CN1250432A - Method for producing carboxylic acids or their esters by carbonylation of olefins - Google Patents

Method for producing carboxylic acids or their esters by carbonylation of olefins Download PDF

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CN1250432A
CN1250432A CN98803397A CN98803397A CN1250432A CN 1250432 A CN1250432 A CN 1250432A CN 98803397 A CN98803397 A CN 98803397A CN 98803397 A CN98803397 A CN 98803397A CN 1250432 A CN1250432 A CN 1250432A
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carboxylic acid
compound
preparing
catalyst system
nitrogen
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M·施阿弗
A·霍恩
W·哈德
F·利伯特
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0239—Quaternary ammonium compounds
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0255—Phosphorus containing compounds
    • B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/20—Carbonyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates

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Abstract

The invention relates to a method for producing carboxylic acids or their esters from olefins and carbon monoxide in the presence of water or alcohols at temperatures of between 100 and 270 DEG C and pressure of between 30 and 100 bar. Said method is characterized in that as halogen-free catalyst system it uses a mixture of a) nickel or a nickel compound; b) at least one of the metals of a group including chromium, molybdenum, wolfram, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, or a compound of these metals; c) at least one non-metallic compound from the group of tertiary or quaternary nitrogen, phosphorus or arsenic compounds and nitrogen-containing heterocyclic compounds.

