CA1258469A - Process for the joint manufacture of carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid esters - Google Patents
Process for the joint manufacture of carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid estersInfo
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- CA1258469A CA1258469A CA000486571A CA486571A CA1258469A CA 1258469 A CA1258469 A CA 1258469A CA 000486571 A CA000486571 A CA 000486571A CA 486571 A CA486571 A CA 486571A CA 1258469 A CA1258469 A CA 1258469A
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- Prior art keywords
- iodide
- mol
- carboxylic
- general formula
- acid esters
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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
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- 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
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
PROCESS FOR THE JOINT MANUFACUTRE OF CARBOXYLIC ACIDS, CARBOXYLIC ANHYDRIDES AND, IF DESIRED, CARBOXYLIC ACID
ESTERS
ABSTRACT OF THE DISCLOSURE:
Carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid esters of the general formulae RCOOH, RCOOCOR and RCOOR, respectively, in which R each time stands for one and the same alkyl radical having from 1 to 4 carbon atoms, are produced jointly. To this end, dialkyl ether of the general formula ROR is react-ed at temperatures of 50 to 250°C and under pressures of 0.1 to 120 bars, with an alcohol of the general for-mula ROH in a molar ratio of 9 : 1 to 1 : 9 under an-hydrous conditions, with carbon monoxide and, if desir-ed, hydrogen in the presence of a catalyst system con-sisting of carbonyl complexes of noble metals belonging to group VIII of the Periodic System; an alkali metal iodide, organophosphonium iodide or organoammonium iodide; an alkyl iodide of the general formula RI; and, if desired, compounds of carbonyl-yielding non-noble metals belonging to groups IV, V, VI, VII or VIII of the Periodic system.
ESTERS
ABSTRACT OF THE DISCLOSURE:
Carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid esters of the general formulae RCOOH, RCOOCOR and RCOOR, respectively, in which R each time stands for one and the same alkyl radical having from 1 to 4 carbon atoms, are produced jointly. To this end, dialkyl ether of the general formula ROR is react-ed at temperatures of 50 to 250°C and under pressures of 0.1 to 120 bars, with an alcohol of the general for-mula ROH in a molar ratio of 9 : 1 to 1 : 9 under an-hydrous conditions, with carbon monoxide and, if desir-ed, hydrogen in the presence of a catalyst system con-sisting of carbonyl complexes of noble metals belonging to group VIII of the Periodic System; an alkali metal iodide, organophosphonium iodide or organoammonium iodide; an alkyl iodide of the general formula RI; and, if desired, compounds of carbonyl-yielding non-noble metals belonging to groups IV, V, VI, VII or VIII of the Periodic system.
Description
lZS8469 HOE 84/H 021 This invention relates to a process for the joint manu-facture of carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid esters, especially acetic acid, acetic anhydride and optionally methyl acetate.
Acetic acid and acetic anhydride belong to the most im-portant aliphatic intermediates, and are predominantly used for making vinyl acetate or cellulose acetate.
Heretofore, acetic acid has almost exclusively been made by oxidizing acetaldehyde, alkanes or alkenes, but pro-cesses for making acetic acid by subjecting methanol to car-bonylation have recently been galning increasing interest.
German Specification DE 17 67 151 C3, for example, describes a process for making carboxylic acids andtor their esters by subjecting a saturated aliphatic alcohol having from 1 to 20 carbon atoms or a halogenated derivative or ester or ether derivative thereof, or phenol to a catalytic conversion re-action, the feed materials aForesaid being reacted with car-bon monoxide under a CO-partial pressure of 0.34 to 207 bar either in liquid phase at 100 to 240C or in gas phase at 200 to 400C in the presence of a rhodium compound and of bromine, iodine or a compound of these halogenes and also in the presence of water, in the event of a halogenated deriva-tive, ester or ether derivative of an alcohol being used.
Heretofore, acetic anhydride has predominantly been made either by reacting acetic acid with a ketene or by subject-ing acetaldehyde to a modified oxidation. More recent routes - have been described in German Specification DE-OS 24 41 502, wherein a carboxylate ester or hydrocarbon ether is reacted with an acyl iodide or bromide under practically anhydrous conditions. The acyl halide is prepared by subjecting an lZ58469 alkyl halide to carbonylation in the presence of a catalyst system formed of a nob.le metal belonging to group VIII of the Periodic System and, optionally, a promQter selected from groups Ia, IIa, IIIa, IVb, VIb, non-noble metals of group VIII, and metals of the lanthanides and actinides of the Periodic System.
German Specification DE 24 5û 965 C2 describes a pro-ces.s For making acetic anhydride by reacting methyl acetate or a methyl acetate/dimethylether-mixture with carbon mon-oxide under pressures of l to 500 bar and at temperaturesof 50 to 250C in the absence of significant proportions of water and in the presence of catalysts containing noble me-tals belonging to the 8th subgroup of the Periodic System or their compounds, iodine and/or iodine compounds and optionally carbonyl-yielding metals, the reaction being ef-fected in the presence of catalysts which additionally con-tain an alkyl or aryl phosphine and/or an organic nitrogen compound, and optionally in the presence of 5 to 50 volume ~O
hydrogen. The feed materials which are preferentially used are methyl acetate/methanol-mixtures containing 18 to 20 ~O
methanol.
