CA1156671A - Manufacture of vicinal glycol esters from synthesis gas - Google Patents
Manufacture of vicinal glycol esters from synthesis gasInfo
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- CA1156671A CA1156671A CA000331035A CA331035A CA1156671A CA 1156671 A CA1156671 A CA 1156671A CA 000331035 A CA000331035 A CA 000331035A CA 331035 A CA331035 A CA 331035A CA 1156671 A CA1156671 A CA 1156671A
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- 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
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Abstract
ABSTRACT
The invention concerns a process for the formation of ester mixtures, comprising esters of monohydrlc and dlhydric alcohols by reactlng synthesis gas (CO + H2) and carboxylic acid, at a temperature of 100 to 350°C and a pressure of at least 34 atmospheres (500 psi) in the presence of 3 catalyst comprising ruthenlum or osmium. Optionally a co-catalyst selected from alkali metal salts, alkaline earth metal salts, quaternary ammonlum salts, iminium salts and quaternary aliphatic phosphonium salts is also employed. A
typical reaction product comprises methyl acetate, ethyl acetate and ethylene glycol diacetate.
The invention concerns a process for the formation of ester mixtures, comprising esters of monohydrlc and dlhydric alcohols by reactlng synthesis gas (CO + H2) and carboxylic acid, at a temperature of 100 to 350°C and a pressure of at least 34 atmospheres (500 psi) in the presence of 3 catalyst comprising ruthenlum or osmium. Optionally a co-catalyst selected from alkali metal salts, alkaline earth metal salts, quaternary ammonlum salts, iminium salts and quaternary aliphatic phosphonium salts is also employed. A
typical reaction product comprises methyl acetate, ethyl acetate and ethylene glycol diacetate.
Description
1~6671 D.75,732-FB
MANUF~CTURE OF VICINAL GLYCOL ESTE~S
FROM SYNT~ESIS GAS
This invention concerns an improved process for preparing alkanol and vicinal glycol ester compounds, including ester derivatives of ethylene glycol, by reaction of oxides of carbon with hydrogen.
~ More particularly, the invention concerns the selective co-synthesis of alkanol and glycol esters, particularly the ester derivative of ethylene glycol, methanol and ethanol, by the catalytic reaction o carbon monoxide and hydrogen in the presence of a liquid medium containing a carboxylic acid co-reactant. Catalysis is effected in the presence of a catalyst containing osmium or ruthenium, with the latter being most preferred. The process is exemplified by, but not limited to the one step co-synthesis of ethylene glycol diacetate, methyl acetate and ethyl acetate from carbon monoxide, hydrogen mixtures in the presence of an acetic acid (HOAc) liquid medium according to the stoichiometry of eqs. (1) to (3):
~2CO + 3H2 + 2HOAc ~ ¦ ~ 2H2o (1) 2co + 4H2 ~ HOAc ~ CH3CH20Ac ~ 2H2o (2) CO + 2H2 + HOAc ~ CH30~c + H20 (3) Methyl acetate, ethyl acetate and glycol diacetate - are all products of recognized commercial valuej particularly as chemical intermediates and extractive solvents~ Methyl and ethyl acetates are used widely as solvents, primarily for surface coatings. Ethylene glycol diacetate is useful in the production of ethylene glycol, an important component in polyester fiber and antifreeze formulations. Free glycol may be generated from its diacetate deriva~ive via hydrolysis as disclosed, for example, in Belgian Patent No. 749,685.
It is the purpose of this invention to provide new routes to the preparation of alkanol and diol Psters using mixtures of carbon monoxide and hydrogen (hereinafter sometimes referred to as synthesis gas or syngas). This is 1~5667~
particularly true where methyl acetate, ethyl acetate and glycol diacetate are the principal products (eqs. 1-3), since in this case acetic acid is the co-reactant medium, and one route to HOAc manufacture is fxom synthesis gas via methanol carbonylation. ("Trends in Petrochemical Technology" by A. M. Brownstein, Chapter 5 (1976~).
In recent years, a large number of patents have been issued dealing with the synthesis of lower molecular weight hydrocarbons, olefins, and alkanols, from synthesis gas. Of particular note, U.S. Patent No. 2,636,o46 discloses the synthesis of polyhydric alcohols and their ~ derivatives by reaction between carbon monoxide and hydrogen at elevated pressures (>1500 atm or 22,000 psi) and temper-atures to 400C using certain cobalt-containing catalysts.
~ore recently, i~ 8elgian Patent No. 793,086 and U.S. Patent No. 3,940,432 there is described the co-synthesis of methanol and ethylene glycol from mixtures of carbon monoxide and hydrogen using a rhodium compl~x catalyst. Typically, CO-hydrogenation is effected at 544 atmospheres (8000 psi) of l:l H2/CO synthesis gas, at 220C, using tetraethylene glycol methyl ether as the solvent, and dicarbonylacetyl-acetonatorhodium(I) in combination with an organic Lewis base as the catalyst precursor. (For a summary of the work, see: R. L. Purett, Annals New York Academy of Sciences, Vol. 295 p. 239 (1977))~ While other metals of Group VIII
of the Periodic Table have been tested for activity under similar conditions, including cobalt, ruthenium, copper, manganese, iridium and platinum, only cobalt was found to have slight activity. The use of ruthenium compounds in particular failed to produce polyfunctional products such as ethylene glycol. ~his is illustrated in U.S. Patent No.
3,833,634 for solutions of triruthenium dodecarbonyl.
The present invention provides a process for the concurrent synthesis of alkanol and vicinal glycol esters which comprises heating a reaction mixture of carbon monoxide and hydrogen, (with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester syntheses), a liquid medium containing one or more carboxylic acids and a catalyst containing ruthenium, osmium or a mixture thereof~
1 1~6671 at a temperature between 100C and 350C, and a superatomos-pheric pressure of at least 34 atmospheres (500 psi).
In one preferred embodiment, the reaction mixture contains, as a co--catalyst one or more alkali metal salts, alkaline earth metal salts, quaternary a onium salts, iminium salts or quaternary phosphonium salts.
Further details of the invention are as follows:
A. Catalyst Composition - Catalysts that are suitable in the practice o this invention contain osmium or ruthenium 1~ or mixtures of these metalsO The ruthenium or osmium-containing catalyst may be chosen from a wide variety of organic or inorganic compounds or complexes, as will be shown and illustrated below. It is only necessary that ths catalyst precursor actually employed contain the transition metal (i.e. ruthenium or osmium) in any of its ionic states.
The actual catalytically active species are then believed to comprise ruthenium or osmium in complex combination with carbon monoxide and hydrogen~ The most effective catalysis is achieved where the ruthenium or osmium hydrocarbonyl species are solubilized in the carboxylic acid co-reactant employed to satisfy the stoichiometry of eq 1 3.
While the invention will be more specifically discussed below in terms of typical ruthenium-containing forms or species, it is understood that osmium may be employed in like forms in most cases without departing from the scope of the invention~
The preferred ruthenium catalyst pxecursors may take many different forms. For instance, the ruthenium may be added to the reaction mixture in an oxide form, as in the case of, for example, ruthenium(IV) oxide, hydrate, anhydrous ruthenium(IV) dioxide and ruthenium(VIII) tetraoxide.
Alternatively, it may be added as the salt of a mineral acid, as in the case o,f ruthenium(III) chloride hydrate, ruthenium~III) bromide, anhydrous ruthenium(III) chloride and ruthenium nitrate, or as the salt of a suitable organic carboxylic acid (see Section B, below), for example, ruthenium(III) acetate, ruthenium(III) propionate, ruthenium butyrate, ruthenium(III) trifluoroacetate, ruthenium octanoate, ruthenium napththenate, ruthenium valerate and ruthenium(III) 1 ~56671 acetylacetonate. The ruthenium may also be added to the reaction zone as a carbonyl or hydrocarbonyl derivative.
Here, suitable examples include triruthenium dodecacarbonyl, hydrocarbonyls such as H2Ru4(CO)13 and H4Ru4(CO)12, and substituted carbonyl species such as the tricarbonylruthenium (II) chloride dimer, [Ru(CO)3C12~2.
In a preferred embodiment of the invention ruthenium is added to the reaction zone as one or more oxide, salt or carbonyl derivative species in combination with one or more group VB tertiary donor ligands. The key elements of the Group VB ligands include nitrogen, phosphorus, arsenic and antimony. These elements, in their trivalent oxidation states, particularly tertiary phosphorus and nitrogen, may be bonded to one or more alkyl, cycloalkyl, aryl, substituted aryl, aryloxide, alkoxide, alkaryl or aralkyl radicals, each containing from 1 to 12 carbon atoms, or they may be part of a heterocyclic ring system, or be mixtures thereo. Illustrative examples of suitable ligands that may be used in this invention include: triphenylphosphine, tri-n-butylphosphine, triphenylpho~phite, triethylphosphite, trimethylphosphite, trimethylphosphine, tri-~-methoxyphenylphosphine, triethyl-phosphine, trimethylarsine, triphenylarsine, txi-~-tolyl-phosphine, tricyclohexylphosphine, dimethylphenylphosphine, trioctylphosphine, tri-o-tolylphosphine, 1,2-bis(diphenyl-phosphino)ethane, triphenylstibine, trimethylamine, triethyl-amine, tripropylamine, tri-n-octylamine, pyridine, 2,2'-dipyridyl, l,10-phenanthroline, quinoline, N,N'dimethyl-piperazine, ~8-bis(dimethylamino)naphthalene and N,N-dimethylaniline.
One or more of these ruthenium-teriary Group VB donor ligand combinations may be preformed, before addition to the reaction mixture, as in the case, for example, of tris ~triphenylphosphine)ruthenium(II) chloride and tricarbonyl-bis(triphenylphosphine)ruthenium or alternati~ely, said complexes may be formed in situ.
The perfor~ances of each of these classes of ruthenium catalyst precursors are illustrated by the accompanying examples, described below.
1 1~667 1 Similar catalyst combinations, containing osmium rather than ruthenium as the transition-metal component, are also suitable for the desired synthesis of alkanol and polyhydric alcohol esters from synthesis gas.
B. _ Carboxylic Acids : Carboxylic acids useful in the process of this invention form the acid moiety of the sesired methyl, ethyl and glycol ester products. Preferably, said acids are also useful as solvents for the transition-metal catalysts, particularly the ruthenium catalyst combin-ations. Suitable carboxylic acids include aliphaticacids, alicyclic monocarboxylic acids, heterocyclic acids and aromatic acids, both substituted and non-substituted.
