JP2001512469A - Method for producing carboxylic acid or its ester by carbonylation of olefin - Google Patents

Abstract

  (57) [Summary] The present invention relates to a process for producing a carboxylic acid or its ester from an olefin and carbon monoxide in the presence of water or an alcohol at a temperature of 100 to 270 ° C. and a pressure of 30 to 100 bar, wherein the halogen-free catalyst system is used. A) nickel or a nickel compound; b) at least one metal of the group of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or compounds of these metals; c) Carboxylic acids or esters thereof, characterized in that a mixture of at least one non-metallic compound from the group of tertiary or quaternary nitrogen compounds, phosphorus compounds or arsenic compounds and nitrogen-containing heterocyclic compounds is used. And a method for producing the same.

Description

The invention relates to a process for the preparation of carboxylic acids or their esters by carbonylation of olefins. The invention relates to a catalyst system free of water or alcohol and halogen, nickel or nickel compounds, at least one noble metal or compounds thereof and For the production of carboxylic acids or their esters by reacting olefins with carbon monoxide at a pressure of 30 to 100 bar and 100 to 270 ° C. in the presence of a mixture of non-metallic nitrogen, arsenic or phosphorus compounds About the method. Weissermel et al., In Industrielle Organische Chemie, 1978, 2nd edition, Verlag Chemie, page 132, refer to the carbonylation of olefins by the Lepe method, for example ethylene, carbon monoxide in the presence of a catalyst. And the production of propionic acid from water. As catalyst, nickel propionate, which reacts under the reaction conditions to nickel carbonyl, is used. High conversions of ethylene are achieved only at high pressures (200-240 bar). These reaction conditions require high technical costs in the construction of suitable reactors as well as special and expensive materials, conditioned by the corrosive nature of the products under the reaction conditions. GB-A 1063617 teaches the carbonylation of olefins using nickel and cobalt catalysts in the presence of boric acid. This also requires high pressures and temperatures. The carbonylation of the olefin can be carried out using a noble metal catalyst at a pressure of about 100 bar. For example, EP-A-4955547 teaches a catalyst consisting of a source of palladium and a bidentate phosphine ligand. However, such catalysts often deactivate after a short reaction time due to the precipitation of metallic palladium. In particular, the phosphine ligands used are not thermostable under the desired reaction conditions. DE-A 44 24 710 describes the carbonylation of olefins using nickel or a mixture of a nickel compound and a noble metal or a noble metal compound as a catalyst system. However, the process described is still unsatisfactory in terms of selectivity and activity with respect to the product to be produced, especially at pressures below 100 bar. The problem therefore arises of avoiding the disadvantages mentioned above and of providing a process for the carbonylation of olefins at pressures below 100 bar with improved selectivity and activity. According to this task, the carboxylic acid is converted from the olefin and carbon monoxide in the presence of water or an alcohol and a halogen-free catalyst system at a temperature of 100 to 270 ° C. and a pressure of 30 to 100 bar, preferably 30 to 80 bar. Or a new and improved method for producing the ester thereof, characterized by the following: a) nickel or nickel compounds, b) chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, At least one metal of the group rhodium, iridium, palladium, platinum, silver, gold or compounds of these metals; c) tertiary or quaternary nitrogen compounds, phosphorus compounds or arsenic compounds and nitrogen-containing heterocyclic compounds A mixture of at least one non-metallic compound from the group of The activity and selectivity of the catalyst system described in DE-A 44 24 710 can be significantly improved with the process according to the invention, in particular at low pressures of less than 100 bar. Furthermore, the catalyst system used in the process according to the invention can be used for carboxylic acids which already have less than 1% of water in the reaction output, even at low water concentrations of 0.5 to 5 mol of water per mol of olefin. The activity is high enough to allow production, which greatly facilitates the work-up of the reaction product. The following reaction