A further process for the joint manuFacture of acetic acid and acetic anhydride has been described in ~uropean Specification EP 00 87 869 Al, wherein a carboxylic acid ester or ether, water and optionally an alcohol are reacted with carbon monoxide in the presence of a catalyst consist-ing of a noble metal belonging to group VIII of the Periodic System, a bromine or iodine promoter, and a copromoter form-ed of a Lewis base or a non-noble metal, to give a mixture of carboxylic acid and carboxylic anhydride, the feed ~2~i8469 mixture containing at least 5.5 weight O water. As regards the total quantity of water and alcohol, it is not allowable for it to exceed 85 O oF the stoichiometric quantity of ester and ether.
Reaction mixtures such as those just described which in addition to acetic acid contain reactive iodine compounds and also water have, however, h.igh corrosiveness for most materials used in industry, including Hastelloy stainless steels, so that it is invariably necessary for these mate-rials to be replaced by expens.i\/e substitutes, e.g. tanta-lum.
It is possible for this dlsadvantage to be set aside by using an anhydrous mixture of dimethylether and methanol readily available in sufficient quantities from substantial-- ly all methanol producers. As has unexpectedly been found, the reaction mixture has con~sidsrably less cnrroslvenes.s in a those cases in which the reaction is effected under anhy-drous conditions. In this case the aCt.iVi.t.Y nf the catalyst re-lative to the entirety of products is at least preserved or even improved, compared with operation in the presence of water. Besides the possibility of adapting the carboxylic acid/carboxylic anhydride-product ratio to commercial requi-rementS,the present process provides for the corresponding carboxylic acid ester to be made as a further commercial product.
The present invention provides more particularly a process for the joint manufacture of carboxylic acids, carb-oxylic anhydrides and, if desired, carboxylic acid esters of }n the general formulae RCOOH, RCOOCOR and RCOOR, respectively, lZS84~i9 in which R each time stands for one and the same alkyl radi-cal having from 1 to 4 carbon atoms, which comprises: react-ins at temperatures of 50 to 250C and under pressures of D.1 to 120 bars, a dialkyl ether of the general formula ROR with an alcohol of the general formula ROH in a molar ratio of 9 :
.
1 to 1 : 9 under anhydrous conditions, with carbon monoxide and, if desired, hydrogen in -the presence of a catalyst sy-.stem consisting of carbonyl complexes of noble metals be-longing to group VIII of the Periodic System; an alkali me-tal iodide, organophosphonium iodide or organoammonium iodi-de; an alkyl iodide of the general formula RI; and, if desi-; red, compounds of carbonyl-yielding non-noble metals belong-ing to groups IV, V, VI, VII or VIII of the Periodic system.
In this way, it is possible to produce acetic acid, acetic anhydride and optionally methyl acetate from dime-thylether, methanol and methyl iodide, for example. The car-bon monoxide used may contain up to lû volume ~ hydrogen.
By varying the dialkylether/alcohol- feed ratio, it is possible to establish practically any desirable product ra-tio.of carboxylic acid/carboxylic anhydride. This is a spe-~ cial advantage of the present invention permitting the pro-; cess to be rapidly acted upon in accordance with require-ments.
It is not absolutely necessary for pure carbon monoxide to be used in the reaction. Relativaly small amounts of inert gas, such as carbon dioxide, nitrogen or methane could not be found to affect the carbonylation provided that the CO-partial pressure inside the reactor is kept constant. A
hydrogen content of up to lû O has even been found positive-3 ly to add to the catalyst activity but to reduce the selec-lZS8469 tivity of the process by the formation of hydrogenation pro-ducts, e.g. ethylidene diacetate or ethyleneglycol diaceta-te.
The catalyst can be selected From all of the metals be-longing to group VIII of the Periodic System (Ru, Rh, Pd, 05, Ir, Pt). Rhodlum has however been found to be the most ac-tive metal. It and all other noble metals should convenient-ly be used in the form of compounds which are soluble under the reaction conditions and form an acti~e noble metal/car-bonyl-complex, e.g. RhC13 . 3H20, / Rh(C0)2Cl_/2, /_Pd(C0)2I_72, 3' ( 3C2)2' PdC12' Pd(C5H72)2- The noble metal compound of group VIII should be present in the reaction mi~ture in a preferred concentration of 0.001 to 0.1 mol/l, more preferably 0.005 to 0.05 mol/l.