For example, this invention contemplates the use of aliphatic monocarboxylic acids of 1 to 12 carbon atoms such as formic acid, acetic, propionic, butyric, isobutyric, valeric, caproic, capric, perlargonic and lauric acids, together with aliphatic dicarboxylic acids of 2 to 6 carbons, such as oxalic, malonic, succinic and adinic acids. Alternatively substituted aliphatic monocarboxylic acids containing one or more functional substituents, such as chlorine or fluorine atoms, or alkoxy, cyano, alkylthio, or amino groups.
Examples of such acids include acetoacetic acid, dichloroacetic acid, trifluoroacetic acid, chloropropionic acid, trichloro-acetic acid, and monofluoroacetic acid. Among suitable aromatic acids are benzoic acid, napthoic acids, toluic acids, chloxobenzoic acids, aminobenzoic acids and phenylacetic acid.
~he alicyclic monocarboxylic acids may contain from 3 to 6 carbons in the (substituted or unsubstituted) ring and may contain one or more carboxyl groups, such as cyclopentane-carboxylic acid or hexahydrobenzoic acid. The heterocyclicacids may contain 1 to 3 fused rings, which may be substituted or unsubstituted, together with one or more cax~oxylic groups, exa~ples include quinolinic, furoic and picolinic acids. Mixtures of said classes of carboxylic acids, in any ratio, may also be used in the inventive process. The preferred carboxylic acids are the aliphatic acids such as acetic acid, propionic acid and butyric acid, and substituted aliphatic acids such as trifluoroacetic acid 1 ~667~
C. Catalyst Concentration - The quantity of ruthenium or osmium catalyst employed in the invention is not critical and may vary over a wide range. In general, the novel process is desirably conducted in the presence of a catalyt-ically effective quantity of the active ruthenium or osmiumspecies which gives the desired ester products in reasonable yields. Reaction proceeds when employing as little as 1 x 10 6 weight percent, and even lesser amounts, of ruthenium or osmium, basis the total weight of the reaction mixture.
The upper concentration is dictated by a variety of factors including catalyst cost, partial pressures of carbon monoxide and hydrogen, operating temperature and choice of carboxylic acid diluent/reactant. A concentration of from 1 x 10 5 to 10 weight percent of ruthenium, or osmium based on the total weight of reaction mixture, is generally desirable in the practice of this invention.
D. Operating Temperature - The temperature range which can usefully be employed in these ester syntheses is variable dependent upon other experimental factors, including the choice of carboxylic acid co-reactant, the pressure, and the concentration and particular choice of catalyst among other things. Again using ruthenium as the active metal/ the range of operability is from 100 to 350C when superatmospheric pressures o~ syngas are employed. A narrower range of 150-260C represents the preferred temperature range when the major products are methyl, ethyl and glycol acetates.
Table I is evidence of how the narrower range is derived.
E. Pressure - Superatmospheric pressures of 34 atmospheres (500 psi) or greater lead to substantial yield of desirable alkanol and vicinal glycol ester by the process of this invention. A preferred operating range for solutions of ruthenium ~III) acetylacetonate in acetic acid is from 68 to 510 atmospheres (1000 to 7500 psi) although pressures .
above 510 atmospheres (7500 psi) also provide useful yields of desired ester. Table I is evidence of this preferred, narrower range of operating pressures. The pressures referred to here represent the total pressure generated by all the reactants, although they are substantially due to the carbon monoxide and hydrogen fractions in these examples.
6 7 ~
F. Gas ComPosition - The relative amounts of carbon monoxide and hydrogen which may be initially present in the syngas mixture are variable, and these amounts may be varied over a wide range. In general, the mole ratio of CO-to-H2 is in the range from 20:1 up to 1:20, preferably from 5:1 to 1:5, although ratios outside these ranges may also be employed. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixtures may also be used in conjunction with up to 50% by volume of c e or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, or neon, they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions such as carbon dioxide; hydrocarbons such as methane, ethane or propane;
ethers such as dimethyl ether, methyl ethyl ether and diethyl ether; alkanols such as methanol; and acid esters such as methyl acetate.
In all syntheses, the amount of carbon monoxide and hydrogen present in the reaction mixture should be suf~icient to satisfy the stoichiometry of eq (1) to (3).
G. Product Distribution - As far as can be determined, without limiting the invention thereby, the ruthenium or osmium catalyst one-step CO-hydrogenation process disclosed herein leads to the formation of three classes of primary products, namely the methanol, ethanol and ethylene glycol ester derivatives of the corresponding co-reactant carboxylic acid. When acetic acid is the co-reactant, the pxincipal products are methyl acetate, ethyl acetate and ethylene glycol diacetate. Minor by-products detected in the liquid product 3C fraction include small amounts of water, glycol monoacetate, propyl acetate and dimethyl ether. Carbon dioxide, methane and dimethyl ether may be detected in the off-gas together . with unreacted carbon monoxide and hydrogen.
H. Mode of OPeration - The novel process of this invention can be conducted in a batch, semi-continuous or continuous fashion. The catalyst may be initially introduced into the reaction zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be ~ ~5~67~
adjusted to optLmize the formation of the desired ester product, and said material may ~e recovered by methods well known in the art, such as distillation, fractionation, extraction and the like. A fraction rich in ruthenium or osmium catalyst components may then be recycled to the reac-tion zone, if desired, and additional egter products generated by CO hydrogenation.
I. Identificat;ion Procedures - The products of CO-hydrogenation have been identified in this work by one or more of the following analytical procedures, viz, gas-liquid phase chromatography (glc), infrared (ir), mass spectrometry, nuclear magnetic resonance ~nmr) and elemental analyses, or a combination of these techniques.
J._ Co-Catalyst - There are several classes of suitable co-catalysts for use in one embodiment of the invention.
One such class which may be added to the reaction mixtures to enhance the activity of the solubilized ruthenium or osmium catalysts æ e the salts of the alkali and alkaline earth metals.
Illustrative examples of ef~ective alkali metal salts include the alkali metal halides, for instance, the fluoride, chloride, bromide and iodide salts, and alkali and alkaline earth metal salts of suitable carboxylic acids. The preferred alkali and alkaline earth metal carboxylates are the acetate, propionate and butyrate salts of sodium, potassium, barium and cesium. These salts may be added over a wide range of concentrations, e.g. from O.Ol to 1O2 moles of alkali or alkaline earth salt per gm atom of ruthenium or osmium present in the reaction mixture. The most preferred ratios are from 5:1 to 15:1 ~See Table II).
The following are typical combinations of ruthenium-co-catalyst combinations useful in the inventive process:
ruthenium chloride-cesium acetate, ruthenium(IV) oxide-cesium acetate) ruthenium chloride-cesium trifluoroacetate, ruthenium chloride-sodium acetate, ruthenium chloride-cesium proprionate, triruthenium dodecacarbonylcesium acetate, ruthenium oxide-cesium fluoride. Theri effectiveness is illustrated in Examples 18 to 28.
Salts o' quaternary ammonium and phosphonium cations are also effective as co-catalysts in the process of this ~5~7~
inventionD Suitable quaternary phosphonium salts are those which are substantially inert under the C0-hydrogenation conditions and which have the formula:
Rl , R2 ~ P R3 X
where Rl, R2, R3 and R4 are organic radicals bonded to the phosphorus atom by a saturated aliphatic carbon atom, and X is an anionic species, preferably of a carboxylic acid, defined below. The organic radicals useful in this instance include those having 1 to 20 carbon akoms in a branched or linear alkyl chain; they include the methyl, ethyl, n-butyl, iso-butyl, octyl, 2-ethylhexyl and dodecyl radicals. Tetramethylphosphonium acetate and tetrabutylphosphonium acetate are typical commercially available phosphonium salts. The cor~esponding quaternary phosphonium and ammonium hydroxides, nitrates and halides, such as the corresponding chlorides, bromides and iodides, are also satisfactory in this instance, as are quaternary ammonium salts of carboxylic acids such as tetra-n-butylammonium acetate, and tetra-n-octylammonium propionate as well as the corresponding iminium salts such as bis ~triphenylphosphine) iminium acetate. Examples 25 17, 18, 32 and 33 provide evidence of the effectiveness of the ruthenium chloride-tetrabutylphosphonium acetate couple.
Similar catalyst combinations, containing osmium rather than rutheniùm as the transition-metal component, are also suitable for the desired synthesis of alkanol and polyhydric alcohol esters from synthesis gas.
Having described the inventive process in general terms, the following examples are submitted to supply specific and illustrative embodiments. All percentages are by weight.
EX~PLE 1 To a degassed sample of acetic acid (50 ml~
contained in a 300 ml ylass-lined reactor equipped for pressurizing, heating and means of agitation is added, under a nitrogen environmentl 0.40 gm of ruthenium acetylacetonate (1.0 mmolei. The reactor is sealed, flushed with C0/~2 and pressured to 184 atmospheres (2700 psi, with synthesis gas (1:1, C0/H2). The mixture is then heated to 220C, with agitation for 18 hr, and then allowed to cool. Gas uptake i5 2702 atmospheres (400 psi.) Excess gas is sampled and vented~ the yellow-red liquid product, analyzed by glc, shows the presence of :
1.9~ methyl acetat~
0.3% ethyl acetate 1.4% ethylene glycol diacetate Yellow, crystalline triruthenium dodecacarbonyl slowly - precipitates from ~his product solution upon standing and upon exposure to air.
The vented off-gas typically has the composition:
47% hydrogen 48~ carbon monoxide 1.3% carbon dioxide
MANUF~CTURE OF VICINAL GLYCOL ESTE~S
FROM SYNT~ESIS GAS
This invention concerns an improved process for preparing alkanol and vicinal glycol ester compounds, including ester derivatives of ethylene glycol, by reaction of oxides of carbon with hydrogen.