scheme illustrates the process according to the invention by taking the reaction of ethylene to propionic acid as an example: Catalyst CH ₂ = CH ₂ + CO + H ₂ O → CH ₃ CH ₂ COOH The process according to the invention Useful starting materials include aliphatic and cycloaliphatic alkenes having preferably 2 to 20, especially preferably 2 to 7, carbon atoms. Examples include ethylene, propylene, iso-butene, 1-butene, 2-butene and isomers of pentene and hexene and cyclohexene, of which ethylene is preferred. These olefins are reacted with water for the production of carboxylic acids or with alcohols for the production of carboxylic esters. These alcohols are preferably aliphatic and cycloaliphatic compounds having 1 to 20 carbon atoms, particularly preferably 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, Includes t-butanol, stearyl alcohol, diols such as ethylene glycol, 1,2-propanediol and 1,6-hexanediol, and cyclohexanol. When reacting the diol, monoesters and diesters are obtained, depending on the selected stoichiometric ratio, with the diol and olefin being used in a molar ratio of about 1: 2 for the production of the diester and of the monoester. The diol is used in excess for the preparation. The starting compound described above is reacted with carbon monoxide, which can be used in pure form or diluted with an inert gas such as nitrogen or argon. The molar ratio of the starting compound olefin to water or alcohol may vary depending on the choice, but usually at least an equimolar amount of water or alcohol is used. In the preparation of the carboxylic acid, 0.5 to 10 mol, preferably 0.5 to 5 mol, of water can be used per mol of olefin. The molar ratio of olefin to carbon monoxide may also vary significantly, with a molar ratio of olefin of 5: 1 to 1: 5 per mole of carbon monoxide being advantageous. In the process according to the invention, the halogen-free catalyst system comprises: a) nickel or a nickel compound; b) chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or a metal of these metals. Using a mixture consisting of at least one metal of the compound and c) at least one non-metallic compound from the group consisting of tertiary or quaternary nitrogen compounds, phosphorus compounds or arsenic compounds and nitrogen-containing heterocyclic compounds. . In order to be able to form active nickel compounds, it is advantageous to add to the reaction mixture soluble compounds, such as acetates, propionates, acetylacetonates, hydroxides and carbonates or mixtures of these compounds. . However, it is also possible to introduce Ni (CO) ₄ as well as nickel metal into the reaction mixture. With particular preference the nickel component is introduced in the form of a salt of the carboxylic acid formed during the reaction. As the second catalyst component, at least one metal from the group of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold, or a compound of these metals is used. However, rhodium and palladium are preferred, and ruthenium and platinum are particularly preferred. These metals can be introduced into the reaction solution, for example, as salts as described above for nickel, ie as acetates, propionates, acetylacetonates, hydroxides or carbonates. Further carbonyl compounds, in particular chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl, dirhenium decacarbonyl, tolyruthenium dodecacarbonyl, triosmium dodecacarbonyl and carbonyl compounds having another ligand, such as rhodium dicarbonylacetyl Acetonate or donor ligands such as phosphine, arsenic and nitrogen bases and metal compounds stabilized by olefins are relevant. Platinum can also be used as dibenzalacetone platinum. Ruthenium is preferably used as acetylacetonate. The metal is either dissolved or suspended in the reaction mixture depending on its solubility. The metals of the catalyst component b) or compounds of these metals can also be used on organic or inorganic inert supports, for example on activated carbon, graphite, aluminum oxide, zirconium oxide and silicon oxide. As third catalyst component, at least one non-metallic compound from the group of tertiary or quaternary nitrogen compounds, phosphorus compounds or arsenic compounds and nitrogen-containing heterocyclic compounds is used. Quaternary nitrogen compounds, phosphorus compounds or arsenic compounds are understood as quaternary ammonium salts, arsonium salts and phosphonium salts. As quaternary nitrogen compounds, arsenic compounds or phosphorus compounds, the third catalyst component c) is preferably of the general formula (I) Wherein E represents nitrogen, phosphorus or