Lithium iodide ~is the most interesting of the alkali - metal iodides which are used as promoter salts, but sodium iodide or potassium iodide can also be employed. Methyltri-butylphosphonium iodide should preferably be used as an or-ganophosphonium iodide, but other quaternary phosphonium iodides, such as methyltriphenylphosphonium iodide, tetrabutylphosphonium iodide or dimethyldibutylphosphoniumiodide can also be used- The organoammonium compound prefe-rably is N,N-dimethylimidazolium iodide, but it can also be selected from N-methylpyridinium iodide, N-methyl-3-picoli-nium iodide, N-methyl-Z,~-lutidinium iodide, N-methyl-3,4-lutidinium iodide, N-methylquinolinium iodide, etc. The concentration of the promoter salt in the reaction mixture should be between 0.01 and 2 mol/l, preferably between 0.1 and 0.8 mol/l.
lZS8~69 The carbonyl complex-formin9 non-noble metals of groups IV, V, UI, VII and VIII which may be used as copromo-ters, should conveniently be used in form oF a readily so-luble ~ compound, e.g. as acetyl acetonate or carbonyl, in the reaction. The concentrations of these copromoters in the reaction mixture should conveniently be between 0.01 and 0.5 mol/l, preferably between û.05 and 0.3 mol/l. Compounds of the metals Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co or Ni are preFerably used.
The alkali metal iodide RI as a constituent typical of the catalyst should be selected From materials in which the alkyl radical R corresponds to the feed products ROR (ether) and ROH (alcohol); failing this, mixed products are obtai-ned. This means that it is necessary For methyl iodide to be used for the production of acetic acid, methyl acetate and acetic anhydride From dimethylether and methanol, whereas ethyl iodide is required to be used For the production oF
propionic acid, ethyl propionate and propionic anhydride from diethylether and ethanol. The concentration of alkyl iodide in the reaction mixture should between 0.1 and 5 mol/l, preferably between 0.5 and 2.5 mol/l.
While the present process is preferably effected in li-quid phase, it is also possible for it to be effected in gas phase in contact with a carrier-supported catalyst. In the two cases, reaction temperature preferably is between 150 and 250C and the operational pressure preferably is between 20 and 60 bar. The carbonylation process can be carried out in a discontinuously and also in a continuously operated production facility.
i2584~9 Example 1 3 mol dimethylether, dissolved in 3 mol methanol, 1 mol methyl iodide, 0,2 mol methyltributylphosphonium iodide and 0.5 g rhodium in form of /_Rh(C0)2Cl_/2 were introduced into an agitator-provided stainless steel (Hastelloy B2) autocla-ve having a capacity of 1 liter, and a pressure of 25 bar was established by injecting carbon monoxide. The whole was heated to the reaction temperature of 180C and a total pressure of 50 bar was maintained over a period of 45 minu-tes by continuing the injection of carbon monoxide. After - cooling with release of pressure, the reaçtion mixture was analyzed gas-chromatographically and found to contain 3 mol acetic acid, 0.8 mol methyl acetate and 2.2 mol acetic an-::
hydride.
Example 2 Example 1 was repeated but the methyltributylphosphoni-um iodide promoter was replaced by 0.2 mol N,N-dimethylimi-dazolium iodide. The resulting product mixture was found to contain 3 mol acetic acid, 0.6 mol methyl acetate and 2.4 mol acetic anhydride.
Example 3 ; Example 1 was repeated but the methyltributylphosphoni-um iodide promoter salt was replaced by 0.2 mol lithium iodide. The resulting product mixture was found to contain 3 mol acetic acid, 0.9 mol methyl acetate and 2.1 mol acetic anhydride.
Example 4 Example 1 was repeated while adding 0.05 mol zirconium acetyl acetonate. After the reaction temperature of 180C
had been reached, a total pressure of 50 bar was established :
lZS84~9 over a period of 30 minutes by continuing the injection of C0. The resulting product mixture was worked up and found to contain 3 mol acetic acid, 0.4 mol methyl acetate and 2.6 mol acetic anhyride.
Example 5 Example 1 was repeated whiLe adding 0.05 mol vanadi-umhexacarbonyl and the batch was further treated as descri-bed in Example 4. The product mixture was worked up and found to contain 3 mol acetic acid, 0.5 mol methyl acetate and 2.5 mol acetic anhydride.
Example 6 Example 1 was repeated while adding 0.05 mol chromace-tylacetonate a~nd the batch was further treated as described in Example 4. The product was worked up and found to contain 3 mol acetic acid, 0.3 mol methyl acetate and Z.7 mol acetic anhydride.
Example 7 Example 1 was repeated while adding û.05 mol dirheni-umdecacarbonyl and the batch was further treated as descri-bed in Example 4. The resulting product mixture contained 3 mol acetic acid, 0.4 mol methyl acetate and 2.6 mol acetic anhydride.
Example 8 Example 1 was repeated while adding 0.05 mol dico-baltoctacarbonyl and the batch was further treated as des-cribed in Example 4. The resulting product mixture contained 3 mol acetic acid, 0.5 mol methyl acetate and 2.5 mol acetlc anhydride.
Example 9
Acetic acid and acetic anhydride belong to the most im-portant aliphatic intermediates, and are predominantly used for making vinyl acetate or cellulose acetate.