~ More particularly, the invention concerns the selective co-synthesis of alkanol and glycol esters, particularly the ester derivative of ethylene glycol, methanol and ethanol, by the catalytic reaction o carbon monoxide and hydrogen in the presence of a liquid medium containing a carboxylic acid co-reactant. Catalysis is effected in the presence of a catalyst containing osmium or ruthenium, with the latter being most preferred. The process is exemplified by, but not limited to the one step co-synthesis of ethylene glycol diacetate, methyl acetate and ethyl acetate from carbon monoxide, hydrogen mixtures in the presence of an acetic acid (HOAc) liquid medium according to the stoichiometry of eqs. (1) to (3):
~2CO + 3H2 + 2HOAc ~ ¦ ~ 2H2o (1) 2co + 4H2 ~ HOAc ~ CH3CH20Ac ~ 2H2o (2) CO + 2H2 + HOAc ~ CH30~c + H20 (3) Methyl acetate, ethyl acetate and glycol diacetate - are all products of recognized commercial valuej particularly as chemical intermediates and extractive solvents~ Methyl and ethyl acetates are used widely as solvents, primarily for surface coatings. Ethylene glycol diacetate is useful in the production of ethylene glycol, an important component in polyester fiber and antifreeze formulations. Free glycol may be generated from its diacetate deriva~ive via hydrolysis as disclosed, for example, in Belgian Patent No. 749,685.
It is the purpose of this invention to provide new routes to the preparation of alkanol and diol Psters using mixtures of carbon monoxide and hydrogen (hereinafter sometimes referred to as synthesis gas or syngas). This is 1~5667~
particularly true where methyl acetate, ethyl acetate and glycol diacetate are the principal products (eqs. 1-3), since in this case acetic acid is the co-reactant medium, and one route to HOAc manufacture is fxom synthesis gas via methanol carbonylation. ("Trends in Petrochemical Technology" by A. M. Brownstein, Chapter 5 (1976~).
In recent years, a large number of patents have been issued dealing with the synthesis of lower molecular weight hydrocarbons, olefins, and alkanols, from synthesis gas. Of particular note, U.S. Patent No. 2,636,o46 discloses the synthesis of polyhydric alcohols and their ~ derivatives by reaction between carbon monoxide and hydrogen at elevated pressures (>1500 atm or 22,000 psi) and temper-atures to 400C using certain cobalt-containing catalysts.
~ore recently, i~ 8elgian Patent No. 793,086 and U.S. Patent No. 3,940,432 there is described the co-synthesis of methanol and ethylene glycol from mixtures of carbon monoxide and hydrogen using a rhodium compl~x catalyst. Typically, CO-hydrogenation is effected at 544 atmospheres (8000 psi) of l:l H2/CO synthesis gas, at 220C, using tetraethylene glycol methyl ether as the solvent, and dicarbonylacetyl-acetonatorhodium(I) in combination with an organic Lewis base as the catalyst precursor. (For a summary of the work, see: R. L. Purett, Annals New York Academy of Sciences, Vol. 295 p. 239 (1977))~ While other metals of Group VIII
of the Periodic Table have been tested for activity under similar conditions, including cobalt, ruthenium, copper, manganese, iridium and platinum, only cobalt was found to have slight activity. The use of ruthenium compounds in particular failed to produce polyfunctional products such as ethylene glycol. ~his is illustrated in U.S. Patent No.
3,833,634 for solutions of triruthenium dodecarbonyl.
The present invention provides a process for the concurrent synthesis of alkanol and vicinal glycol esters which comprises heating a reaction mixture of carbon monoxide and hydrogen, (with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester syntheses), a liquid medium containing one or more carboxylic acids and a catalyst containing ruthenium, osmium or a mixture thereof~
1 1~6671 at a temperature between 100C and 350C, and a superatomos-pheric pressure of at least 34 atmospheres (500 psi).
In one preferred embodiment, the reaction mixture contains, as a co--catalyst one or more alkali metal salts, alkaline earth metal salts, quaternary a onium salts, iminium salts or quaternary phosphonium salts.
Further details of the invention are as follows:
A. Catalyst Composition - Catalysts that are suitable in the practice o this invention contain osmium or ruthenium 1~ or mixtures of these metalsO The ruthenium or osmium-containing catalyst may be chosen from a wide variety of organic or inorganic compounds or complexes, as will be shown and illustrated below. It is only necessary that ths catalyst precursor actually employed contain the transition metal (i.e. ruthenium or osmium) in any of its ionic states.
The actual catalytically active species are then believed to comprise ruthenium or osmium in complex combination with carbon monoxide and hydrogen~ The most effective catalysis is achieved where the ruthenium or osmium hydrocarbonyl species are solubilized in the carboxylic acid co-reactant employed to satisfy the stoichiometry of eq 1 3.
While the invention will be more specifically discussed below in terms of typical ruthenium-containing forms or species, it is understood that osmium may be employed in like forms in most cases without departing from the scope of the invention~
The preferred ruthenium catalyst pxecursors may take many different forms. For instance, the ruthenium may be added to the reaction mixture in an oxide form, as in the case of, for example, ruthenium(IV) oxide, hydrate, anhydrous ruthenium(IV) dioxide and ruthenium(VIII) tetraoxide.
Alternatively, it may be added as the salt of a mineral acid, as in the case o,f ruthenium(III) chloride hydrate, ruthenium~III) bromide, anhydrous ruthenium(III) chloride and ruthenium nitrate, or as the salt of a suitable organic carboxylic acid (see Section B, below), for example, ruthenium(III) acetate, ruthenium(III) propionate, ruthenium butyrate, ruthenium(III) trifluoroacetate, ruthenium octanoate, ruthenium napththenate, ruthenium valerate and ruthenium(III) 1 ~56671 acetylacetonate. The ruthenium may also be added to the reaction zone as a carbonyl or hydrocarbonyl derivative.
Here, suitable examples include triruthenium dodecacarbonyl, hydrocarbonyls such as H2Ru4(CO)13 and H4Ru4(CO)12, and substituted carbonyl species such as the tricarbonylruthenium (II) chloride dimer, [Ru(CO)3C12~2.
In a preferred embodiment of the invention ruthenium is added to the reaction zone as one or more oxide, salt or carbonyl derivative species in combination with one or more group VB tertiary donor ligands. The key elements of the Group VB ligands include nitrogen, phosphorus, arsenic and antimony. These elements, in their trivalent oxidation states, particularly tertiary phosphorus and nitrogen, may be bonded to one or more alkyl, cycloalkyl, aryl, substituted aryl, aryloxide, alkoxide, alkaryl or aralkyl radicals, each containing from 1 to 12 carbon atoms, or they may be part of a heterocyclic ring system, or be mixtures thereo. Illustrative examples of suitable ligands that may be used in this invention include: triphenylphosphine, tri-n-butylphosphine, triphenylpho~phite, triethylphosphite, trimethylphosphite, trimethylphosphine, tri-~-methoxyphenylphosphine, triethyl-phosphine, trimethylarsine, triphenylarsine, txi-~-tolyl-phosphine, tricyclohexylphosphine, dimethylphenylphosphine, trioctylphosphine, tri-o-tolylphosphine, 1,2-bis(diphenyl-phosphino)ethane, triphenylstibine, trimethylamine, triethyl-amine, tripropylamine, tri-n-octylamine, pyridine, 2,2'-dipyridyl, l,10-phenanthroline, quinoline, N,N'dimethyl-piperazine, ~8-bis(dimethylamino)naphthalene and N,N-dimethylaniline.
One or more of these ruthenium-teriary Group VB donor ligand combinations may be preformed, before addition to the reaction mixture, as in the case, for example, of tris ~triphenylphosphine)ruthenium(II) chloride and tricarbonyl-bis(triphenylphosphine)ruthenium or alternati~ely, said complexes may be formed in situ.
The perfor~ances of each of these classes of ruthenium catalyst precursors are illustrated by the accompanying examples, described below.
1 1~667 1 Similar catalyst combinations, containing osmium rather than ruthenium as the transition-metal component, are also suitable for the desired synthesis of alkanol and polyhydric alcohol esters from synthesis gas.
B. _ Carboxylic Acids : Carboxylic acids useful in the process of this invention form the acid moiety of the sesired methyl, ethyl and glycol ester products. Preferably, said acids are also useful as solvents for the transition-metal catalysts, particularly the ruthenium catalyst combin-ations. Suitable carboxylic acids include aliphaticacids, alicyclic monocarboxylic acids, heterocyclic acids and aromatic acids, both substituted and non-substituted.
For example, this invention contemplates the use of aliphatic monocarboxylic acids of 1 to 12 carbon atoms such as formic acid, acetic, propionic, butyric, isobutyric, valeric, caproic, capric, perlargonic and lauric acids, together with aliphatic dicarboxylic acids of 2 to 6 carbons, such as oxalic, malonic, succinic and adinic acids. Alternatively substituted aliphatic monocarboxylic acids containing one or more functional substituents, such as chlorine or fluorine atoms, or alkoxy, cyano, alkylthio, or amino groups.
Examples of such acids include acetoacetic acid, dichloroacetic acid, trifluoroacetic acid, chloropropionic acid, trichloro-acetic acid, and monofluoroacetic acid. Among suitable aromatic acids are benzoic acid, napthoic acids, toluic acids, chloxobenzoic acids, aminobenzoic acids and phenylacetic acid.
~he alicyclic monocarboxylic acids may contain from 3 to 6 carbons in the (substituted or unsubstituted) ring and may contain one or more carboxyl groups, such as cyclopentane-carboxylic acid or hexahydrobenzoic acid. The heterocyclicacids may contain 1 to 3 fused rings, which may be substituted or unsubstituted, together with one or more cax~oxylic groups, exa~ples include quinolinic, furoic and picolinic acids. Mixtures of said classes of carboxylic acids, in any ratio, may also be used in the inventive process. The preferred carboxylic acids are the aliphatic acids such as acetic acid, propionic acid and butyric acid, and substituted aliphatic acids such as trifluoroacetic acid 1 ~667~
C. Catalyst Concentration - The quantity of ruthenium or osmium catalyst employed in the invention is not critical and may vary over a wide range. In general, the novel process is desirably conducted in the presence of a catalyt-ically effective quantity of the active ruthenium or osmiumspecies which gives the desired ester products in reasonable yields. Reaction proceeds when employing as little as 1 x 10 6 weight percent, and even lesser amounts, of ruthenium or osmium, basis the total weight of the reaction mixture.
The upper concentration is dictated by a variety of factors including catalyst cost, partial pressures of carbon monoxide and hydrogen, operating temperature and choice of carboxylic acid diluent/reactant. A concentration of from 1 x 10 5 to 10 weight percent of ruthenium, or osmium based on the total weight of reaction mixture, is generally desirable in the practice of this invention.