Description

Process for preparing carboxylic acids or esters by carbonylation of olefins
The invention relates to a process for preparing carboxylic acids or carboxylic esters by reacting olefins with carbon monoxide in the presence of water or alcohol and a halogen-free catalyst system (nickel or nickel compounds, mixtures of at least one noble metal or compound thereof and a nonmetallic nitrogen, arsenic or phosphorus compound) at 30 to 100bar and 100 to 270 ℃.
Weissermel et al describe in industrial organic chemistry (second edition, 1978, chemical Press, page 132) the carbonylation of olefins by the Reppe process, for example the preparation of propionic acid from ethylene, carbon monoxide and water in the presence of a catalyst. Nickel propionate acts as a catalyst, which is converted to nickel carbonyl under the reaction conditions. High ethylene conversions were obtained only at high pressures (200-240 bar). These reaction conditions entail high technical requirements in a suitable reactor configuration and require special and expensive materials due to the corrosive nature of the products under the reaction conditions.
GB-A1063617 discloses the carbonylation of olefins with nickel and cobalt catalysts in the presence of boric acid. High pressures and temperatures are also necessary in this case.
The carbonylation of olefins can be carried out using a noble metal catalyst at a pressure of about 100 bar. Thus, EP-A14995547 discloses catalysts composed of ligands derived from palladium and bidentate phosphines. However, catalysts of this type are frequently deactivated after a short reaction time by the deposition of metallic palladium, and in particular the phosphine ligands used are not thermally stable under the desired reaction conditions.
DE-A4424710 describes the carbonylation of olefins using a nickel or nickel compound and a noble metal or noble metal compound as the catalyst system. However, this process is still not satisfactory in terms of selectivity and activity of the products prepared, in particular at pressures lower than 100 bar.
The object of the present invention is to provide a process for the carbonylation of olefins which does not have the above-mentioned disadvantages and which is improved in terms of selectivity and activity at pressures of up to 100 bar.
We have found that this object is achieved by a novel and improved process for preparing carboxylic acids or carboxylic esters from olefins and carbon monoxide in the presence of water or alcohols and in the presence of a halogen-free catalyst system at from 100 to 270 ℃ and from 30 to 100bar, preferably from 30 to 80 bar. The method comprises the following steps of adopting a mixture of a, b and c as a catalyst system:
a) nickel or a nickel compound,
b) at least one metal selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or a compound of one of these metals,
c) at least one non-metallic compound selected from the group consisting of trivalent or tetravalent nitrogen, phosphorus or arsenic compounds and nitrogen-containing heterocyclic compounds.
Compared with the catalyst system described in DE-A4424710, the activity and selectivity can be greatly increased by the process of the invention, in particular at low pressures of up to 100 bar. In addition, the catalyst system of the process according to the invention is highly active, even at low water contents of 0.5 to 5mol of water per mole of olefin, so that carboxylic acids having a water content of less than 1% in the reaction output can be prepared, which greatly simplifies the treatment of the reaction products.
The following reaction equation shows the process according to the invention in the case of an example of an implementation of the conversion of ethylene to propionic acid:
suitable starting materials for the process according to the invention are aliphatic and cycloaliphatic alkenes, preferably having from 2 to 20 carbon atoms, particularly preferably from 2 to 7. Examples which may be mentioned are the isomers of ethylene, propylene, isobutene, 1-butene, 2-butene, pentene and hexene; and cyclohexene, of which ethylene is preferred.
These olefins are reacted with water to produce carboxylic acids or with alcohols to produce carboxylic acid esters. These alcohols include aliphatic and cycloaliphatic compounds, which preferably have from 1 to 20 carbon atoms, particularly preferably from 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, octadecanol, glycols, such as ethylene glycol, 1, 2-propanediol and 1, 6-hexanediol, and cyclohexanol. If reacted with a diol, monoesters and diesters can be obtained, depending on the chosen stoichiometric ratio, with diesters being prepared with a molar ratio of diol to olefin of about 1: 2, and monoesters being prepared with an excess of diol.
The starting compounds are reacted with carbon monoxide, which may be pure or diluted with an inert gas such as nitrogen or argon.
The molar ratio of olefin to water or alcohol starting compound can vary within wide limits but generally at least equimolar amounts ofwater or alcohol are used. In the production of the carboxylic acid, 0.5 to 10mol, preferably 0.5 to 5mol of water per mol of olefin may be used.
The molar ratio of olefin to carbon monoxide may also vary widely, with a preferred molar ratio being from 5: 1 to 1: 5 moles of olefin per mole of carbon monoxide.
The halogen-free catalyst used in the process of the invention is a mixture of a, b and c
a) Nickel or a nickel compound,
b) at least one metal selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or a compound of one of these metals,
c) at least one non-metallic compound selected from the group consisting of trivalent or tetravalent nitrogen, phosphorus or arsenic compounds and nitrogen-containing heterocyclic compounds.
In order that the active nickel compounds may be formed, it is expedient to add to the reaction mixture compounds which are soluble therein, such as acetates, propionates, acetylacetonates, hydroxides and carbonates or mixtures of these compounds. However, it is also possible to add Ni (CO) to the reaction mixture4And metallic nickel. Particular preference is given to adding the nickel component in the form of a salt of the carboxylic acid formed in the reaction.
