionic acid.

Example 3

The pressure vessel described in Example 1 is charged with 12 parts of water, 12 parts of iodoethane, 0.72 parts of nickel iodide (NiI), 1.4 parts of chromium hexacarbonyl, 14.3 parts of lithium iodide and 60 parts of tetrahydrofuran as solvent. The vessel is flushed with argon, whereupon hydrogen is added up to an overpressure of 6.9 bar and then carbon monoxide up to a pressure of 34.5 bar. The vessel is then heated ^{to 180 ° C. with stirring.} The pressure is then brought to 62 bar with ethylene. The pressure is kept at 62 bar by adding a 1: 1 mixture of ethylene and carbon monoxide as required, and the temperature is kept at 180 ^° C. After one hour of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic acid at a rate of 1, 21 moles per liter per hour with all of the olefin converted having been converted to propionic acid.

example

A pressure vessel, stirred with a magnetic stirrer and lined with glass, is charged with 12 parts of water, 12 parts of ethyl iodide, 0.72 parts of nickel iodide (NiI ₂ ), 1.43 parts of molybdenum hexacarbonyl, 14 parts of lithium iodide and 60 parts of tetrahydrofuran as solvent. The vessel is flushed with argon, whereupon carbon monoxide is added up to an overpressure of 20.7 bar. The vessel is then heated ^{to 180 ° C. with stirring.} The pressure is then brought to 52 bar with ethylene. The pressure is kept at 52 bar by adding a 1: 1 mixture of ethylene and carbon monoxide, if necessary, and the temperature is maintained at 180 ^° C. After one hour of reaction, gas chromatography shows Analysis of the reaction mixture shows the formation of propionic acid at a rate of 4.63 moles per liter per hour, with all of the converted olefin having been converted to propionic acid.

Example 5

The procedure described in Example 4 is repeated except that the molybdenum hexacarbonyl is used here replaced by an equal amount of tungsten carbonyl. To After one hour of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic acid at a rate of 2.6 moles per liter per hour with all of the ethylene converted to propionic acid has been converted.

Example 6

The reaction vessel described in Example 1 is charged one with 11.4 parts of water, 11.4 parts of ethyl iodide, 0.7 parts of nickel iodide (Nil "), 1.4 parts of molybdenum hexacarbonyl, 18 parts of lithium iodide and 57 parts of tetrahydrofuran as solvents. The vessel is purged with argon,

on adding ethylene up to a pressure of 6.9 bar and then carbon monoxide up to a pressure of 41.4 bar. The vessel is then heated ^{to 180 ° C. with stirring.} The pressure is kept at 52 bar by adding a 1: 1 mixture of ethylene and carbon monoxide as required, and the temperature is kept at 180 ^° C. After 0.5 hours of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic acid with a Rate of 6.3 moles per liter per hour with all of the reacted ethylene converted to propionic acid.

Example 7

The reactor described in Example 1 is charged with 12 parts of water, 12 parts of ethyl iodide, 0.7 parts of nickel iodide, 1.4 parts of molybdenum hexacarbonyl, 14 parts of cesium iodide and 60 parts of tetrahydrofuran as solvents. That The reaction vessel is flushed with argon, whereupon it is first heated to a pressure of 6.9 bar and then with hydrogen.

Brings carbon monoxide to a pressure of 34.5 bar. The reaction vessel is then heated ^{to 180 ° C. with stirring.} The pressure is then increased to 62 bar with ethylene and kept at 62 bar by adding a 1: 1 mixture of ethylene and carbon monoxide as required. The temperature is maintained to 18O ⁰ C. After one hour of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic acid in a rate of 1.7 mole per liter per hour, where the entire unreacted ethylene has been converted into propionic acid.

■ Comparative example A

The procedure described in Example 2 is repeated with the exception that no molybdenum hexacarbonyl is added. After one hour of reaction, gas chromatographic analysis of the reaction mixture shows the formation of propionic acid at a rate of only _0.12 mol per liter and hour.

example

A pressure vessel, stirred with a magnetic stirrer and lined with glass, is charged with 68 parts of propionic acid, 12 parts of iodoethane, 0.8 part of nickel iodide, 1.6 parts of molybdenum hexacarbonyl and 16 parts of lithium iodide. The reaction vessel is flushed with argon, whereupon it is first brought to 6.9 bar with hydrogen and then to a pressure of 34.5 bar with carbon monoxide. The reaction vessel "is under R'ühren to 16O ⁰ C e" rhitzt and brought the pressure with ethylene to 55 bar. The pressure is kept at 55 bar by adding a 1: 1 mixture of ethylene and carbon monoxide, if necessary, and the temperature is maintained at 160 ^° C. After a reaction time of 50 minutes, gas chromatographic analysis of the reaction mixture shows the formation of propionic anhydride at one rate of 10 moles per liter and hour, all of the converted ethylene having been converted into propionic anhydride.

Example 9

A pressure vessel, stirred with a magnetic stirrer and lined with glass, is charged with 68 parts of propionic acid, 1.6 parts of molybdenum hexacarbonyl, 0.8 part of nickel iodide, 12 parts of ethyl iodide and 16 parts of lithium iodide. The reaction vessel is purged with argon, whereupon it. first, with hydrogen to 6.9 bar and then with carbon monoxide to a pressure of 34.5 bar. The reaction vessel is ^{heated to 180 °} C. with stirring and the pressure is brought to 52 bar with ethylene. The pressure is required, the addition of a 1: kept 1 mixture of ethylene and carbon monoxide at 52 bar and the Tempereitur is maintained at 180 ⁰ C. After a reaction time of 1 hour shows a gas chromatographic analysis of the reaction mixture, the formation of propionic anhydride at a rate of 7.1 mol per liter and hour, with all of the converted ethylene being converted into propionic anhydride

that is.