D. Operating Temperature - The temperature range which can usefully be employed in these ester syntheses is variable dependent upon other experimental factors, including the choice of carboxylic acid co-reactant, the pressure, and the concentration and particular choice of catalyst among other things. Again using ruthenium as the active metal/ the range of operability is from 100 to 350C when superatmospheric pressures o~ syngas are employed. A narrower range of 150-260C represents the preferred temperature range when the major products are methyl, ethyl and glycol acetates.
Table I is evidence of how the narrower range is derived.
E. Pressure - Superatmospheric pressures of 34 atmospheres (500 psi) or greater lead to substantial yield of desirable alkanol and vicinal glycol ester by the process of this invention. A preferred operating range for solutions of ruthenium ~III) acetylacetonate in acetic acid is from 68 to 510 atmospheres (1000 to 7500 psi) although pressures .
above 510 atmospheres (7500 psi) also provide useful yields of desired ester. Table I is evidence of this preferred, narrower range of operating pressures. The pressures referred to here represent the total pressure generated by all the reactants, although they are substantially due to the carbon monoxide and hydrogen fractions in these examples.
6 7 ~
F. Gas ComPosition - The relative amounts of carbon monoxide and hydrogen which may be initially present in the syngas mixture are variable, and these amounts may be varied over a wide range. In general, the mole ratio of CO-to-H2 is in the range from 20:1 up to 1:20, preferably from 5:1 to 1:5, although ratios outside these ranges may also be employed. Particularly in continuous operations, but also in batch experiments, the carbon monoxide-hydrogen gaseous mixtures may also be used in conjunction with up to 50% by volume of c e or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, or neon, they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions such as carbon dioxide; hydrocarbons such as methane, ethane or propane;
ethers such as dimethyl ether, methyl ethyl ether and diethyl ether; alkanols such as methanol; and acid esters such as methyl acetate.
In all syntheses, the amount of carbon monoxide and hydrogen present in the reaction mixture should be suf~icient to satisfy the stoichiometry of eq (1) to (3).
G. Product Distribution - As far as can be determined, without limiting the invention thereby, the ruthenium or osmium catalyst one-step CO-hydrogenation process disclosed herein leads to the formation of three classes of primary products, namely the methanol, ethanol and ethylene glycol ester derivatives of the corresponding co-reactant carboxylic acid. When acetic acid is the co-reactant, the pxincipal products are methyl acetate, ethyl acetate and ethylene glycol diacetate. Minor by-products detected in the liquid product 3C fraction include small amounts of water, glycol monoacetate, propyl acetate and dimethyl ether. Carbon dioxide, methane and dimethyl ether may be detected in the off-gas together . with unreacted carbon monoxide and hydrogen.
H. Mode of OPeration - The novel process of this invention can be conducted in a batch, semi-continuous or continuous fashion. The catalyst may be initially introduced into the reaction zone batchwise, or it may be continuously or intermittently introduced into such a zone during the course of the synthesis reaction. Operating conditions can be ~ ~5~67~
adjusted to optLmize the formation of the desired ester product, and said material may ~e recovered by methods well known in the art, such as distillation, fractionation, extraction and the like. A fraction rich in ruthenium or osmium catalyst components may then be recycled to the reac-tion zone, if desired, and additional egter products generated by CO hydrogenation.
I. Identificat;ion Procedures - The products of CO-hydrogenation have been identified in this work by one or more of the following analytical procedures, viz, gas-liquid phase chromatography (glc), infrared (ir), mass spectrometry, nuclear magnetic resonance ~nmr) and elemental analyses, or a combination of these techniques.
J._ Co-Catalyst - There are several classes of suitable co-catalysts for use in one embodiment of the invention.
One such class which may be added to the reaction mixtures to enhance the activity of the solubilized ruthenium or osmium catalysts æ e the salts of the alkali and alkaline earth metals.
Illustrative examples of ef~ective alkali metal salts include the alkali metal halides, for instance, the fluoride, chloride, bromide and iodide salts, and alkali and alkaline earth metal salts of suitable carboxylic acids. The preferred alkali and alkaline earth metal carboxylates are the acetate, propionate and butyrate salts of sodium, potassium, barium and cesium. These salts may be added over a wide range of concentrations, e.g. from O.Ol to 1O2 moles of alkali or alkaline earth salt per gm atom of ruthenium or osmium present in the reaction mixture. The most preferred ratios are from 5:1 to 15:1 ~See Table II).
The following are typical combinations of ruthenium-co-catalyst combinations useful in the inventive process:
ruthenium chloride-cesium acetate, ruthenium(IV) oxide-cesium acetate) ruthenium chloride-cesium trifluoroacetate, ruthenium chloride-sodium acetate, ruthenium chloride-cesium proprionate, triruthenium dodecacarbonylcesium acetate, ruthenium oxide-cesium fluoride. Theri effectiveness is illustrated in Examples 18 to 28.
Salts o' quaternary ammonium and phosphonium cations are also effective as co-catalysts in the process of this ~5~7~
inventionD Suitable quaternary phosphonium salts are those which are substantially inert under the C0-hydrogenation conditions and which have the formula:
Rl , R2 ~ P R3 X
where Rl, R2, R3 and R4 are organic radicals bonded to the phosphorus atom by a saturated aliphatic carbon atom, and X is an anionic species, preferably of a carboxylic acid, defined below. The organic radicals useful in this instance include those having 1 to 20 carbon akoms in a branched or linear alkyl chain; they include the methyl, ethyl, n-butyl, iso-butyl, octyl, 2-ethylhexyl and dodecyl radicals. Tetramethylphosphonium acetate and tetrabutylphosphonium acetate are typical commercially available phosphonium salts. The cor~esponding quaternary phosphonium and ammonium hydroxides, nitrates and halides, such as the corresponding chlorides, bromides and iodides, are also satisfactory in this instance, as are quaternary ammonium salts of carboxylic acids such as tetra-n-butylammonium acetate, and tetra-n-octylammonium propionate as well as the corresponding iminium salts such as bis ~triphenylphosphine) iminium acetate. Examples 25 17, 18, 32 and 33 provide evidence of the effectiveness of the ruthenium chloride-tetrabutylphosphonium acetate couple.
Similar catalyst combinations, containing osmium rather than rutheniùm as the transition-metal component, are also suitable for the desired synthesis of alkanol and polyhydric alcohol esters from synthesis gas.
Having described the inventive process in general terms, the following examples are submitted to supply specific and illustrative embodiments. All percentages are by weight.
EX~PLE 1 To a degassed sample of acetic acid (50 ml~
contained in a 300 ml ylass-lined reactor equipped for pressurizing, heating and means of agitation is added, under a nitrogen environmentl 0.40 gm of ruthenium acetylacetonate (1.0 mmolei. The reactor is sealed, flushed with C0/~2 and pressured to 184 atmospheres (2700 psi, with synthesis gas (1:1, C0/H2). The mixture is then heated to 220C, with agitation for 18 hr, and then allowed to cool. Gas uptake i5 2702 atmospheres (400 psi.) Excess gas is sampled and vented~ the yellow-red liquid product, analyzed by glc, shows the presence of :
1.9~ methyl acetat~
0.3% ethyl acetate 1.4% ethylene glycol diacetate Yellow, crystalline triruthenium dodecacarbonyl slowly - precipitates from ~his product solution upon standing and upon exposure to air.
The vented off-gas typically has the composition:
47% hydrogen 48~ carbon monoxide 1.3% carbon dioxide
2.2~ methane _ --In the preparation, C0-hydrogenation i5 carried out as described in Example 1, except that the charge mixture consists of 0.4~6 gm of triruthenium dodecacarbonyl (0.66 mmole~ solubilized in 50 ml of acetic acid. Analysis of the product liquid by glc shows the presence of :
4.2% methyl acetate 0.5~ ethyl acetate 0.4~ e~hylene glycol diacetate In this preparation, CC-hydrogenation is carried out as described in Example 1 except that the charge mixture consists of 0.71 gm of tricarbonylbis(triphenyl-~` :
~ 1~6~71 phosphine~ ruthenium ~1,0 mmole~ in 50 ml of glacial acetic acid. Analysis of the product liquid shows :
4.2% methyl acetate 0.5~ ethyl acetate 0.4~ e~hylene glycol diacetate In this preparation, CC-hydrogenation is carried out as described in Example 1 except that the charge mixture consists of 0.71 gm of tricarbonylbis(triphenyl-~` :
~ 1~6~71 phosphine~ ruthenium ~1,0 mmole~ in 50 ml of glacial acetic acid. Analysis of the product liquid shows :
3.4 wt. % methyl acetate 0.8 wt. % ethyl acetate 0.2 wt. ~ ethylene glycol diacetate .
In this preparation, C0-hydrogenation i5 carried out as described in Example 1, except that the charge mixture consists of 0.722 gm of ruthenium (III) hexa-fluoroacetylacetonate (1 mmole) in 50 ml of acetic acid.
10 Analysis of the product liquid shows :
5.7% methyl acetate 0.2% ethyl acetate 0.26% ethylene glycol diacetate In this preparation, C0-hydrogenation is carried out as described in Example 1, except that the charge mixture consists of 0.40 gm of ruthenium (III) acetylacetonate (1 mmole), 0.40 gm of tri-n-butylphosphine, and 50 ml of acetic acid. Analysis of the product liquid 20 shows the presence of significant quantities of methyl acetate, ethyl acetate and ethylene glycol diacetate.
E X A M P ~ E 6 In this preparation~ C0-hydrogenation is carried out as described in Example 1, except that the charge 25 mixture consists of 0.598 gm of triosmium dodecacarbonyl (0~66 mmole) solubilized in 50 ml of acetic acid.Analysis of the product liquid by glc shows the presence of methyl acetate and ethylene glycol diacetate.
E X A M P L ~ S 7 T0 12 In these examples, using the techniques and procedures , of Example 1, the effect of varying the operating temperature and pressure upon the yield and distribution of acetic ester products has been examined. The standard catalyst here is ruthenium (III) acetylacetonate (1-2 mmole) 35 solubilized in glacial acetic acid. The results are summarized in Table 1, It is evident from the data that methyl, ethyl and ethylene ~lycol acetates may each be generated via C0 hydrogenation with the solubilized ruthenium catalyst at least over the operating temperature, pressure ranges o~ 180-260C and 88.5 to 500 atmospheres ~1300-7350 psi) ` I 156671 N
O ~ ~ u~. ~r N . . . .
t~ O O O O ~ O
O 1:) O ~ ~
h 1~ O O O O O N
~-1 ::~
O r~
~ Q) H 5 O O ~ ~ U~ I`
~ O I` N 0 Il') 0 'i O N
C) 5: O O ~I t~ N Ll'l ~rl Ql _I h ~ ~ 8 o U 8 m o~ ~ ~ ~ ~
U? O ~D _I N ~ U~ I`
Et X Q) ~ O ~ ~ ~ ~ O
D O
P~ ~ ~r CD ~ N ~ Ll~) OD U~
~0 --1-1 ~ C~ N N N N ~D
a) E _I N ~ t~
OE~
E r~ o x ~ l .