The second catalyst component used is at least one metal or one compound of these metals selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver and gold, with rhodium, palladium and ruthenium and platinum being particularly preferred. These metals are added to the reaction solution, for example, as the salts provided above for nickel, i.e. as acetates, propionates, acetylacetonates,hydroxides or carbonates. Carbonyl compounds are also suitable, in particular chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl, rhenium decacarbonyl, ruthenium dodecacarbonyl, osmium dodecacarbonyl and carbonyl compounds with other ligands, such as rhodium dicarbonyl acetylacetonate, or metal compounds stabilized by electron-donating ligands, such as phosphine, arsenic and nitrogen radicals and olefins. Platinum is also used as platinum dibenzylideneacetone. Ruthenium is preferably used as acetylacetonate. These metals are present in the reaction mixture as a solution or as a suspension, depending on the relative solubility properties. The metals or compounds of these metals in the catalyst component b) may also be used on inert organic or inorganic supports such as activated carbon, graphite, alumina, zirconia and silica.
The third catalyst component used is at least one non-metallic compound selected from the group consisting of trivalent or tetravalent nitrogen, phosphorus or arsenic compounds and nitrogen-containing heterocyclic compounds.
Quaternary nitrogen, phosphorus or arsenic compounds are quaternary ammonium, arsonium and phosphonium salts.
The third catalyst component c) preferably contains a compound of the formula (I) as a quaternary nitrogen, arsenic or phosphorus compound:
Figure A9880339700071
wherein E is nitrogen, phosphorus or arsenic, X-Is a halogen-free anion such as nitrate or hydroxide, but preferably the anion of the carboxylic acid formed in the reaction, R1，R2，R3And R4Are aliphatic radicals such as alkyl radicals, preferably having 1 to 18 carbon atoms and being linear or branched, particularly preferably C1～C8Alkyl groups such as methyl, ethyl, n-propyl, n-butyl and octyl.
R1，R2，R3And R4It may also be a cycloaliphatic group such as cyclopentyl or cyclohexyl, an aryl group such as phenyl or an alkyl-substituted aryl group such as tolyl, or an araliphatic group such as benzyl.
The third catalyst component c) preferably contains a compound of the formula (II) as trivalent nitrogen, phosphorus or arsenic compound:
wherein, E, R1，R2And R3Has the meaning indicated by the formula (I) above.
Suitable nitrogen-containing heterocyclic compounds as third catalyst component C) are pyridine, mono-to tri-C1～C4Alkyl-substituted pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazines, pyrazoles, imidazoles, thiazoles and oxazoles, preferably unsubstituted or mono-C1-C4Alkyl-substituted pyridines, quinolines, isoquinolines, pyrimidines, pyridazines, pyrazoles, imidazoles, thiazoles and oxazoles, and their N-C with non-halogen anions1～C4By alkylation or N, N-C1～C4Dialkylated X-salts, in which X-has the meaning indicated above, are preferably pyridine, N-methylpyridinium, imidazole and N, N-dimethylimidazolium salts.
The molar ratio of nickel contained in the first component a) to the second component b) of the catalyst system is 1: 1 to 100,000: 1, preferably 100: 1 to 50,000: 1. The total content of the catalytically active metals in components a) and b) in the reaction solution is 0.1 to 5% by weight, calculated as metal. The molar ratio of nickel in component a) to the third non-metallic catalyst component c) is generally from 2: 1 to 1: 20, preferably from 1: 1 to 1: 10. The content of the non-metal catalyst component c) in the reaction solution is 1to 50% by weight.
The reaction can be carried out without solvent or with solvent. Solvents suitable for this purpose are, for example, acetone, ethers, dioxane, dimethoxyethane, tetraethyleneglycol dimethyl ether, aprotic polar solvents such as N-methylpyrrolidone and aromatic hydrocarbons such as toluene. Preferably, the reaction produces 20 to 95 wt% aqueous carboxylic acid solution, preferably 50 to 80 wt%.
The preparation of carboxylic esters by the process of the invention is preferably carried out in a solvent which is a suitable alcohol and contains from 1 to 5% by weight of water.
Preferably, the propionic acid is prepared using aqueous propionic acid as solvent.
The reaction is usually carried out at 100 to 270 ℃, preferably 170 to 250 ℃ and 30 to 100bar, preferably 30 to 80bar, particularly preferably 40 to 60 bar.
The olefin and water starting components are mixed in a reactor with or without solvent prior to reaction with the catalyst system. Followed by heating to reaction temperature, adjusting the reaction pressure by injecting carbon monoxide or, when short chain olefins are used, by injecting a mixture of such olefins and carbon monoxide.
The reaction is generally completed after 0.5 to 3 hours. The reaction can be carried out continuously or batchwise in reactors such as reaction tanks, bubble columns, tubular reactors or circulating reactors.
The product of the process is in a preferred embodiment separated off by the discharge from the pressure-release reaction. The nickel carbonyl is then removed from the liquid by passing a gas, such as air or nitrogen. The nickel carbonyl can be separated from the inert gas and processed to a nickel compound, which can then be returned to the reaction. The liquid phase in the reaction output contains, in addition to the product of the process, dissolved or suspended catalyst which is separated off by distillation and, if necessary, is subsequently rectified. The bottom product containing the catalyst after distillation is returned to the reaction. Also, if necessary, the catalyst component separated before the distillation and the volatile catalyst component separated as a low boiling substance or as a by-product stream in the distillation are recycled after the respective treatments.
The process of the invention allows the preparation of products with high space-time yields and high selectivities.
Example (b): example 1: batch experiments for the preparation of propionic acid
A solution of 2.13g of basic nickel carbonate and 12mg of ruthenium acetylacetonate in a mixture of 90g of propionic acid and 10g of water was introduced into a 300ml reaction vessel equipped with a magnetic stirring bar. 20g of a 40% strength tetrabutylammonium hydroxide solution ([ NBu]s) were subsequently added4]OH). Then a starting pressure of 30bar was set with a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene and the reaction solution was heated to 200 ℃. After the reaction temperature was reached, the final pressure was set at 60bar and this pressure was maintained by injecting the CO/ethylene gas mixture every 15 minutes. After 1 hour, the mixture is cooled to room temperature and the pressure is released, the reaction is dischargedTitration and gas analysis. The results are shown in Table 1. Example 2