Example 10

° The process described in Example 8 is repeated with the exception that the reaction ^{temperature is kept at 140 0} C and the reaction time is 1 hour. A subsequent gas chromatographic analysis of the reaction mixture shows the formation of propionic anhydride at a rate of 3.2 mol per liter and hour, all of the converted ethylene having been converted to propionic anhydride.

Example 11.

The procedure described in Example 9 is repeated with the exception - that one - the molybdenum hexacarbonyl here, replaced by an equal amount of tungsten hexacarbonyl. After one hour of reaction, gas chromatography shows Analysis of the reaction mixture shows the formation of propionic anhydride at a rate of 1.8 moles per liter and hour during which all of the reacted ethylene has been converted to propionic anhydride.

Example 12

The procedure described in Example 9 is repeated with the exception that the lithium iodide is through a replaced equal amount of potassium iodide. After two hours of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic anhydride at a rate of 0.7 mol per liter per hour, all of the reacted ethylene having been converted to propionic anhydride.

Example 13

The procedure described in Example 9 is repeated except that the lithium iodide is replaced by a similar Amount of cesium iodide is replaced. After one hour of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of propionic anhydride at a rate of 1.9 mol per liter per hour, with all of the converted ethylene in propionic anhydride has been convicted.

Example 14

The procedure described in Example 9 is repeated with the ¹ Ausnähme that after the one hour reaction, no hydrogen is supplied. A subsequent gas chromatographic analysis of the reaction mixture shows the formation of propionic anhydride at a rate of 2.3 mol per liter and hour, all of the converted ethylene having been converted into propionic anhydride.

Comparative example B

The procedure described in Example 9 is followed with the exception of repeats that no lithium iodide is supplied. After one hour of reaction, gas chromatography shows Analysis of the reaction mixture shows the formation of propionic anhydride at a rate of only 0.2 mol per liter and hour.

Comparative Example C

The procedure described in Example 9 is repeated except that no molybdenum hexacarbonyl is added will. After one hour of reaction, gas chromatographic analysis of the reaction mixture shows the formation of Propionic anhydride at a rate of only 0.5 moles per liter per hour.

Example 15

In this example, a Parr bomb (Hastelloy) stirred with a magnetic stirrer and lined with glass used as a reaction vessel. You load the bomb with you Tetrahydrofuran (57 parts), ethyl iodide (12 parts), nickel iodide (0.68 parts), molybdenum hexacarbonyl (1.4 parts), lithium iodide (13.6 parts) and methanol (16 parts), whereupon they are flushed with argon and treated with carbon monoxide up to one

The reaction vessel is ^{heated to 180 °} C. with stirring and then brought to a pressure of 55 bar by adding ethylene. The pressure is increased by adding equal amounts of carbon monoxide and ethylene, if necessary kept at 55 bar, and the

^The temperature is kept at 18 0 ^° C. After 0.5 hours of reaction, a gas chromatographic analysis of the reaction mixture shows the formation of methyl propionate at a rate of 1.75 mol per liter and hour.

Example 16

The procedure described in Example 15 is repeated except that the molybdenum hexacarbonyl is through an equal amount of tungsten hexacarbonyl is replaced. A subsequent gas chromatographic analysis of the reaction mixture shows the formation of methyl propionate in one Speed of 0.55 moles per liter per hour.

Example 17

The procedure described in Example 15 is repeated except that the molybdenum hexacarbonyl replaced by an equal amount of chromium hexacarbonyl. A subsequent gas chromatographic analysis of the reaction mixture shows the formation of methyl propionate at a rate of 0.52 moles per liter per hour.

1 Comparative Example D.

The procedure described in Example 15 is repeated again, except that the molybdenum hexacarbonyl of the 5 omits loading. A subsequent gas chromatographic Analysis of the reaction mixture shows that no methyl propionate has formed.

Claims (5)

Ί Ί ^ ¹ SR "^:; π \ J vJ \ .Y \ J J »Y vj Case 1240A THE HALCON SD GROUP, INC. New York, N.Y., V.St.A. Process for producing a carboxylic acid, a carboxylic acid anhydride or a carboxylic acid ester Claims {ly ^: Process for the preparation of a carboxylic acid, a carboxylic acid anhydride or a carboxylic acid ester, by reacting an olefin with carbon monoxide in the presence of water, a carboxylic acid and / or an alcohol, in the presence of a halide and in the presence of a catalyst, characterized in that the catalyst consists of a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium-nickel-alkali metal cocatalyst component. 2. The method according to claim 1, characterized that the cocatalyst component consists of molybdenum-nickel-alkali metal. - ο - 3. The method according to claim 1, characterized in that the alkali metal is lithium is. 4. The method according to claim 3, characterized that the cocatalyst consists of molybdenum-nickel-lithium. 5. Liquid phase carbonylation catalyst, characterized in that it consists of a molybdenum-nickel-alkali metal, a tungsten-nickel-alkali metal or a chromium-nickel-alkali metal cocatalyst component and a halide component and has the following formula
15th X: T: Z: Q, where X is molybdenum, tungsten or chromium, T is nickel, X and T either in the zero-valent state or in the form a halide, oxide, carboxylate having 1 to 20 carbon atoms, carbonyl or hydride are present, Z is a halide source which is hydrogen halide, Halogen, an alkyl halide having 1 to 20 carbon atoms in the alkyl group, or an alkali metal halide, and Q is the alkali metal component and is in the form of a Iodide, bromide, chloride or carboxylate for X and T defined type is present, the molar ratio of X: T ranges from 0.1 to 10: 1, the molar ratio of X + T.: Q of 0.1 to 10: 1 ranges and the molar ratio of Z: X + T ranges from 0.01 to 0.1: 1.