_ ~3 -~ 14 ~
.
Following the procedure of Example 1, O,80 sm of ruthenium ac~tylacetonate (2.0 mmolel is added to a degassed sample of acetic acid (50 ml~ set in the 300 ml glass-lined reactor. The reac~or is sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with 1:1 synthesis gas. The mixture is then heated to 220C with agitation, for 18 hrs. and allowed to cool.
Gas uptake is 68 atmospheres (1000 psi). Excess gas is vented and a small (l ml) liquid sampled recovered for analysis. Glc shows the presence of:
12.3~ methyl acetate 1.0~ ethylene glycol diacetate 0.5% ethyl acetate The remainder of the product liquid is recycled to the 300 ml reactor, repressured with 1:1 synthesis gas, and CO-hydrogenation effected as described above. The final product after repeated cycling shows the following composition:
44.9% methyl acetate - 2.2~ ethylene glycol diacetate 1.4~ ethyl acetate together with unreacted acetic acid and an aqueous by -product. The methyl acetate, ethyl acetate and ethylene glycol diacetate are recovered as overhead fractions via distillation under reduced pressure (O.l-lOmm Hg). A
bottoms fraction (2 gm) plus crystallized triruthenium dodecacarbonyl (0.2 gm) are recycled to the reactor with fresh acetic acid (50 ml), and conversion of CO/H2 tc acetate esters is carried out as described above.
Recovered, clear, yellow liquid product (46 ml) shows the presence of :
11.6~ methyl acetate 2.2~ ethvlene glycol diacetate 0.5~ ethyl acetate 1 ~ ~667 ~
The followiny Examples 14 and 15 provided for purposes of comparison show that seeming equivalent catalysts, c0~21t and rhodium are relatively ine~fective for use in the process here.
E _X A M P ~ E 14 (For C~parison) To a degassed ~mple of acetic acid (S0 ml) contained in a 3Q0 ml glass-lined reactor equipped for pressurizing, heating and means of agitation is added, under a nitrogen environment, 0.80 gm of rhodium ~III) acetylacetonate (l.O mmole). The reacto.r is sealed, flushed with C0/H2 and pressured to 184 atmospheres ~2700 psi) with synthesis gas (184 atm,l.l, C0/H2).
The mixture is then heated to 220C, with agitation, for 18 hr, and then allowed to cool~ Excess gas is sampled and vented, the liquid product, analyzed by glc, shows the presence of 0.5~ methyl acetate 1.2~ ethyl acetate 0.1% glycol diacetate E X A M P L E 15 lFor Comparison) In this preparation, C0-hydrogenation is carried out as described in Example 14, except that the charge mixture consists of 0.34 gm of dicobalt octacarbonyl (1 mmole) and 50 ml of acetic acid. Analysis of the product liquid (49 ml) by glc shows the presence of :
0.7% methyl acetate 2.7~ ethyl acetate 0.1% glycol diacetate Following the procedure of Fxample 1, 0.40 gm of ruthenium (III) acetylacetonate (1.0 mmole) and 50 ml of trifluoroacetic acid are charged to a glass-lined, 450 ml reactor. The reactor is sealedr flushed with 35 C0/H2, pressured to 272 atmospheres (4G00 psi) with C0/H2 (1:1) and heated to 220C overnight. Gas uptake is 95.25 atmospheres (1400 psi3, Upon cooling~ the green liquid product, containing suspended solids, is recovered and analyzed ~y glc. Analysis shows this material to consist of:
37~ methyl ~rifluoroacetate 29 3% ethyl trifluoroacetate 2.2% ethylene glycol di (tri~luoroacetate) 43.0~ unreacted trifluroacetic acid The following Examples 17 to 36 illustrate the embodiment of the invention employing a co-catalyst.
.
To an 850ml glass-lined autoclave reactor equipped for pressurizing, heating, cooling and means of agitation is charged 1.04gm of ruthenium chloride, hydrate (4.0 mmole), lS 12.7~m of tetrabutylphosphonium acetate (40 mmole) and acetic acid (50 gm). Upon stirring, all solids dissolve to give a clear, deep-red solution. The reactor is then sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (a 1:1 mixture of hydrogen and carbon monoxide.) Over a period of 60-75 minutes, the autoclave is heated, with agitation, to 220C, and held at temperature overnight. Total gas uptake is 122.5 atmos-pheres (1800 psi). After cooling, the excess gases are sampled and vented, and the deep -red liquid product (58 ml) removed for analysis. There is no solid product fraction.
Analyses of this liquid fraction by gas-liquid phase chromatography (glc) shows the presence of :
- 63.9 wt. % methyl acetate 6.28 wto ~ ethylene glycol diacetate 30 S.9 wt. ~ ethyl acetate lg~ 7 wto ~ unreacted acetic acid To a 300 ml glass-lined autoclave equipped for pressurizing, heating and means of agitation is charged 0.52 gm of ruthenium chloride, hydrate (2.0 mmole3, 19.08 gm of tetrabutylphosphonium acetate (60 mmole) and cetic acid (25 gm~, The mixture is stirred to dissolve solids, the reactor sealed~ flushed with CO/Hz and pressured to 272 atmosphere (4000 psi~ with synthesis gas (1:1, CO/H2). Over a period of 60-75 minutes, the autoclave is heated, with agitation, to 220C and held at temperature overnight. Total gas uptaXe is 105.5 atmospheres (1550 psij. After cooling, the excess gas is vented and the deep-red liquid product (43 ml) removed from the reactor.
Analysis of this liquid fraction by glc shows the presence of :
52.3 wt.% methyl acetate 6.71 wt.% ethylene glycol diacetate
In this preparation, C0-hydrogenation i5 carried out as described in Example 1, except that the charge mixture consists of 0.722 gm of ruthenium (III) hexa-fluoroacetylacetonate (1 mmole) in 50 ml of acetic acid.
10 Analysis of the product liquid shows :
5.7% methyl acetate 0.2% ethyl acetate 0.26% ethylene glycol diacetate In this preparation, C0-hydrogenation is carried out as described in Example 1, except that the charge mixture consists of 0.40 gm of ruthenium (III) acetylacetonate (1 mmole), 0.40 gm of tri-n-butylphosphine, and 50 ml of acetic acid. Analysis of the product liquid 20 shows the presence of significant quantities of methyl acetate, ethyl acetate and ethylene glycol diacetate.
E X A M P ~ E 6 In this preparation~ C0-hydrogenation is carried out as described in Example 1, except that the charge 25 mixture consists of 0.598 gm of triosmium dodecacarbonyl (0~66 mmole) solubilized in 50 ml of acetic acid.Analysis of the product liquid by glc shows the presence of methyl acetate and ethylene glycol diacetate.
E X A M P L ~ S 7 T0 12 In these examples, using the techniques and procedures , of Example 1, the effect of varying the operating temperature and pressure upon the yield and distribution of acetic ester products has been examined. The standard catalyst here is ruthenium (III) acetylacetonate (1-2 mmole) 35 solubilized in glacial acetic acid. The results are summarized in Table 1, It is evident from the data that methyl, ethyl and ethylene ~lycol acetates may each be generated via C0 hydrogenation with the solubilized ruthenium catalyst at least over the operating temperature, pressure ranges o~ 180-260C and 88.5 to 500 atmospheres ~1300-7350 psi) ` I 156671 N
O ~ ~ u~. ~r N . . . .
t~ O O O O ~ O
O 1:) O ~ ~
h 1~ O O O O O N
~-1 ::~
O r~
~ Q) H 5 O O ~ ~ U~ I`
~ O I` N 0 Il') 0 'i O N
C) 5: O O ~I t~ N Ll'l ~rl Ql _I h ~ ~ 8 o U 8 m o~ ~ ~ ~ ~
U? O ~D _I N ~ U~ I`
Et X Q) ~ O ~ ~ ~ ~ O
D O
P~ ~ ~r CD ~ N ~ Ll~) OD U~
~0 --1-1 ~ C~ N N N N ~D
a) E _I N ~ t~
OE~
E r~ o x ~ l .
_ ~3 -~ 14 ~
.
Following the procedure of Example 1, O,80 sm of ruthenium ac~tylacetonate (2.0 mmolel is added to a degassed sample of acetic acid (50 ml~ set in the 300 ml glass-lined reactor. The reac~or is sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with 1:1 synthesis gas. The mixture is then heated to 220C with agitation, for 18 hrs. and allowed to cool.
Gas uptake is 68 atmospheres (1000 psi). Excess gas is vented and a small (l ml) liquid sampled recovered for analysis. Glc shows the presence of:
12.3~ methyl acetate 1.0~ ethylene glycol diacetate 0.5% ethyl acetate The remainder of the product liquid is recycled to the 300 ml reactor, repressured with 1:1 synthesis gas, and CO-hydrogenation effected as described above. The final product after repeated cycling shows the following composition:
44.9% methyl acetate - 2.2~ ethylene glycol diacetate 1.4~ ethyl acetate together with unreacted acetic acid and an aqueous by -product. The methyl acetate, ethyl acetate and ethylene glycol diacetate are recovered as overhead fractions via distillation under reduced pressure (O.l-lOmm Hg). A
bottoms fraction (2 gm) plus crystallized triruthenium dodecacarbonyl (0.2 gm) are recycled to the reactor with fresh acetic acid (50 ml), and conversion of CO/H2 tc acetate esters is carried out as described above.
Recovered, clear, yellow liquid product (46 ml) shows the presence of :
11.6~ methyl acetate 2.2~ ethvlene glycol diacetate 0.5~ ethyl acetate 1 ~ ~667 ~
The followiny Examples 14 and 15 provided for purposes of comparison show that seeming equivalent catalysts, c0~21t and rhodium are relatively ine~fective for use in the process here.