Heretofore, acetic acid has almost exclusively been made by oxidizing acetaldehyde, alkanes or alkenes, but pro-cesses for making acetic acid by subjecting methanol to car-bonylation have recently been galning increasing interest.
German Specification DE 17 67 151 C3, for example, describes a process for making carboxylic acids andtor their esters by subjecting a saturated aliphatic alcohol having from 1 to 20 carbon atoms or a halogenated derivative or ester or ether derivative thereof, or phenol to a catalytic conversion re-action, the feed materials aForesaid being reacted with car-bon monoxide under a CO-partial pressure of 0.34 to 207 bar either in liquid phase at 100 to 240C or in gas phase at 200 to 400C in the presence of a rhodium compound and of bromine, iodine or a compound of these halogenes and also in the presence of water, in the event of a halogenated deriva-tive, ester or ether derivative of an alcohol being used.
Heretofore, acetic anhydride has predominantly been made either by reacting acetic acid with a ketene or by subject-ing acetaldehyde to a modified oxidation. More recent routes - have been described in German Specification DE-OS 24 41 502, wherein a carboxylate ester or hydrocarbon ether is reacted with an acyl iodide or bromide under practically anhydrous conditions. The acyl halide is prepared by subjecting an lZ58469 alkyl halide to carbonylation in the presence of a catalyst system formed of a nob.le metal belonging to group VIII of the Periodic System and, optionally, a promQter selected from groups Ia, IIa, IIIa, IVb, VIb, non-noble metals of group VIII, and metals of the lanthanides and actinides of the Periodic System.
German Specification DE 24 5û 965 C2 describes a pro-ces.s For making acetic anhydride by reacting methyl acetate or a methyl acetate/dimethylether-mixture with carbon mon-oxide under pressures of l to 500 bar and at temperaturesof 50 to 250C in the absence of significant proportions of water and in the presence of catalysts containing noble me-tals belonging to the 8th subgroup of the Periodic System or their compounds, iodine and/or iodine compounds and optionally carbonyl-yielding metals, the reaction being ef-fected in the presence of catalysts which additionally con-tain an alkyl or aryl phosphine and/or an organic nitrogen compound, and optionally in the presence of 5 to 50 volume ~O
hydrogen. The feed materials which are preferentially used are methyl acetate/methanol-mixtures containing 18 to 20 ~O
methanol.
A further process for the joint manuFacture of acetic acid and acetic anhydride has been described in ~uropean Specification EP 00 87 869 Al, wherein a carboxylic acid ester or ether, water and optionally an alcohol are reacted with carbon monoxide in the presence of a catalyst consist-ing of a noble metal belonging to group VIII of the Periodic System, a bromine or iodine promoter, and a copromoter form-ed of a Lewis base or a non-noble metal, to give a mixture of carboxylic acid and carboxylic anhydride, the feed ~2~i8469 mixture containing at least 5.5 weight O water. As regards the total quantity of water and alcohol, it is not allowable for it to exceed 85 O oF the stoichiometric quantity of ester and ether.
Reaction mixtures such as those just described which in addition to acetic acid contain reactive iodine compounds and also water have, however, h.igh corrosiveness for most materials used in industry, including Hastelloy stainless steels, so that it is invariably necessary for these mate-rials to be replaced by expens.i\/e substitutes, e.g. tanta-lum.
It is possible for this dlsadvantage to be set aside by using an anhydrous mixture of dimethylether and methanol readily available in sufficient quantities from substantial-- ly all methanol producers. As has unexpectedly been found, the reaction mixture has con~sidsrably less cnrroslvenes.s in a those cases in which the reaction is effected under anhy-drous conditions. In this case the aCt.iVi.t.Y nf the catalyst re-lative to the entirety of products is at least preserved or even improved, compared with operation in the presence of water. Besides the possibility of adapting the carboxylic acid/carboxylic anhydride-product ratio to commercial requi-rementS,the present process provides for the corresponding carboxylic acid ester to be made as a further commercial product.
The present invention provides more particularly a process for the joint manufacture of carboxylic acids, carb-oxylic anhydrides and, if desired, carboxylic acid esters of }n the general formulae RCOOH, RCOOCOR and RCOOR, respectively, lZS84~i9 in which R each time stands for one and the same alkyl radi-cal having from 1 to 4 carbon atoms, which comprises: react-ins at temperatures of 50 to 250C and under pressures of D.1 to 120 bars, a dialkyl ether of the general formula ROR with an alcohol of the general formula ROH in a molar ratio of 9 :
.
1 to 1 : 9 under anhydrous conditions, with carbon monoxide and, if desired, hydrogen in -the presence of a catalyst sy-.stem consisting of carbonyl complexes of noble metals be-longing to group VIII of the Periodic System; an alkali me-tal iodide, organophosphonium iodide or organoammonium iodi-de; an alkyl iodide of the general formula RI; and, if desi-; red, compounds of carbonyl-yielding non-noble metals belong-ing to groups IV, V, VI, VII or VIII of the Periodic system.