The experiment was performed as described in example 1, but with 10g of triethylamine instead of tetrabutylammonium hydroxide. The results are shown in Table 1. Example A
The experiment was carried out as described in example 1, but no nitrogen compound was added. The results are shown in Table 1. Example B
The experiment was carried out as described in example 1, but without the ruthenium catalyst. The results are shown in Table 1. Example C
The experiment was carried out as described in example 1, but without the nickel catalyst. The results are shown in Table 1.
TABLE 1
Examples Ni [mmol] Ru [mmol] Alkali [mmol] STY(PA) [g/l/h] S(PA) [％] Ethane (III) [l/h] S (ethylene) [％] S(P) [％] S(DEK) [％]
1 17 0.03 30 [NBu4]OH 137 81 0.8 15 1.4 0.5
2 17 0.03 86 NET3 165 83 1.0 16 - -
A 17 0.03 - 20 40 0.9 30 1.4 0.5
B 17 30 [NBu4]OH - - 0.2 65 11 24
C 0.03 30 [NBu4]OH 2 6 0.8 33 9 14
Space-time yield (STY)
S ═ selectivity
PA ═ propionic acid
P ═ propionaldehyde, by-product
DEK ═ acetone, by-product
Percent by weight
In examples 1 and 2 according to the invention, significantly higher space-time yields and selectivities were achieved at 60bar with catalysts consisting of nickel, ruthenium and tetrabutylammonium hydroxide or triethylamine than in comparative experiment A with only two metal catalyst components. Comparative experiments B and C show that the addition of tetrabutylammonium hydroxide to one of the two catalyst metals does not form an active catalyst system. Experiments 1, 2, a and C show that the addition of nitrogen-containing components accelerates the carbonylation reaction in particular, and that less ethane, propionaldehyde and acetone are formed as by-products. Example 3
A solution of 2.13g of basic nickel carbonate and 12mg of ruthenium acetylacetonate in a mixture of 60g of propionic acid and 40g of 40% strength aqueous tetrabutylammonium hydroxide solution is introduced into a 300ml reaction vessel (1000rpm) having an air-filled stirrer. The starting pressure was set to 30bar with a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene and the reaction solution was heated to 200 ℃. After the reaction temperature was reached, the final pressure was set to 75bar and the pressure waskept constant by continuously injecting the CO/ethylene gas mixture. After two hours, the mixture was cooled to room temperature and the pressure was released and the reaction discharge was analyzed by titration and gas analysis. The results are shown in Table 2.
Example D
In the reaction vessel described in example 3, 2.13g of basic nickel carbonate and 12mg of ruthenium acetylacetonate in a mixture of 60g of propionic acid and 40g of water and a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene were charged to an initial pressure of 30bar and the reaction solution was heated to 200 ℃. After the reaction temperature was reached, the final pressure was adjusted to 75bar and kept constant by continuously injecting the CO/ethylene gas mixture. After two hours, the mixture was cooled to room temperature and the pressure was released and the reaction discharge was analyzed by titration and gas analysis. The results are shown in Table 2.
Example 4
The experiment was carried out as described in example 3, but at 55 bar. The results are shown in Table 2. Example 5
The experiment was carried out as described in example 3 but with 60g of propionic acid, 25g of 40% strength aqueous tetrabutylammonium hydroxide solution and 15g of water as solvent and at a pressure of 55 bar. The results are shown in Table 2. Example E
The experiment was carried out as described in example D but at a pressure of 55 bar. The results are shown in Table 2.
TABLE 2
Examples P [bar] Ni [mmol] Ru [mmol] Alkali [mmol] STY(PA) [g/l/h] S(PA) [％] Ethane (III) [l/h] S (ethylene) [％] S(P) [％] S(DEK) [％]
3 75 17 0.03 60 [NBu4]OH 349 95 0.4 2.4 0.6 0.6
D 75 17 0.03 - 133 91 0.3 5.1 0.8 1.1
4 55 17 0.03 60 [NBu4]OH 176 90 0.6 6.8 0.6 0.4
5 55 17 0.03 370 [NBu4]OH 208 92 0.5 5.2 0.5 -
E 55 17 0.03 - 86 85 0.3 8.9 0.5 0.4
Space-time yield (STY)
S ═ selectivity
PA ═ propionic acid
P ═ propionaldehyde, by-product
DEK ═ acetone, by-product
Percent by weight
Example 6
In 80g of propionic acid and 20g of 40% strength aqueous tetrabutylammonium hydroxide solution ([ H]2O]12g) was added to a 300ml reaction kettle equipped with a magnetic stir bar. The starting pressure was set to 30bar with a gas mixture consisting of 50% by volume of CO and 50% by volume of ethylene and the reaction solution temperature was heated to 200 ℃. To achieve the inverseAfter the temperature was applied, the final pressure was set to 100bar and the pressure was kept constant by injecting the CO/ethylene gas mixture every half hour. After two hours, the mixture was cooled to room temperature and the pressure was released. 126g of liquid reaction output were obtained from the reaction. Chromatographic and titrimetric analysis revealed the composition and the results are given in table 3.
Example 7
A solution of 2.13g of basic nickel carbonate and 12mg of ruthenium acetylacetonate in a mixture of 90g of propionic acid and 10g of water and 10g of triethylamine is introduced into a 300ml reaction vessel equipped with a magnetic stirrer bar. The starting pressure was set to 30bar with a gas mixture of 50% by volume CO and 50% by volume ethylene and the reaction temperature was heated to 200 ℃. After the reaction temperature was reached, the final pressure was set at 100bar and kept constant by injecting the CO/ethylene gas mixture every half hour. After two hours, the mixture was cooled to room temperature and the pressure was released. 134g of liquid reaction output were obtained from the reaction. Gas chromatography and titration analysis revealed the composition, and the results are listed in table 3.
TABLE 3
Examples P [bar] Ni [mmol] Ru [mmol] Alkali [mmol] STY(PA) [g/l/h] PA [％] P [％] DEK [％] H2O
6 100 17 0.03 30 [NBu4]OH 152 87.5 0.2 0.2 2.1
7 100 17 0.03 86 NEt3 157 90.7 0.1 0.2 ＜0.1
Examples 6 and 7 show that catalyst systems consisting of a nickel compound, a ruthenium compound and a nitrogen-containing compound such as triethylamine or tetrabutylammonium hydroxide have a high activity even at very low water contents.