E _X A M P ~ E 14 (For C~parison) To a degassed ~mple of acetic acid (S0 ml) contained in a 3Q0 ml glass-lined reactor equipped for pressurizing, heating and means of agitation is added, under a nitrogen environment, 0.80 gm of rhodium ~III) acetylacetonate (l.O mmole). The reacto.r is sealed, flushed with C0/H2 and pressured to 184 atmospheres ~2700 psi) with synthesis gas (184 atm,l.l, C0/H2).
The mixture is then heated to 220C, with agitation, for 18 hr, and then allowed to cool~ Excess gas is sampled and vented, the liquid product, analyzed by glc, shows the presence of 0.5~ methyl acetate 1.2~ ethyl acetate 0.1% glycol diacetate E X A M P L E 15 lFor Comparison) In this preparation, C0-hydrogenation is carried out as described in Example 14, except that the charge mixture consists of 0.34 gm of dicobalt octacarbonyl (1 mmole) and 50 ml of acetic acid. Analysis of the product liquid (49 ml) by glc shows the presence of :
0.7% methyl acetate 2.7~ ethyl acetate 0.1% glycol diacetate Following the procedure of Fxample 1, 0.40 gm of ruthenium (III) acetylacetonate (1.0 mmole) and 50 ml of trifluoroacetic acid are charged to a glass-lined, 450 ml reactor. The reactor is sealedr flushed with 35 C0/H2, pressured to 272 atmospheres (4G00 psi) with C0/H2 (1:1) and heated to 220C overnight. Gas uptake is 95.25 atmospheres (1400 psi3, Upon cooling~ the green liquid product, containing suspended solids, is recovered and analyzed ~y glc. Analysis shows this material to consist of:
37~ methyl ~rifluoroacetate 29 3% ethyl trifluoroacetate 2.2% ethylene glycol di (tri~luoroacetate) 43.0~ unreacted trifluroacetic acid The following Examples 17 to 36 illustrate the embodiment of the invention employing a co-catalyst.
.
To an 850ml glass-lined autoclave reactor equipped for pressurizing, heating, cooling and means of agitation is charged 1.04gm of ruthenium chloride, hydrate (4.0 mmole), lS 12.7~m of tetrabutylphosphonium acetate (40 mmole) and acetic acid (50 gm). Upon stirring, all solids dissolve to give a clear, deep-red solution. The reactor is then sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (a 1:1 mixture of hydrogen and carbon monoxide.) Over a period of 60-75 minutes, the autoclave is heated, with agitation, to 220C, and held at temperature overnight. Total gas uptake is 122.5 atmos-pheres (1800 psi). After cooling, the excess gases are sampled and vented, and the deep -red liquid product (58 ml) removed for analysis. There is no solid product fraction.
Analyses of this liquid fraction by gas-liquid phase chromatography (glc) shows the presence of :
- 63.9 wt. % methyl acetate 6.28 wto ~ ethylene glycol diacetate 30 S.9 wt. ~ ethyl acetate lg~ 7 wto ~ unreacted acetic acid To a 300 ml glass-lined autoclave equipped for pressurizing, heating and means of agitation is charged 0.52 gm of ruthenium chloride, hydrate (2.0 mmole3, 19.08 gm of tetrabutylphosphonium acetate (60 mmole) and cetic acid (25 gm~, The mixture is stirred to dissolve solids, the reactor sealed~ flushed with CO/Hz and pressured to 272 atmosphere (4000 psi~ with synthesis gas (1:1, CO/H2). Over a period of 60-75 minutes, the autoclave is heated, with agitation, to 220C and held at temperature overnight. Total gas uptaXe is 105.5 atmospheres (1550 psij. After cooling, the excess gas is vented and the deep-red liquid product (43 ml) removed from the reactor.
Analysis of this liquid fraction by glc shows the presence of :
52.3 wt.% methyl acetate 6.71 wt.% ethylene glycol diacetate
4.2 w~. % ethyl acetate 25.4 wt. % unreacted acetic acid A similar product distribution ls achieved using an equivalent amount of ruthenium (IV) dioxide as the catalyst precursor and tetraethylphosphonium acetate of tetramethylphosphonium acetate as the co-catalyst component.
.
To the autoclave reactor of Example 17 is charged 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 8.0 gm o~ cesium acetate and acetic acid (50 gm)~ Upon stirring, all solids dissolve to give a clear, deep-red solution. The reactor is then sealed, flushed with C/~2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (1:1 ~2/CO). Over a period of 90 minutes, the autoclave is heated, with agitation, to 220C and held at temperature overnight. Total gas uptake is 68 atmospheres (1000 psi). After cooling, the excess gases are sampled and vented, and the liquid product recovered for analysis. Gas-liquid chromotography shows - the presence of :
l ~56~71 - 18 _ 42,0 wt.~ methyl acetate
.
To the autoclave reactor of Example 17 is charged 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 8.0 gm o~ cesium acetate and acetic acid (50 gm)~ Upon stirring, all solids dissolve to give a clear, deep-red solution. The reactor is then sealed, flushed with C/~2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (1:1 ~2/CO). Over a period of 90 minutes, the autoclave is heated, with agitation, to 220C and held at temperature overnight. Total gas uptake is 68 atmospheres (1000 psi). After cooling, the excess gases are sampled and vented, and the liquid product recovered for analysis. Gas-liquid chromotography shows - the presence of :
l ~56~71 - 18 _ 42,0 wt.~ methyl acetate
5,7 wt.~ ethyl acetate 3,2 wt,~ ethylene glycol diacetate 48.g wt.% unreacted acetic acid S ~
Following the procedure of Example 19, 1.04 gm of ruthenium chloride hydrate (4.0 mmole), acetic acid (50 gm) and ~arious ~uantities of cesium acetate (O to 60 mmole) are charged to the glass-lined reactorO
The reactor is sealed, ~lushed with C0/H2 pressured to 272 atmospheres (4G00 psi) with H2/C0(1:1) and heated to 220C overnight. Upon cooling, the li~uid product is recover~ and analyzed by glc. Table II summarizes the resultsO The formation of methyl acetate and ethylene glycol diacetate both appears to be ~avoured by the addition of cesium salt. 80th the ruthenium chloride and cesium acetate salts are readily solubilized in acetic acid, and initial (Cs) / (Ru~ ratios of S to 15 appear to provide the highest yields of glycol diacetate.
~: ~ ,, . ~ ~ U:l O O N ~ ~
U
~a ~1 ~ ~
~ ~ ~ _l g O
t3 ~ ~ O ~ O --:5 .
O ' C~ ~Q ~ CO
, dP , ~ 0~ oo ~ er ~ er u~
HO ::C ~ ''i O O O O
Es3 .~
~a ra O --I ~ ~ O Ln ~) ~ ,t ~0 E ~1 O ~ ~ O O O
,~
U-a~
O ~ ~ ~ ~ In C~l ~ ~
~1 . . .
To a 450 ml glass-lined autoclave reactor equipped for pressurizing, heating, cooling and means of agitation is charged 0.383 gm of ruthenium oxide, hydrate (2.0 mmole), 4.0 gm of cesium acetate and glacial acetic acid ~25 gm).
~he reactor is then sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (1:1, CO/H2). Over a period of 90 minutes, the clave is heated, with agitation, to 220C and held at temperature overnight.
Total gas uptake is 54.5 atmospheres (800 psi). After cooling, the excess gases are sampled and vented, and the brown liquid product (28 gm~ containing suspended solids is removed fox analysis. The liquid fraction shows the presence of :
7.3 wt.~ methyl acetate 2.59 wt. % ethylene glycol diacetate 1.8 wt. ~ ethyl acetate The vented off-gases typically have the composition:
44% hydrogen 39~ carbon monoxide 11% carbon dioxide 3.3% methane ~ollowing the procedures of Example 19, 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 3.28 gm of sodium acetate (40 mmole) and 50 gm of acetic acid are charged to a glass-lined reactor. The reactor is flushed with CO/H2 pressured to 272 atmospheres (4000 psi) with CO/H2 (1 and heated to 220C overnight, gas uptake is 54.5 atmospheres (800 psi). Upon cooling, the licuid product is recovered and ~alyzed by glc. Data are as ollo~s:
27.8 ~t.~ methyl acetate 1.8 wt. % ethyl acetate 1.67 wt. % ethylene glycol diacetate -Following the proceduxes of Example 19, 1.04 gm of ruthen~um chloride hydrate ~4.0 mmole), 201 gm of cesium propionate (10 mmolej and 25 ml of propionic acid are charged to a glass-lined, 450 ml reactor. The reactor is sealed, flushed with C0/H2, pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight.
~hen cooling, the yellow liquid product is recovered and analyzed by glc as ~ollows:
28.1% methyl propionate 1.30~ ethylene glycol dipropionate 0.3% ethyl propionate 64.9% unreacted propionic acid The residual off-gas consists primarily of unreacted carbon monoxid~ and hydrogen, viz:
47% hydrogen 43% carbon monoxide 7.2% carbon dioxide A similar product distribution is achieved using the equivalent amount of barium propionate as co-catalys~
instead of cesium propionate.
~ E X A M P L E 29 Following the procedure of Example 26, 0.763 gm of ruthenium oxide hydrate (4.0 mmole), 12.0 ~m of bis (tri-phenylphosphine) iminium acetate and 50 sm of acetic acid are charged to the glass~lined reactor. The reactor is flushed with C0/H2, pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight. Upon cooling, the liquid product is recovered and analyzed by glc.
Analysis shows the presence of .
26.7 wt. % of methyl acetate 9.5 wt. % of ethyl acetate 7.6 wt. % of water 1.39 wt~ % of glycol diacetate
Following the procedure of Example 19, 1.04 gm of ruthenium chloride hydrate (4.0 mmole), acetic acid (50 gm) and ~arious ~uantities of cesium acetate (O to 60 mmole) are charged to the glass-lined reactorO
The reactor is sealed, ~lushed with C0/H2 pressured to 272 atmospheres (4G00 psi) with H2/C0(1:1) and heated to 220C overnight. Upon cooling, the li~uid product is recover~ and analyzed by glc. Table II summarizes the resultsO The formation of methyl acetate and ethylene glycol diacetate both appears to be ~avoured by the addition of cesium salt. 80th the ruthenium chloride and cesium acetate salts are readily solubilized in acetic acid, and initial (Cs) / (Ru~ ratios of S to 15 appear to provide the highest yields of glycol diacetate.