In this way, it is possible to produce acetic acid, acetic anhydride and optionally methyl acetate from dime-thylether, methanol and methyl iodide, for example. The car-bon monoxide used may contain up to lû volume ~ hydrogen.
By varying the dialkylether/alcohol- feed ratio, it is possible to establish practically any desirable product ra-tio.of carboxylic acid/carboxylic anhydride. This is a spe-~ cial advantage of the present invention permitting the pro-; cess to be rapidly acted upon in accordance with require-ments.
It is not absolutely necessary for pure carbon monoxide to be used in the reaction. Relativaly small amounts of inert gas, such as carbon dioxide, nitrogen or methane could not be found to affect the carbonylation provided that the CO-partial pressure inside the reactor is kept constant. A
hydrogen content of up to lû O has even been found positive-3 ly to add to the catalyst activity but to reduce the selec-lZS8469 tivity of the process by the formation of hydrogenation pro-ducts, e.g. ethylidene diacetate or ethyleneglycol diaceta-te.
The catalyst can be selected From all of the metals be-longing to group VIII of the Periodic System (Ru, Rh, Pd, 05, Ir, Pt). Rhodlum has however been found to be the most ac-tive metal. It and all other noble metals should convenient-ly be used in the form of compounds which are soluble under the reaction conditions and form an acti~e noble metal/car-bonyl-complex, e.g. RhC13 . 3H20, / Rh(C0)2Cl_/2, /_Pd(C0)2I_72, 3' ( 3C2)2' PdC12' Pd(C5H72)2- The noble metal compound of group VIII should be present in the reaction mi~ture in a preferred concentration of 0.001 to 0.1 mol/l, more preferably 0.005 to 0.05 mol/l.
Lithium iodide ~is the most interesting of the alkali - metal iodides which are used as promoter salts, but sodium iodide or potassium iodide can also be employed. Methyltri-butylphosphonium iodide should preferably be used as an or-ganophosphonium iodide, but other quaternary phosphonium iodides, such as methyltriphenylphosphonium iodide, tetrabutylphosphonium iodide or dimethyldibutylphosphoniumiodide can also be used- The organoammonium compound prefe-rably is N,N-dimethylimidazolium iodide, but it can also be selected from N-methylpyridinium iodide, N-methyl-3-picoli-nium iodide, N-methyl-Z,~-lutidinium iodide, N-methyl-3,4-lutidinium iodide, N-methylquinolinium iodide, etc. The concentration of the promoter salt in the reaction mixture should be between 0.01 and 2 mol/l, preferably between 0.1 and 0.8 mol/l.
lZS8~69 The carbonyl complex-formin9 non-noble metals of groups IV, V, UI, VII and VIII which may be used as copromo-ters, should conveniently be used in form oF a readily so-luble ~ compound, e.g. as acetyl acetonate or carbonyl, in the reaction. The concentrations of these copromoters in the reaction mixture should conveniently be between 0.01 and 0.5 mol/l, preferably between û.05 and 0.3 mol/l. Compounds of the metals Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Co or Ni are preFerably used.
The alkali metal iodide RI as a constituent typical of the catalyst should be selected From materials in which the alkyl radical R corresponds to the feed products ROR (ether) and ROH (alcohol); failing this, mixed products are obtai-ned. This means that it is necessary For methyl iodide to be used for the production of acetic acid, methyl acetate and acetic anhydride From dimethylether and methanol, whereas ethyl iodide is required to be used For the production oF
propionic acid, ethyl propionate and propionic anhydride from diethylether and ethanol. The concentration of alkyl iodide in the reaction mixture should between 0.1 and 5 mol/l, preferably between 0.5 and 2.5 mol/l.
While the present process is preferably effected in li-quid phase, it is also possible for it to be effected in gas phase in contact with a carrier-supported catalyst. In the two cases, reaction temperature preferably is between 150 and 250C and the operational pressure preferably is between 20 and 60 bar. The carbonylation process can be carried out in a discontinuously and also in a continuously operated production facility.
i2584~9 Example 1 3 mol dimethylether, dissolved in 3 mol methanol, 1 mol methyl iodide, 0,2 mol methyltributylphosphonium iodide and 0.5 g rhodium in form of /_Rh(C0)2Cl_/2 were introduced into an agitator-provided stainless steel (Hastelloy B2) autocla-ve having a capacity of 1 liter, and a pressure of 25 bar was established by injecting carbon monoxide. The whole was heated to the reaction temperature of 180C and a total pressure of 50 bar was maintained over a period of 45 minu-tes by continuing the injection of carbon monoxide. After - cooling with release of pressure, the reaçtion mixture was analyzed gas-chromatographically and found to contain 3 mol acetic acid, 0.8 mol methyl acetate and 2.2 mol acetic an-::
hydride.