arsenic and X ⁻ represents a halogen-free anion, such as a nitrate ion or a hydroxide ion, but particularly preferably the carboxylic acid formed during the reaction. R ¹ , R ² , R ³ and R ⁴ represent anions of acids and are aliphatic groups, for example alkyls having preferably 1 to 18 carbon atoms and being straight-chain or branched Radicals, particularly preferably C ₁ -C ₈ -alkyl radicals, such as, for example, methyl, ethyl, n-propyl, n-butyl and octyl]. R ¹ , R ² , R ³ and R ⁴ are alicyclic groups such as cyclopentyl or cyclohexyl, aromatic groups substituted by aromatic groups such as phenyl or alkyl groups, such as tolyl or aromatic aliphatic groups, such as It may represent benzyl. As a tertiary nitrogen compound, a phosphorus compound or an arsenic compound, the third catalyst component c) is preferably of the general formula (II): Wherein E, R ¹ , R ² and R ³ represent those described in Formula I above. As the nitrogen-containing heterocyclic compound, pyridine, pyridine substituted with ₁ to ₄ carbon atoms, quinoline, isoquinoline, pyrimidine, pyridazine, pyrazine, pyrazole, imidazole, thiazole and oxazole are the third catalyst components c. Pyridine, pyridine, quinoline, isoquinoline, pyrimidine, pyridazine, pyrazine, pyrazole, imidazole, thiazole and oxazole, optionally monosubstituted by C ₁ -C ₄ -alkyl and N—C ₁ at nitrogen -C ₄ - or alkylated or _{N, N-C 1 ~C 4} - is dialkylated, halogen-free anion X ^- (in this case, X ^- represents one of the) these salts with Pyridine, N-methylpyridinium salt, imidazo And N, N- dimethyl imidazolinium salts. The molar ratio of nickel contained in the first component a) of the catalyst system to the second catalyst component b) is from 1: 1 to 100000: 1, preferably from 100: 1 to 50,000: 1. The content of catalytically active metals in the reaction solution of components a) and b), calculated as metals, amounts to a total of 0.1 to 5% by weight. The molar ratio of the nickel of component a) to the third nonmetallic catalyst component c) is generally between 2: 1 and 1:20, preferably between 1: 1 and 1:10. The content of nonmetallic catalyst component c) in the reaction solution is from 1 to 50% by weight. The reaction may be carried out with or without a solvent. Solvents such as acetone, ether, dioxane, dimethoxyethane, tetraethylene glycol dimethyl ether, aprotic polar solvents such as N-methylpyrrolidone and aromatic hydrocarbons such as toluene are suitable for this purpose. It is advantageous to carry out the reaction for preparing the carboxylic acid in 20 to 95% by weight, preferably 50 to 80% by weight, of aqueous carboxylic acid. The preparation of the carboxylic esters is carried out by the process according to the invention, preferably in the respective alcohols which may contain 1 to 5% by weight of water as solvent. When producing propionic acid, the use of aqueous propionic acid as solvent is advantageous. The reaction is usually carried out at from 100 to 270 ° C., preferably at from 170 to 250 ° C., and at a pressure of from 30 to 100 bar, preferably from 30 to 80 bar, particularly preferably from 40 to 60 bar. The starting olefin, water and the catalyst system may optionally be mixed in a solvent in a reactor before the reaction. They are then heated to the reaction temperature, the reaction pressure being adjusted by injection of carbon monoxide or, if short-chain olefins are used, by injection of a mixture of this olefin and carbon monoxide. Usually, the reaction is terminated after 0.5 to 3 hours. The reaction can be carried out continuously or intermittently in a reactor, for example a reactor, a bubble column, a tubular reactor or a reflux reactor. In an advantageous embodiment for the isolation of the process products, the reaction output is depressurized. The nickel carbonyl is then removed from the liquid by passing a gas, for example air or nitrogen, through. Nickel carbonyl can be separated off with an inert gas and worked up to give a nickel compound which can then be fed back into the reaction. The liquid phase of the reaction effluent which contains, besides the process product, a soluble or suspended catalyst, is worked up by distillation, the process product optionally being isolated after further rectification. The catalyst-containing distillation bottoms are re-fed to the reaction. It is likewise possible to refeed the catalyst components which have optionally been separated off as well as the volatile catalyst components which have been separated off as low-boiling substances or as a side stream of the distillation after a corresponding work-up. The process according to the invention enables the production of process products with high selectivity and high space-time yields. EXAMPLES Example 1 Intermittent Testing for Propionic Acid Production In a 300 ml autoclave with a magnetic stirrer, 2.13 g of basic nickel carbonate and 12 mg of acetylacetonatoruthenium in a mixture consisting of 90 g of propionic acid and 10 g of water. Was charged. Subsequently, 20 g of a 40% aqueous tetrabutylammonium hydroxide solution ([NBu ₄ ] OH) were added. Thereafter, the prepressure is adjusted to 30 bar with a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene, and the reaction solution is heated to 200 ° C. After reaching the reaction temperature, the final pressure is adjusted to 60 bar, and the CO / ethene gas mixture is held by a post-press for 15 minutes. After 1 hour, it was cooled to room temperature, depressurized and the reaction output was investigated by titration and gas analysis. The results are summarized in Table 1. Example 2 The test was carried out as described in Example 1. However, 10 g of triethylamine (NEt ₃ ) was used instead of tetrabutylammonium hydroxide. The results are clear from Table 1. Example A The test was carried out as described in Example 1, except that no nitrogen compound was added. The results are summarized in Table 1. Example B The test was carried out as described in Example 1, except that no ruthenium catalyst was used. The results are summarized in Table 1. Example C The test was carried out as described in Example 1, except that no nickel catalyst was added. The results are summarized in Table 1. RZA = space-time yield S = selectivity PS = propionic acid PA = propionaldehyde, by-product DEK = diethyl ketone, by-product% = weight percent In Examples 1 and 2 according to the invention, nickel, ruthenium and tetrahydroxide Using a catalyst consisting of butylammonium or triethylamine at 60 bar, it was possible to achieve a significantly higher space-time yield and selectivity than the comparative test A using both metal catalyst components alone. Comparative Examples B and C showed that the addition of tetrabutylammonium hydroxide to one of both catalyst metals did not result in an active catalyst system. Tests 1, 2, A and C show that the added nitrogen component particularly accelerates the carbonylation reaction, but significantly reduces the formation of by-products ethane, propionaldehyde and diethyl ketone. Example 3 Autoclave equipped with 2.13 g of basic nickel carbonate and 12 mg of acetylacetonatoruthenium in a mixture of 60 g of propionic acid and 40 g of a 40% aqueous solution of tetrabutylammonium hydroxide. did. Thereafter, the pre-pressure was adjusted to 30 bar using a gas mixture consisting of 50% by volume of C 2 O and 50% by volume of ethylene, and the reaction solution was heated to 200 ° C. After reaching the reaction temperature, the final pressure was adjusted to 75 bar and kept constant by continuous post-pressing of a gas mixture of CO / ethene. After 2 hours, it was cooled to room temperature, depressurized and the reaction output was investigated by titration and gas analysis. Table 2 summarizes the results. Example D The autoclave described in Example 3 was charged with a solution consisting of 2.13 g of basic nickel carbonate and 12 mg of acetylacetonatoruthenium in a mixture consisting of 60 g of propionic acid and 40 g of water. Thereafter, the pre-pressure was adjusted to 30 bar with a mixture consisting of 50% by volume of CO and 50% by volume of ethylene, and the reaction solution was heated to 200.degree. After reaching the reaction temperature, the final pressure was adjusted to 75 bar and kept constant by continuous post-pressing of a gas mixture of CO / ethene. After 2 hours, it was cooled to room temperature, depressurized and the reaction output was investigated by titration and gas analysis. The results are summarized in Table 2. Example 4 The test was carried out as described in example 3, except that the pressure was 55 bar. Table 2 summarizes the results. Example 5 The test was carried out as described in Example 3, but using 60 g of propionic acid, 25 g of a 40% aqueous solution of tetrabutylammonium hydroxide and 15 g of water as solvent and at a pressure of 55 bar. Table 2 summarizes the results. Example E The procedure was as described in Example D, except that the pressure was 55 bar. Table 2 summarizes the results. RZA = space-time yield S = selectivity PS = propionic acid PA = propionaldehyde, by-product DEK = diethyl ketone, by-product% = weight percent Example 6 80 g of propionic acid in a 300 ml autoclave with a magnetic stirrer And a solution consisting of 2.13 g of basic nickel carbonate and 12 mg of acetylacetonatoruthenium in 20 g of a 40% aqueous solution of tetrabutylammonium hydroxide ([H ₂ O] = 12 g). Thereafter, the pre-pressure was adjusted to 30 bar using a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene, and the reaction solution was heated to 200 ° C. After reaching the reaction temperature, the final pressure was adjusted to 100 bar and maintained by pressing after half an hour of the gas mixture of CO / ethene. After 2 hours, it was cooled to room temperature and depressurized. 