~: ~ ,, . ~ ~ U:l O O N ~ ~
U
~a ~1 ~ ~
~ ~ ~ _l g O
t3 ~ ~ O ~ O --:5 .
O ' C~ ~Q ~ CO
, dP , ~ 0~ oo ~ er ~ er u~
HO ::C ~ ''i O O O O
Es3 .~
~a ra O --I ~ ~ O Ln ~) ~ ,t ~0 E ~1 O ~ ~ O O O
,~
U-a~
O ~ ~ ~ ~ In C~l ~ ~
~1 . . .
To a 450 ml glass-lined autoclave reactor equipped for pressurizing, heating, cooling and means of agitation is charged 0.383 gm of ruthenium oxide, hydrate (2.0 mmole), 4.0 gm of cesium acetate and glacial acetic acid ~25 gm).
~he reactor is then sealed, flushed with CO/H2 and pressured to 272 atmospheres (4000 psi) with synthesis gas (1:1, CO/H2). Over a period of 90 minutes, the clave is heated, with agitation, to 220C and held at temperature overnight.
Total gas uptake is 54.5 atmospheres (800 psi). After cooling, the excess gases are sampled and vented, and the brown liquid product (28 gm~ containing suspended solids is removed fox analysis. The liquid fraction shows the presence of :
7.3 wt.~ methyl acetate 2.59 wt. % ethylene glycol diacetate 1.8 wt. ~ ethyl acetate The vented off-gases typically have the composition:
44% hydrogen 39~ carbon monoxide 11% carbon dioxide 3.3% methane ~ollowing the procedures of Example 19, 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 3.28 gm of sodium acetate (40 mmole) and 50 gm of acetic acid are charged to a glass-lined reactor. The reactor is flushed with CO/H2 pressured to 272 atmospheres (4000 psi) with CO/H2 (1 and heated to 220C overnight, gas uptake is 54.5 atmospheres (800 psi). Upon cooling, the licuid product is recovered and ~alyzed by glc. Data are as ollo~s:
27.8 ~t.~ methyl acetate 1.8 wt. % ethyl acetate 1.67 wt. % ethylene glycol diacetate -Following the proceduxes of Example 19, 1.04 gm of ruthen~um chloride hydrate ~4.0 mmole), 201 gm of cesium propionate (10 mmolej and 25 ml of propionic acid are charged to a glass-lined, 450 ml reactor. The reactor is sealed, flushed with C0/H2, pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight.
~hen cooling, the yellow liquid product is recovered and analyzed by glc as ~ollows:
28.1% methyl propionate 1.30~ ethylene glycol dipropionate 0.3% ethyl propionate 64.9% unreacted propionic acid The residual off-gas consists primarily of unreacted carbon monoxid~ and hydrogen, viz:
47% hydrogen 43% carbon monoxide 7.2% carbon dioxide A similar product distribution is achieved using the equivalent amount of barium propionate as co-catalys~
instead of cesium propionate.
~ E X A M P L E 29 Following the procedure of Example 26, 0.763 gm of ruthenium oxide hydrate (4.0 mmole), 12.0 ~m of bis (tri-phenylphosphine) iminium acetate and 50 sm of acetic acid are charged to the glass~lined reactor. The reactor is flushed with C0/H2, pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight. Upon cooling, the liquid product is recovered and analyzed by glc.
Analysis shows the presence of .
26.7 wt. % of methyl acetate 9.5 wt. % of ethyl acetate 7.6 wt. % of water 1.39 wt~ % of glycol diacetate
6~71 Similar methyl, ethyl and glycol acetate yield distributions are achieved using an equivalent quantity of bis (triphenylphosphine~ iminium nitrate, tetramethy-lammonium acetate and/or tetrapropylammonium acetate as the co-catalyst component, instead of bis (triphenylphosphine) iminium acetate.
Here the procedures, ruthenium catalyst and solvent of Example 17 are employed, but the reactor is pressured to 4000 psi with a 2:1 mixture of hydrogen and carbon monoxide.
After heating to 220C, with agitation, the cooled liquid product shows the presence of :
29.4 wt.% methyl acetate 11.4 wt.% ethyl acetate 0~9 wt.~ ethylene glycol diacetate lS 5.4 wt.~ water 48.3 wt.% unreacted acetic acid .
Again the procedures, ruthenium catalyst and solvent of Example.17 are employed, but the reactor is pressured to 272 atmospheres t4000 psi) with a 1:2 mixture of hydrogen and carbon monoxide. After heating to 220C
with agitation, the cooled liquid shows the presence of:
33.6 wt.~ methyl acetate 11.8 wt.~ ethyl acetate 2.60 wt.~ ethylene glycol diacetate 47.4 wt.% unreacted acetic acid .
To an 850 ml glass-lined autoclave equipped with pressurizing, heating, cooling and means of agitation is charged 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 12.7 gm of tetrabutylphosphonium acetate and glacial acetic acid (50 gm). The reactor is then sealed, flushed with C0/H2 and pressured to 136 atmospheres (2000 psi) with synthesis gas (1:1, C0/H2~. Heat is applied to the reac~or and contents, the mixture agita~ed, and when the temperature reaches 220C~ the pressure is raised to 429 atmospheres (6300 psi) with 1:1 synthesis gas. The 1 ~56671 temperature is maintained at 220C overnight, the pressure is held in the range 408 to 429 a~mospheres (6000 to 6300 psi) by continuous addition o~ more syngas. Upon cooling, the excess gases are sampled and vented, and the deep-red liquid product 162 gm) is removed for ~nalysis. There is no solid product. The liquid fraction, analyzed by glc, shows the presence of:
61.9 wt.% methyl acetate 8 2 wt.~ ethyl acetate 5.61 wt.% e~hylene glycol diacetate 18.3 wt.~ unreacted acetic acid E X A M P L_E 33 Following the procedure of Example 32, 1.04 gm of ruthenium chloride, hydrate (4.0 mmole), 50 gm of glacial acetic acid and 10.72 gm of tetrabutylphosphonium acetate, freshly prepared from tri-n-butylphosphine and n-butyl acetate, are charged to an 850 ml glass-lined autoclave. The reactor is sealed, flushed with C0/~2 and pressured to 136 atmospheres (2000 psi) with synthesis gas (l:l,C0/H2). Heat is applied to the reactor and contents, the mixture agitated, and when the temperature reaches 220~, the pressure is raised to 429 atmospheres (6300 psi) with 1:1 synthesis gas. The temperature is maintained at 220C
overnight, the pressure is held in the range 408 to 429 atmospheres (6000-630G psi) by continuous addition of more syngas. Upon cooling, the excess gases are sampled and vented, and the deep-red liquid product (62 gm) is recovered for analysis. There is no solid product. The liquid fraction, analyzed by glc, shows the presence of:
66.8 wt.~ methyl acetate
Here the procedures, ruthenium catalyst and solvent of Example 17 are employed, but the reactor is pressured to 4000 psi with a 2:1 mixture of hydrogen and carbon monoxide.
After heating to 220C, with agitation, the cooled liquid product shows the presence of :
29.4 wt.% methyl acetate 11.4 wt.% ethyl acetate 0~9 wt.~ ethylene glycol diacetate lS 5.4 wt.~ water 48.3 wt.% unreacted acetic acid .
Again the procedures, ruthenium catalyst and solvent of Example.17 are employed, but the reactor is pressured to 272 atmospheres t4000 psi) with a 1:2 mixture of hydrogen and carbon monoxide. After heating to 220C
with agitation, the cooled liquid shows the presence of:
33.6 wt.~ methyl acetate 11.8 wt.~ ethyl acetate 2.60 wt.~ ethylene glycol diacetate 47.4 wt.% unreacted acetic acid .