Example 2 Example 1 was repeated but the methyltributylphosphoni-um iodide promoter was replaced by 0.2 mol N,N-dimethylimi-dazolium iodide. The resulting product mixture was found to contain 3 mol acetic acid, 0.6 mol methyl acetate and 2.4 mol acetic anhydride.
Example 3 ; Example 1 was repeated but the methyltributylphosphoni-um iodide promoter salt was replaced by 0.2 mol lithium iodide. The resulting product mixture was found to contain 3 mol acetic acid, 0.9 mol methyl acetate and 2.1 mol acetic anhydride.
Example 4 Example 1 was repeated while adding 0.05 mol zirconium acetyl acetonate. After the reaction temperature of 180C
had been reached, a total pressure of 50 bar was established :
lZS84~9 over a period of 30 minutes by continuing the injection of C0. The resulting product mixture was worked up and found to contain 3 mol acetic acid, 0.4 mol methyl acetate and 2.6 mol acetic anhyride.
Example 5 Example 1 was repeated whiLe adding 0.05 mol vanadi-umhexacarbonyl and the batch was further treated as descri-bed in Example 4. The product mixture was worked up and found to contain 3 mol acetic acid, 0.5 mol methyl acetate and 2.5 mol acetic anhydride.
Example 6 Example 1 was repeated while adding 0.05 mol chromace-tylacetonate a~nd the batch was further treated as described in Example 4. The product was worked up and found to contain 3 mol acetic acid, 0.3 mol methyl acetate and Z.7 mol acetic anhydride.
Example 7 Example 1 was repeated while adding û.05 mol dirheni-umdecacarbonyl and the batch was further treated as descri-bed in Example 4. The resulting product mixture contained 3 mol acetic acid, 0.4 mol methyl acetate and 2.6 mol acetic anhydride.
Example 8 Example 1 was repeated while adding 0.05 mol dico-baltoctacarbonyl and the batch was further treated as des-cribed in Example 4. The resulting product mixture contained 3 mol acetic acid, 0.5 mol methyl acetate and 2.5 mol acetlc anhydride.
Example 9
2 mol dimethylether, dissolved in 4 mol methanol, 1.2 ~Z58469 mol methyl iodide, 0.2 mol methyltributylphosphonium iodide and 0.5 gram rhodium in form of L Rh(C0)2Cl_/2 were introd-used into an agitator-provided stainless steel (Hastelloy B2) autoclave having a capacity of l liter. Next, 25 bar carbon monoxide and 2.5 bar hydrogen were injected. The ; whole was heated to the reaction temperature of 180C and a total pressure of 50 bar was maintained over a period of 45 : minutes by continuous injection of a gas mixture of 90 mol carbon monoxide and 10 mol ~ hydrogen. After cooling with release of pressure, the reaction mixture was analyzed gas-chromatographically and found to contain 4.4 mol acetic acid, 0.2 mol methyl acetate, l.0 mol acetic anhydride and 0.4 mol ethylidene diacetate.
Example 10 Example 9 was repeated but the rhodium catalyst l.uas re-placed by 0.5 9 palladium in form of palladium acetylaceto-nate. The resulting product mixture contained 4.7 mol acetic acid, 0.1 mol methyl acetate, 0.5 mol acetic anhydride and 0.7 mol ethylidene diacetate.
Example ll
Example 10 Example 9 was repeated but the rhodium catalyst l.uas re-placed by 0.5 9 palladium in form of palladium acetylaceto-nate. The resulting product mixture contained 4.7 mol acetic acid, 0.1 mol methyl acetate, 0.5 mol acetic anhydride and 0.7 mol ethylidene diacetate.
Example ll
3 mol diethylether, 2 mol ethanol, l mol ethyl iodide, 0.2 mol methyltributylphosphonium iodide and 0.5 9 rhodium in form of ~Rh(C0)2Cl_/2 ~ere introduced into the autoclave already described and a pressure of 25 bar was establish by injecting carbon monoxide. The whole was heated to 180 C
and a reaction pressure of 50 bar was maintained over a pe-riod of 3 hours by continuous injection of carbon monoxide.
The reaction product was worked up and found to contain 2 mol propionic acid, 1.2 mol ethyl propionate and 1.8 mol 3 propionic anhydride.
Example 12 3 mol dimethylether, dissolved in 3 mol methanol, 1 mol methyl iodide, 0.2 mol tetrabutylphosphonium iodide and O.S g r~ rhodium in form of / R~(C0)2C1_/2 were introduced into the autocla~/e already described and a pressure of 25 bar was established by injecting carbon monoxide. The whole was heated to 180C and a total pressure oF 50 bar was maintained over a period of 40 minutes by contlnuous injection of carbon monoxide. After cooling with release of pressure, the reac-tion mixture was analyzed gas-chromatographically and found to contain 3 mol acetic acid, 0.7 mol methyl acetate and 2.3 mol acetic anhydride.