126 g of liquid reaction product were obtained. According to analysis by gas chromatography and titration, the compositions summarized in Table 3 below were obtained. Example 7 A 300 ml autoclave with a magnetic stirrer was charged with a solution consisting of 2.13 g of basic nickel carbonate and 12 mg of acetylacetonatoruthenium in a mixture consisting of 90 g of propionic acid and 10 g of water and 10 g of triethylamine. Thereafter, the pre-pressure was adjusted to 30 bar using a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene, and the reaction solution was heated to 200 ° C. After reaching the reaction temperature, the final pressure was adjusted to 100 bar and maintained by pressing after half an hour of the CO / ethene gas mixture. After 2 hours, it was cooled to room temperature and depressurized. 134 g of a liquid reaction discharge were obtained. According to analysis by gas chromatography and titration, the compositions summarized in Table 3 below were obtained. From Examples 6 and 7, it is clear that catalyst systems consisting of nickel compounds, ruthenium compounds and nitrogen-containing compounds, such as triethylamine or tetrabutylammonium hydroxide, have a high activity even at very low water concentrations.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (72) Inventor Wolfgang Harder Germany D-69469 Weinheim Bergwaldstrasse 16 (72) Inventor Ferdinand Rippert Germany D-67098 Bad Durkheim Welsling 16

Claims (1)

[Claims] 1. In a process for producing carboxylic acids or their esters from olefins and carbon monoxide in the presence of water or alcohol at a temperature of 100 to 270 ° C. and a pressure of 30 to 100 bar, halogen-free in the absence of a fixed bed of activated carbon. As catalyst systems comprising: a) nickel or nickel compounds b) at least one of the group of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or compounds of these metals Metal, c) a carboxylic or tertiary or quaternary nitrogen compound, a phosphorus compound or an arsenic compound and a mixture comprising at least one non-metallic compound from the group of the nitrogen-containing heterocyclic compounds. A method for producing an acid or an ester thereof. 2. 2. The process for preparing a carboxylic acid or its ester according to claim 1, wherein the components of the catalyst system are present in a): b): c) molar ratio of 1: 1: 0.5 to 10,000: 1: 200,000. 3. The catalyst system has the general formula (I): [Wherein E represents nitrogen, phosphorus or arsenic, R ¹ , R ² , R ³ and R ⁴ represent an aliphatic, alicyclic, aromatic aliphatic or aromatic group, and X ⁻ Represents a halogen-free anion.] The method for producing a carboxylic acid or an ester thereof according to claim 1 or 2, wherein 4. The catalyst system has the general formula (II): Wherein E represents nitrogen, phosphorus or arsenic, and R ¹ , R ² and R ³ represent an aliphatic, alicyclic, aromatic aliphatic or aromatic group. The method for producing a carboxylic acid or an ester thereof according to any one of claims 1 to 3, further comprising a compound. 5. The method for producing a carboxylic acid or an ester thereof according to claim 1 or 2, wherein the content of the nonmetallic compound c) in the reaction solution is 1 to 50% by weight. 6. The method for producing a carboxylic acid or an ester thereof according to any one of claims 1 to 5, wherein the reaction solution contains 0.5 to 10 mol of water per 1 mol of the olefin. 7. The process for producing a carboxylic acid or an ester thereof according to claim 1, wherein the reaction is carried out at a temperature of 170 ° C. to 250 ° C. and a pressure of 40 to 60 bar. 8. The method for producing a carboxylic acid or an ester thereof according to any one of claims 1 to 7, wherein carbon monoxide and an olefin are used in a molar ratio of 5: 1 to 1: 5. 9. The method for producing a carboxylic acid or an ester thereof according to any one of claims 1 to 7, wherein ethylene is used as the olefin.