Claims (11)

1. A process for preparing carboxylic acids or carboxylic acid esters from olefins and carbon monoxide in the presence of water or alcohols at from 100 to 270 ℃ and from 30 to 100bar, which comprises using as halogen-free catalyst system a mixture of a, b and c:
a) nickel or a nickel compound,
b) at least one metal selected from the group consisting of chromium, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or a compound of one of these metals,
c) at least one non-metallic compound selected from the group consisting of trivalent or tetravalent nitrogen, phosphorus or arsenic compounds and nitrogen-containing heterocyclic compounds.
2. A process for preparing a carboxylic acid or ester according to claim 1 wherein the catalyst system components are present in a molar ratio of a) to b) to c) of from 1: 0.5 to 100,000: 1: 200,000.
3. A process for preparing a carboxylic acid or ester according to claim 1 or 2, wherein the catalyst system comprises a tetravalent compound of formula (I):wherein E is nitrogen, phosphorus or arsenic, R1，R2，R3And R4Is an aliphatic, cycloaliphatic, araliphatic or aromatic radical, X-Is a halogen-free anion.
4. A process for preparing a carboxylic acid or ester according to any one of claims 1 to 3 wherein the catalyst system comprises a trivalent compound of formula (II):
Figure A9880339700022
wherein E is nitrogen, phosphorus or arsenic, R1，R2And R3Is an aliphatic, cycloaliphatic, araliphatic orAn aromatic group.
5. A process for producing a carboxylic acid or a carboxylic acid ester as claimed in claim 1 or 2, wherein the content of the non-metal compound in the reaction solution is 1 to 50% by weight.
6. A process forproducing a carboxylic acid or a carboxylic acid ester as claimed in any one of claims 1 to 5, wherein the reaction solution contains 0.5 to 10mol of water per mol of the olefin.
7. A process for preparing a carboxylic acid or ester according to any one of claims 1 to 6 wherein the reaction is carried out at from 170 to 250 ℃ and from 40 to 60 bar.
8. A process for preparing a carboxylic acid or ester according to any one of claims 1 to 7 wherein the carbon monoxide and olefin are used in a molar ratio of from 5: 1 to 1: 5.
9. A process for preparing a carboxylic acid or ester according to any one of claims 1 to 7 wherein the olefin used is ethylene.
10. Halogen-free catalyst system, as defined in at least one of claims 1 to 4, suitable for carrying out the process for preparing hydroxy acids or carboxylic esters according to at least one of claims 1 to 9.
11. Use of a catalyst system as defined in at least one of claims 1 to 4 for the preparation of carboxylic acids or carboxylic acid esters from olefins and carbon monoxide in the presence of water or alcohols.
CN98803397A 1997-02-21 1998-02-09 Method for producing carboxylic acids or their esters by carbonylation of olefins Pending CN1250432A (en)

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US4257973A (en) * 1971-11-05 1981-03-24 E. I. Du Pont De Nemours And Company Process of making acids or esters from unsaturated compounds
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KR20000075494A (en) 2000-12-15

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