Example 13 5 mol dimethylether, 1 mol methanol, 1 mol methyl iodi-de, 0.2 mol methyltributylphosphonium iodide and 0.5 9 rho-dium in form of /_Rh(C0)2Cl_/2 were used. A C0-pressure oF
25 bar was established and the reaction mixture was heated to 180C. A total pressure of 50 bar was maintained over a pe-riod of 45 minutes by continuous injection of carbon monoxi-de. After cooling with release of pressure, the reaction mixture was analyzed gas-chromatographlcally and found to contain 1 mol acetic acid, 1.4 mol methyl acetate and 3.6 mol acetic anhydride.
Example 14 1 mol dimethylether, 5 mol methanol, 1 mol methyl iodi-de, 0.2 mol methyltributylphosphonium iodide and 0.5 9 rho-dium in form of ~ Rh(C0)2Cl_/2were used and treated in the manner described in Example 13. The reaction product was analyzed gas-chromatographically and found to contain 5 mol acetic acid, 0.8 mol methyl acetate and 0.2 mol acetic anhydride.
lo
and a reaction pressure of 50 bar was maintained over a pe-riod of 3 hours by continuous injection of carbon monoxide.
The reaction product was worked up and found to contain 2 mol propionic acid, 1.2 mol ethyl propionate and 1.8 mol 3 propionic anhydride.
Example 12 3 mol dimethylether, dissolved in 3 mol methanol, 1 mol methyl iodide, 0.2 mol tetrabutylphosphonium iodide and O.S g r~ rhodium in form of / R~(C0)2C1_/2 were introduced into the autocla~/e already described and a pressure of 25 bar was established by injecting carbon monoxide. The whole was heated to 180C and a total pressure oF 50 bar was maintained over a period of 40 minutes by contlnuous injection of carbon monoxide. After cooling with release of pressure, the reac-tion mixture was analyzed gas-chromatographically and found to contain 3 mol acetic acid, 0.7 mol methyl acetate and 2.3 mol acetic anhydride.
Example 13 5 mol dimethylether, 1 mol methanol, 1 mol methyl iodi-de, 0.2 mol methyltributylphosphonium iodide and 0.5 9 rho-dium in form of /_Rh(C0)2Cl_/2 were used. A C0-pressure oF
25 bar was established and the reaction mixture was heated to 180C. A total pressure of 50 bar was maintained over a pe-riod of 45 minutes by continuous injection of carbon monoxi-de. After cooling with release of pressure, the reaction mixture was analyzed gas-chromatographlcally and found to contain 1 mol acetic acid, 1.4 mol methyl acetate and 3.6 mol acetic anhydride.
Example 14 1 mol dimethylether, 5 mol methanol, 1 mol methyl iodi-de, 0.2 mol methyltributylphosphonium iodide and 0.5 9 rho-dium in form of ~ Rh(C0)2Cl_/2were used and treated in the manner described in Example 13. The reaction product was analyzed gas-chromatographically and found to contain 5 mol acetic acid, 0.8 mol methyl acetate and 0.2 mol acetic anhydride.
lo
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS.
1. A process for the joint manufacture of carboxylic acids, carboxylic anhydrides and carboxylic acid esters of the general formulae RCOOH, RCOOCOR and RCOOR, respectively, in which R each time stands for one and the same alkyl radical having from 1 to 4 carbon atoms, which process comprises reacting at temperatures of 50 to 250°C and under pressures of 0.1 to 120 bars, a dialkyl ether of the general formula ROR with an alcohol of the general formula ROH in a molar ratio of 9:1 to 1:9 under anhydrous conditions, with carbon monoxide in the presence of a catalyst system consisting of carbonyl complexes of noble metals belonging togroupVIII of the Periodic System, an alkali metal iodide, organophosphonium iodide or organoammonium iodide and an alkyl iodide of the general formula RI.
2. A process as claimed in claim 1, wherein acetic acid, methyl acetate and acetic anhydride are produced from dimethylether, methanol and methyl iodide.