To an 850 ml glass-lined autoclave equipped with pressurizing, heating, cooling and means of agitation is charged 1.04 gm of ruthenium chloride hydrate (4.0 mmole), 12.7 gm of tetrabutylphosphonium acetate and glacial acetic acid (50 gm). The reactor is then sealed, flushed with C0/H2 and pressured to 136 atmospheres (2000 psi) with synthesis gas (1:1, C0/H2~. Heat is applied to the reac~or and contents, the mixture agita~ed, and when the temperature reaches 220C~ the pressure is raised to 429 atmospheres (6300 psi) with 1:1 synthesis gas. The 1 ~56671 temperature is maintained at 220C overnight, the pressure is held in the range 408 to 429 a~mospheres (6000 to 6300 psi) by continuous addition o~ more syngas. Upon cooling, the excess gases are sampled and vented, and the deep-red liquid product 162 gm) is removed for ~nalysis. There is no solid product. The liquid fraction, analyzed by glc, shows the presence of:
61.9 wt.% methyl acetate 8 2 wt.~ ethyl acetate 5.61 wt.% e~hylene glycol diacetate 18.3 wt.~ unreacted acetic acid E X A M P L_E 33 Following the procedure of Example 32, 1.04 gm of ruthenium chloride, hydrate (4.0 mmole), 50 gm of glacial acetic acid and 10.72 gm of tetrabutylphosphonium acetate, freshly prepared from tri-n-butylphosphine and n-butyl acetate, are charged to an 850 ml glass-lined autoclave. The reactor is sealed, flushed with C0/~2 and pressured to 136 atmospheres (2000 psi) with synthesis gas (l:l,C0/H2). Heat is applied to the reactor and contents, the mixture agitated, and when the temperature reaches 220~, the pressure is raised to 429 atmospheres (6300 psi) with 1:1 synthesis gas. The temperature is maintained at 220C
overnight, the pressure is held in the range 408 to 429 atmospheres (6000-630G psi) by continuous addition of more syngas. Upon cooling, the excess gases are sampled and vented, and the deep-red liquid product (62 gm) is recovered for analysis. There is no solid product. The liquid fraction, analyzed by glc, shows the presence of:
66.8 wt.~ methyl acetate
7.3 wto % ethyl acetate 6.11 wt.% ethylene glycol diacetate 2.07 wt. ~ ethylene glycol monoacetate E X A M P L ~ 34_ Following the procedure of Example 30, 1.04 gm of ruthenium chloride hydrate (4.0 mmole), acetic acid (50 gm), together with cesium acetate (40 mmole) and triethylphosphite (12 mmole), are charged to the glass-lined reactor. The reactor is sealed, flushed with C0/H2 pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight. Upon cooling, the deep-red liquid product is recovered and analyzed by glc as follows:
22.1 wt ~ methyl acetate 17.6 wt ~ ethyl acetate 2.86 wt % ethylene glycol diacetate 54.5 wt % unreacted acetic acid Following the procedure of Example 19, 1.04 gm - of ruthenium chloride hydrate (4.0 mmole), acetic acid (50 gm), together with cesium acetate (40 mmole) and triphenylphosphite (12 mmole) are charged to the glass-lined reactor. The reactor is sealed, flushed with C0/H2j 20 pressured to 27~ atmospheres (4000 psi) with C0/H2 (1:1) and heatea to 220C overnight. Upon cooling, the deep-red liquid product (52 ml) is recovered and analyzed by glc as follows:- -26.6 wt % methyl acetate 16.5 wt ~ ethyl acetate 2.55 wt ~ ethylene glycol diacetate 50.8 wt ~ unreacted glacial acetic acid Following the procedure of Example 19, 1.04 gm of ruthenium chloride, hydrate (4.0 mmole), acetic acid (50 gm), together with cesium acetate (40 mmole) and triethylamine (4 mmole), are charged to the glass-lined reactor. The reactor is sealed, flushed ~ith C0/H2 (1:1), pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight. Upon cooling, the deep-red liquid product is recovered and analyzed ~y glc as follows:-~ 15~71 38,1 ~t ~ methyl acetate
22.1 wt ~ methyl acetate 17.6 wt ~ ethyl acetate 2.86 wt % ethylene glycol diacetate 54.5 wt % unreacted acetic acid Following the procedure of Example 19, 1.04 gm - of ruthenium chloride hydrate (4.0 mmole), acetic acid (50 gm), together with cesium acetate (40 mmole) and triphenylphosphite (12 mmole) are charged to the glass-lined reactor. The reactor is sealed, flushed with C0/H2j 20 pressured to 27~ atmospheres (4000 psi) with C0/H2 (1:1) and heatea to 220C overnight. Upon cooling, the deep-red liquid product (52 ml) is recovered and analyzed by glc as follows:- -26.6 wt % methyl acetate 16.5 wt ~ ethyl acetate 2.55 wt ~ ethylene glycol diacetate 50.8 wt ~ unreacted glacial acetic acid Following the procedure of Example 19, 1.04 gm of ruthenium chloride, hydrate (4.0 mmole), acetic acid (50 gm), together with cesium acetate (40 mmole) and triethylamine (4 mmole), are charged to the glass-lined reactor. The reactor is sealed, flushed ~ith C0/H2 (1:1), pressured to 272 atmospheres (4000 psi) with C0/H2 (1:1) and heated to 220C overnight. Upon cooling, the deep-red liquid product is recovered and analyzed ~y glc as follows:-~ 15~71 38,1 ~t ~ methyl acetate
8.1 wt ~ ethyl aceta~e 2.69 wt % ethylene glycol diacetate 47.6 wt % unreacted acetic acid
Claims (21)
- The embodiments of the invention in which an ex-clusive property or privilege is claimed are defined as follows:
l. A process for the concurrent synthesis of alkanol and vicinal glycol esters which comprises heating a reaction mixture of carbon monoxide and hydrogen (with sufficient carbon monoxide and hydrogen to satisfy the stoichiometry of the desired ester syntheses, a liquid medium containing one or more carboxylic acids and a catalyst containing ruthenium, osmium or a mixture thereof at a temperature between 100°C and 350°C, and a super-atmospheric pressure of at least 34 atmospheres (500 psi). - 2. A process as claimed in Claim l wherein the catalyst is a ruthenium oxide.
- 3. A process as claimed in Claim 2 wherein the ruthenium oxide is ruthenium (IV) dioxide, ruthenium (IV) dioxide hydrate or ruthenium (VIII) tetraoxide.
- 4. A process as claimed in Claim l wherein the catalyst is the salt of a carboxylic acid.
- 5. A process as claimed in Claim 4 wherein the salt is ruthenium acetate, ruthenium propionate, ruthenium butyrate, ruthenium trifluoroacetate, ruthenium acetylacetonate or ruthenium hexafluoroacetylacetonate.
- 6. A process as claimed in Claim l wherein the catalyst is the salt of a mineral acid.
- 7. A process as claimed in Claim 6 wherein the salt is ruthenium chloride hydrate, ruthenium bromide or anhydrous ruthenium chloride.
- 8. A process as claimed in Claim 1, 2 or 3 wherein the catalyst contains ruthenium and one or more Group VB tertiary donor ligands.
- 9. A process as claimed in Claim 1, 2 or 3 wherein the catalyst contains ruthenium and a Group VB tertiary donor ligand which is triphenylphosphine, tri-n-butylphosphine, triphenylphosphite, triethylphosphite, trimethyl-phosphine, triphenylarsine, trimethylamine, triethylamine, tripropylamine or tri-n-octylamine.
- 10. A process as claimed in Claim 1, 2 or 3 wherein the carboxylic acid co-reactant is an aliphatic carboxylic acid having 1 to 12 carbon atoms.
- 11. A process as claimed in Claim 1, 2 or 3 wherein the carboxylic acid co-reactant is acetic acid, propionic acid or butyric acid.
- 12. A process as claimed in Claim 1, 2 or 3 wherein the carboxylic acid co-reactant is a substituted aliphatic carboxylic acid.
- 13. A process as claimed in Claim 1, 2 or 3 wherein the carboxylic acid co-reactant is trifluoroacetic acid, dichloroacetic acid or monofluoroacetic acid.
- 14. A process as claimed in Claim 1, 2 or 3 wherein the ruthenium catalyst is a residual catalyst from previous syntheses o alcohol and vicinal glycol esters from Co/lH2 mixtures.
- 15. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species selected from alkali metal salts, alkaline earth metal salts, quaternary ammonium salts, iminium salts and quaternary aliphatic phosphonium salts.
- 16. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species which is an alkali metal salt of carboxylic acid .
- 17. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species which is cesium acetate, cesium propionate, cesium butyrate, sodium acetate or cesium trifluoroacetate.
- 18. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species which is a quaternary ammonium or phosphonium salt of a carboxylic acid.
- 19. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species which is tetramethylammonium acetate, tetrapropylammonium acetate tetramethylphosphonium acetate or tetrabutyl-phosphonium acetate.
- 20. A process as claimed in Claim 1, 2 or 3 wherein the reaction mixture comprises a co-catalyst species which is bis (triphenylphosphine) iminium acetate or bis (triphenylphosphine) iminium nitrate.
- 21. A process as claimed in Claim 15 wherein the reaction mixture comprises 5 to 15 moles, per gram atom of ruthenium or osmium, of a co-catalyst species selected from alkali metal salts, alkaline earth metal salts, quaternary ammonium salts iminium salts and quaternary aliphatic phosphonium salts.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US92169878A | 1978-07-03 | 1978-07-03 | |
| US92169978A | 1978-07-03 | 1978-07-03 | |
| US921,698 | 1978-07-03 | ||
| US921,699 | 1978-07-03 | ||
| US96794378A | 1978-12-11 | 1978-12-11 | |
| US96865578A | 1978-12-11 | 1978-12-11 | |
| US968,655 | 1978-12-11 | ||
| US967,943 | 1978-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1156671A true CA1156671A (en) | 1983-11-08 |
Family
ID=27506004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000331035A Expired CA1156671A (en) | 1978-07-03 | 1979-07-03 | Manufacture of vicinal glycol esters from synthesis gas |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU525120B2 (en) |
| BR (1) | BR7904194A (en) |
| CA (1) | CA1156671A (en) |
| FR (1) | FR2430404A1 (en) |
| GB (1) | GB2024811B (en) |
| IT (1) | IT1122004B (en) |
| NL (1) | NL7905114A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55104217A (en) * | 1979-02-05 | 1980-08-09 | Texaco Development Corp | Synthesis of ethylene from mixture of carbon monoxide and hydrogen |
| US4540810A (en) * | 1979-09-20 | 1985-09-10 | Texaco Development Corporation | Manufacture of alkanol and glycol esters |
| US4703064A (en) * | 1979-11-15 | 1987-10-27 | Union Carbide Corporation | Process for producing alcohols |
| DE3071425D1 (en) * | 1980-01-31 | 1986-03-27 | Ici Plc | Production of ethylene glycol from synthesis gas |
| US4540712A (en) * | 1980-03-31 | 1985-09-10 | Union Carbide Corporation | Process for producing methanol from synthesis gas |
| US4317946A (en) | 1980-06-27 | 1982-03-02 | The Halcon Sd Group, Inc. | Process for producing ethylene glycol via catalytic hydrogenation of glycolaldehyde |
| CA1172262A (en) * | 1980-12-24 | 1984-08-07 | Barbara K. Warren | Process for the production of ethylene glycol |
| CA1179315A (en) * | 1981-06-30 | 1984-12-11 | Union Carbide Corporation | Process for producing alcohols |
| GB2129430A (en) * | 1982-10-27 | 1984-05-16 | Bp Chem Int Ltd | Preparing ethyl acetate and ethylidene diacetate |
| WO2011027211A2 (en) * | 2009-09-07 | 2011-03-10 | Council Of Scientific & Industrial Research | Process for preparation of pure alkyl esters from alkali metal salt of carboxylic acid |
| US8912240B2 (en) | 2013-02-22 | 2014-12-16 | Eastman Chemical Company | Production of methanol and ethanol from CO or CO2 |
-
1979
- 1979-06-08 GB GB7920060A patent/GB2024811B/en not_active Expired
- 1979-06-19 AU AU48159/79A patent/AU525120B2/en not_active Ceased
- 1979-07-02 NL NL7905114A patent/NL7905114A/en not_active Application Discontinuation
- 1979-07-02 IT IT24048/79A patent/IT1122004B/en active
- 1979-07-02 FR FR7917119A patent/FR2430404A1/en active Granted
- 1979-07-02 BR BR7904194A patent/BR7904194A/en unknown
- 1979-07-03 CA CA000331035A patent/CA1156671A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1122004B (en) | 1986-04-23 |
| GB2024811A (en) | 1980-01-16 |
| FR2430404B1 (en) | 1984-05-25 |
| AU4815979A (en) | 1980-01-10 |
| IT7924048A0 (en) | 1979-07-02 |
| AU525120B2 (en) | 1982-10-21 |
| BR7904194A (en) | 1980-03-25 |
| FR2430404A1 (en) | 1980-02-01 |
| GB2024811B (en) | 1982-10-13 |
| NL7905114A (en) | 1980-01-07 |
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