3. A process as claimed in claim 1, wherein the carbon monoxide used contains up to 10 volume % hydrogen.
4. A process as claimed in claim 1, 2 or 3, wherein the catalyst system further comprises compounds of carbonyl-yielding non-noble metals belonging to groups IV, V, VI, VII or VIII of the Periodic System.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3429179.2 | 1984-08-08 | ||
| DE19843429179 DE3429179A1 (en) | 1984-08-08 | 1984-08-08 | METHOD FOR THE SIMULTANEOUS PRODUCTION OF CARBONIC ACIDS AND CARBONIC ACID ANHYDRIDES AND IF ANY. CARBONIC ACID ESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1258469A true CA1258469A (en) | 1989-08-15 |
Family
ID=6242594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000486571A Expired CA1258469A (en) | 1984-08-08 | 1985-07-10 | Process for the joint manufacture of carboxylic acids, carboxylic anhydrides and, if desired, carboxylic acid esters |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0170965B1 (en) |
| JP (1) | JPS6147428A (en) |
| AT (1) | ATE45722T1 (en) |
| AU (1) | AU576260B2 (en) |
| BR (1) | BR8503725A (en) |
| CA (1) | CA1258469A (en) |
| DE (2) | DE3429179A1 (en) |
| MX (1) | MX163194B (en) |
| ZA (1) | ZA855954B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124290A (en) * | 1990-10-30 | 1992-06-23 | Hoechst Aktiengesellschaft | Process for removing metallic corrosion products from carbonylation reactions carried out under anhydrous conditions |
| US5672743A (en) * | 1993-09-10 | 1997-09-30 | Bp Chemicals Limited | Process for the production of acetic acid |
| US5760279A (en) * | 1995-06-19 | 1998-06-02 | Bp Chemicals Limited | Process for the carbonylation of alkyl alcohols |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3429180A1 (en) * | 1984-08-08 | 1986-02-20 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING ACETIC ACID ANHYDRIDE AND GGF. ACETIC ACID |
| CA1299195C (en) * | 1986-06-16 | 1992-04-21 | G. Paull Torrence | Addition of hydrogen to carbon monoxide feed gas in producing acetic acid by carbonylation of methanol |
| DE3823645C1 (en) * | 1988-07-13 | 1989-11-30 | Hoechst Ag | |
| GB9021454D0 (en) * | 1990-10-03 | 1990-11-14 | Bp Chem Int Ltd | Process |
| DE4034867A1 (en) * | 1990-11-02 | 1992-05-07 | Hoechst Ag | CONTINUOUS PROCESS FOR THE SIMULTANEOUS PRODUCTION OF ACETIC ACID AND ACETIC ACID ANHYDRIDE |
| CA2093752C (en) * | 1992-04-15 | 1999-06-15 | David W. Studer | Integrated process for oxygenated acetyl compounds from synthesis gas via dimethyl ether |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2836084A1 (en) * | 1978-08-17 | 1980-03-06 | Hoechst Ag | METHOD FOR PRODUCING ACETIC ACID ANHYDRIDE |
| DE2939839A1 (en) * | 1979-10-02 | 1981-04-23 | Hoechst Ag, 6000 Frankfurt | METHOD FOR PRODUCING ACETIC ACID ANHYDRIDE |
| JPS5930687B2 (en) * | 1980-04-22 | 1984-07-28 | 三菱瓦斯化学株式会社 | Method for producing ethylidene diacetate and/or acetic anhydride |
| EP0075337B1 (en) * | 1981-09-22 | 1985-10-23 | Shell Internationale Researchmaatschappij B.V. | Process for the co-production of carboxylic acids and carboxylic acid esters |
| DE3144772A1 (en) * | 1981-11-11 | 1983-05-19 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING ACETIC ACID ANHYDRIDE AND ACETIC ACID |
| CA1218999A (en) * | 1983-01-25 | 1987-03-10 | Eit Drent | Process for the preparation of carboxylic acids and/or esters |
-
1984
- 1984-08-08 DE DE19843429179 patent/DE3429179A1/en not_active Withdrawn
-
1985
- 1985-07-10 CA CA000486571A patent/CA1258469A/en not_active Expired
- 1985-07-22 EP EP85109147A patent/EP0170965B1/en not_active Expired
- 1985-07-22 AT AT85109147T patent/ATE45722T1/en not_active IP Right Cessation
- 1985-07-22 DE DE8585109147T patent/DE3572473D1/en not_active Expired
- 1985-08-07 AU AU45886/85A patent/AU576260B2/en not_active Ceased
- 1985-08-07 JP JP60172553A patent/JPS6147428A/en active Granted
- 1985-08-07 ZA ZA855954A patent/ZA855954B/en unknown
- 1985-08-07 BR BR8503725A patent/BR8503725A/en not_active IP Right Cessation
- 1985-08-07 MX MX206225A patent/MX163194B/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124290A (en) * | 1990-10-30 | 1992-06-23 | Hoechst Aktiengesellschaft | Process for removing metallic corrosion products from carbonylation reactions carried out under anhydrous conditions |
| US5672743A (en) * | 1993-09-10 | 1997-09-30 | Bp Chemicals Limited | Process for the production of acetic acid |
| US5942460A (en) * | 1993-09-10 | 1999-08-24 | Bp Chemicals Limited | Catalyst system |
| US5760279A (en) * | 1995-06-19 | 1998-06-02 | Bp Chemicals Limited | Process for the carbonylation of alkyl alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3429179A1 (en) | 1986-02-20 |
| AU576260B2 (en) | 1988-08-18 |
| JPH0371418B2 (en) | 1991-11-13 |
| EP0170965A2 (en) | 1986-02-12 |
| EP0170965A3 (en) | 1987-05-20 |
| EP0170965B1 (en) | 1989-08-23 |
| ATE45722T1 (en) | 1989-09-15 |
| JPS6147428A (en) | 1986-03-07 |
| ZA855954B (en) | 1986-04-30 |
| BR8503725A (en) | 1986-05-13 |
| DE3572473D1 (en) | 1989-09-28 |
| AU4588685A (en) | 1986-02-13 |
| MX163194B (en) | 1991-10-15 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |