CA1169881A - Process for preparing glycol ethers - Google Patents
Process for preparing glycol ethersInfo
- Publication number
- CA1169881A CA1169881A CA000384691A CA384691A CA1169881A CA 1169881 A CA1169881 A CA 1169881A CA 000384691 A CA000384691 A CA 000384691A CA 384691 A CA384691 A CA 384691A CA 1169881 A CA1169881 A CA 1169881A
- Authority
- CA
- Canada
- Prior art keywords
- cobalt
- alcohol
- aldehyde
- containing compound
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
Abstract
ABSTRACT OF THE DISCLOSURE
This invention pertains to the production of glycol monoalkyl ethers and dialkyl ethers by reaction of an al-dehyde, and an alcohol with carbon monoxide and hydrogen in the presence of a catalyst comprising a cobalt containing compound and a cyclopentadienyl ligand.
This invention pertains to the production of glycol monoalkyl ethers and dialkyl ethers by reaction of an al-dehyde, and an alcohol with carbon monoxide and hydrogen in the presence of a catalyst comprising a cobalt containing compound and a cyclopentadienyl ligand.
Description
~6~81 BACKGROU~lD OF l~IE I NVE~T I ON
Field of the Invention This invention relates to a process for the pre-paration of glycol monoalkyl- and dialkyl ethers by the reaction of synthesis gas, an aldehyde and an alcohol using a specific catalyst system.
Prior Art There is an ever increasing need for a wide variety of glycol monoalkyl-and dialkyl-ethers of differing carbon numbexs and structures which have become important present articles of commerce. Such ethers are employed in a wide variety of applications as solvents/ reaction media, etc.
In conventional processes an olefin oxide such as ethylene oxide is first prepared from an olefin and reacted with suitable alcohol. Since the cost of materials derived from petroleum sources has been rising rapidly, research efforts are now being made to find a new process for producing these glycol ethers which does not utilize an olefin as a s-tarting material. One of the newer methods for the preparation of glycol monoalkylethers, in which an acetal is reacted with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst is described in German Patent Nos. 875,802 and 890,945. This process suffers from several disadvan-tages including a low selectivity of the glycol ether and decomposition of the carbonyl catalyst during recovery of the product from -the raction mixture.
In U. S. Patent 4,071,568 a process for makin~
glycol monoethers is disclosed in which the catalyst util-ized is cobalt carbonyl combined with a trivalent organic phosphorus compound such as tri-n-butyl phosphine which is reported to give better selectivity.
g ~ ~
One of the objects of this invention is to provide a novel process ~or preparing glycol monoalkyl-and dialkyl-ethers by means of a unique catalyst system in Which the feedstock utilized comprises an aldehyde, an alcohol and synthesis gas.
Another object of this invention is to provide a process for producing glycol alkylethers in high yield.
SUMMARY OF THE INVENTION
In this invention glycol monoalkylethers and dialkylethers are prepared by reaction of an aldehyde, a monohydric alcohol and synthesis gas in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadienyl ligand at superatmospheric pres-sures.
The procQss of this invention is shown in the following equations where for purposes of illustration the reaction of carbon monoxide, hydrogen, formaldehyde and an alcohol is shown:
(1) CO~2H2~cHo~Ro~ L~and ~ HOCH2CH2OR+H2O
Field of the Invention This invention relates to a process for the pre-paration of glycol monoalkyl- and dialkyl ethers by the reaction of synthesis gas, an aldehyde and an alcohol using a specific catalyst system.
Prior Art There is an ever increasing need for a wide variety of glycol monoalkyl-and dialkyl-ethers of differing carbon numbexs and structures which have become important present articles of commerce. Such ethers are employed in a wide variety of applications as solvents/ reaction media, etc.
In conventional processes an olefin oxide such as ethylene oxide is first prepared from an olefin and reacted with suitable alcohol. Since the cost of materials derived from petroleum sources has been rising rapidly, research efforts are now being made to find a new process for producing these glycol ethers which does not utilize an olefin as a s-tarting material. One of the newer methods for the preparation of glycol monoalkylethers, in which an acetal is reacted with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst is described in German Patent Nos. 875,802 and 890,945. This process suffers from several disadvan-tages including a low selectivity of the glycol ether and decomposition of the carbonyl catalyst during recovery of the product from -the raction mixture.
In U. S. Patent 4,071,568 a process for makin~
glycol monoethers is disclosed in which the catalyst util-ized is cobalt carbonyl combined with a trivalent organic phosphorus compound such as tri-n-butyl phosphine which is reported to give better selectivity.
g ~ ~
One of the objects of this invention is to provide a novel process ~or preparing glycol monoalkyl-and dialkyl-ethers by means of a unique catalyst system in Which the feedstock utilized comprises an aldehyde, an alcohol and synthesis gas.
Another object of this invention is to provide a process for producing glycol alkylethers in high yield.
SUMMARY OF THE INVENTION
In this invention glycol monoalkylethers and dialkylethers are prepared by reaction of an aldehyde, a monohydric alcohol and synthesis gas in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadienyl ligand at superatmospheric pres-sures.
The procQss of this invention is shown in the following equations where for purposes of illustration the reaction of carbon monoxide, hydrogen, formaldehyde and an alcohol is shown:
(1) CO~2H2~cHo~Ro~ L~and ~ HOCH2CH2OR+H2O
(2) Co+~H2+~cHo~2RoH Lisand~ RC}I2CH2R~2~2 A wide variety of alcohols and aldehydes may be employed in the process of this invention.
A high degree of selectivity is exhibited by the reaction of this invention. For example, when formaldehyde and butanol are reacted with carbon monoxide and hydrogen in the process of this invention combined yields of ethylene gly-ol monobutyl-and dibutyl-ethers as high as 55 percent, based on the formaldehyde chargPd to the reactor have been obtained.
~ 1 6~8~1 DETAILED DESCRIPTION OF THE INVENTION
This inven-tion relates to a process for pr0paring monoalkylethers and dialkylethers by a process which comprises reacting a mixture of hydrogen, carbon monoxide, an aldehyde of the formula:
RCHO, wherein R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms and an alcohol of the formula:
R'OH, wherein R' .is alkyl of from 1 to 10 carbon atoms, in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadiene-type ligand at superatmospheric pressures of 500 psi or greater until substantial formation of the said glycol monoalkylethers and dialkylethers has been achieved and recovering the said ethers from the reaction mixture.
In carrying out the reaction of this invention selectively to produce high yields of the desixed glycol monoalkylethers and dialkylethers it is necessary to supply sufficient carbon monoxide, hydrogen, aldehyde and alcohol to at least satisfy the stoichiometry of equations (1) and (2) above although an excess of one or more of the reactants over the stoichiometric amounts may be present.
Catalysts that are suitable for use in th0 practice of this invention contain cobalt. The cobalt-containing compounds may be chosen from a wide vari~-;.y of organic or inorganic compounds, complexes, etc., as will be shown and illustrated below. It is only necessary that the catalyst precursor actually employed contain said metal in any of its ionic states. The actual catalytically active species is
A high degree of selectivity is exhibited by the reaction of this invention. For example, when formaldehyde and butanol are reacted with carbon monoxide and hydrogen in the process of this invention combined yields of ethylene gly-ol monobutyl-and dibutyl-ethers as high as 55 percent, based on the formaldehyde chargPd to the reactor have been obtained.
~ 1 6~8~1 DETAILED DESCRIPTION OF THE INVENTION
This inven-tion relates to a process for pr0paring monoalkylethers and dialkylethers by a process which comprises reacting a mixture of hydrogen, carbon monoxide, an aldehyde of the formula:
RCHO, wherein R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms and an alcohol of the formula:
R'OH, wherein R' .is alkyl of from 1 to 10 carbon atoms, in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadiene-type ligand at superatmospheric pressures of 500 psi or greater until substantial formation of the said glycol monoalkylethers and dialkylethers has been achieved and recovering the said ethers from the reaction mixture.
In carrying out the reaction of this invention selectively to produce high yields of the desixed glycol monoalkylethers and dialkylethers it is necessary to supply sufficient carbon monoxide, hydrogen, aldehyde and alcohol to at least satisfy the stoichiometry of equations (1) and (2) above although an excess of one or more of the reactants over the stoichiometric amounts may be present.
Catalysts that are suitable for use in th0 practice of this invention contain cobalt. The cobalt-containing compounds may be chosen from a wide vari~-;.y of organic or inorganic compounds, complexes, etc., as will be shown and illustrated below. It is only necessary that the catalyst precursor actually employed contain said metal in any of its ionic states. The actual catalytically active species is
-3-I l 69881 then believed to comprise cobalt in complex combination with the ligand and with carbon monoxide and hydrogen. The most effective catalyst is achieved where the cobalt hydrocarbonyl species is solubilized in the alcohol co-reactant employed.
The cobalt-containing catalyst precursors may take many different forms. For instance, the cobalt may be added to the reaction mixture in an oxide form, as in the case of, for example, cobalt(II) oxide (CoO~ or cobalt (II, III) oxide (Co3O4). Alternatively, it may be added as the salt of a mineral acid, as in the case of cobalt(II) chloride (CoC12), cobalt(II) chloride hydrate (CoCl2 6~2O~, cobalt(II) bromide (CoBr2), cobalt(II) iodide (CoI2) and cobalt(II) nitrate hydrate (Co(NO3)2.6E2O), etc., or as the salt of a suitable organic carboxylic acid, for example, cobalt(II) formate, cobalt(II~ acetate, cobalt(II) propionate, cobalt naphthenate, cobalt acetylacetonate, etc. The cobalt may also be added to the reaction zone as a carbonyl or hydro-carbonyl derivative. Here, suitable examples include dicobalt octacarbonyl (Co2(CO)8), cobalt hydrocarbonyl (HCo(CO)4) and substituted carbonyl species.
Preferred cobalt-containing compounds include oxides of cobalt, cobalt salts of a mineral acid, cobalt salts of organic carboxylic acids and cobalt carbonyl or hydrocarbonyl derivatives. Among these, particularly preferred are cobalt(II) chloride, cobalt acetylacetonate, cobalt(II) acetate, cobalt(II) propionate, and dicobalt octacarbonyl.
In the process of thi~ invention the reaction is conducted in the presence of a catalyst comprising a cobalt--containing compound and a cyclopentadienyl ligand. The '' cobalt-containing compound employed may be a cobalt carbonyl or a compound capable of ~orming a cobalt carbonyl under reaction conditions. The catalyst may be introduced into -the reaction system as a preformed complex by combining the cobalt-containing compound with the cyclopentadienyl ligand to form a complex where the cyclopentadiene is coordinated to the cobalt as a "pentahapto" ligand. This preformed complex is then introduced into the reaction mixture.
Alternatively, the cyclopentadienyl ligand and the cobalt-containing compound may be separately introduc~d into thereaction system where the complex is formed under reaction conditions.
Cyclopendienyl ligands which may be utilized with the cobalt-containing compounds in this process include cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, pentamethylcyclopentadiene, tert-amylcyclopentadiene, _-butylcyclopentadiene, cyclopenta-dienyl methyl ketone, phenyl cyclopentadienyl ketone, chlor-ocarbonylcyclopentadiene, N,N-dimethylaminomethylcyclo-~0 pentadiene, cyclopentadienyl acetonitrile, cyclopentadienylcarboxylic acid, cyclopendienyl acetic acid and cyclopenta-dienyl methyl carbinol, etc. When cyclopentadiene, for example, is coordinated with a metal s~ch as cobalt to form a cyclopendienyl-metal species ~he resulting compound falls within the general category of being a "pentahapto" ligand, i.e., pentahapto cyclopentadienyl cobalt.
A preferred clas of the cyclopentadienyl ligands includes cyclopentadiene, methylcyclopentadiene, peneta-methylcyclopentadiene, tert-amylcyclopentadiene and n butyl cyclopentadiene.
~ :~ 6~38~ ~
A preferred class of preformed cobalt catalysts includes the cyclopentadienylcobalt carbonyl complexes exemplified by cyclopentadienylcobalt dicarbonayl.
The number of gram moles of ligand employed per gram atom of cobalt can be varied widely and is generally in the range of 0.1 to 100 and preferably from 0.5 to 5.
Alcohols useful as starting materials in the process of this invention have the formula:
R'OH
where R' is alkyl of from 1 to 10 carbon atoms. Suitable alcohols include methanol, ethanol, propanol, butanol, heptanol, decanol, etc. and isomers thereof.
Aldehydes which may be utilized in the process of this invention include compounds of formula:
RCHO
where R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms as exemplified by methyl, ethyl, butyl, hexyl, nonyl, ekc. and isomers thereof.
Compounds capable of releasing an aldehyde under reaction conditions such as aldehyde polymers including paraform-aldehyde and trioxane may be utilized in the process of this invention~ The preerred aldehydes are formaldehyde and paraformaldehyde.
The ~uantity of cobalt catalyst employed in the instant invention is not critical and may vary over a wide range. In general, the novel process is desirably conducted in the presence of a catalytically effective quantity of one or more of the active cobalt species together with one or more of the cyclopentadienyl ligands which gives the desired products in reasonable yields. The reaction proceeds when employing as little as about 1 x 10 6 weigh-t percent and even lesser amounts of cobalt, 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, etc.
A cobalt catalyst concentration of ~rom about l x lO 5 to about lO weight percent cobalt, based on the total weight of reaction mixture, is generally desirable in the practice of this invention.
The temperature range which can usefully be employed in these syntheses is a variable dependent upon other experi-mental factors, including the choice of the aldehyde, the alcohol, the pressure, and the concentration and choice of particular species of the cobalt-containing compound and the cyclopentadienyl ligand among other things. The range of operability is from about 50 to about 300~C when super-atmospheric pressures of syngas are employed. A narrower range of about 100 to about 250C represents the preferred temperature range.
Superatmospheric pressures of 500 psi or greater lead to s~stantial yields of desirable glycol ethers by the process of this invention. A preferred operating range is from about lO00 psi to about 5000 psi, although pressures above 5000 psi also provide useful yields of the desired acid. The pressures referred to here repr~sent the total pressure generated by all the reactants, although they are substantialiy due to the carbon monoxide and hydrogen fractions in these examples.
The relative amounts of carbon monoxide and hydro-gen which may be initially present in the syngas mixture are variable, and these amounts may be varied over a wide range.
1 1 698~ ~
In general, the mole ratio of CO:H2 is in the range from about 20:1 up to about 1:20, preferably from about 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 ~e used in conjunction with up to 50% by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ethex.
In all these syntheses in order to achieve a high degree of sel~ctivity the amount of carbon monoxide, hydrogen, aldehyde and alcohol present in the reaction mixture should be sufficient to at least satisfy the stoichiometry of eq (l) or (2) depending upon the desired glycol alkylether.
Excess carbon monoxide and/or hydrogen or any of the reactants over the stoichiometric amounts may be present, i desired.
As far as can be determined, without limiting the invention thereby, the cobalt-catalyst one-step process disclosed herein leads primarily to the formation of glycol alkylether products. In the case then where formaldehyde and methanol are the co-reactants, the principal products axe ethylene glycol monomethylether and ethylene glycol dimethylether. By-products such as wa~er and dimetho~y-methane are also datected in the liguid product fraction.
The novel process of this invention can be conducted in a batch, semi-continuous or continuous fashion.
~ ~ 69~
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 syn-the-sis reaction. Operating conditions can be adjusted to optimize the formation of the desired ester product, and said material may be recovered by methods well known in the art, such as distillation, fractionation, extraction and the like. A fraction rich in cobalt catalyst components may then be recycled to the reaction zone, if desired, and additional products generated.
The products 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 techni~ues. Analyses have, for the rnost part, been by parts in weight; all -tem-; peratures are in degrees centigrade and all pressures in pounds per square inch gauge (psi).
The following examples which illustrate various embodiments of the invention are to be considerd not limi-tative.
- E X A M P L E
To a 450 ml glass-lined pressure reactor was charged a mixture of dicobalt octacarbonyl (2 mmole Co), pentamethylcyclopentadiene (2 mmole) and paraformaldehyde ~0.1 mole) in 37.1 g of n-butanol (0.5 mole). After flushing with nitrogen, the reactor was sealed and flushed with a gaseous mixture containing equal molar amounts of carbon mono~ide and hydrogen following which it was pressured to 2700 psi with a gaseous mixture containing 2 moles of hydro-gen per mole of carbon monoxide and finally heated to 160C
9_ ~ ~ 6 9 ~
with agitation. After 4 hours at 160C the reactor was allowed to cool, the excess gas was sampled and vented and a deep-red liquid product (42.7 g) was recovered.
Analysis by glc of the liquid product showed the presence of:
13.2 wt % ethylene glycol monobutyl ether 1.2 wt % ethylene glycol dibutyl ether 5.7 wt % water 78.3 wt % unreacted n-butanol Estimated yield of ethylene glycol monobutyl ether (basis paraformaldehyde charged) was 48 mole percent. Total glycol monobutyl and dibutyl ether yield was 51 mole per-cent.
Cobalt recovery in the liquid product solution is > 95%.
Typical off-gas samples showed the presence of:
33.9% carbon monoxide 59.6% hydrogen
The cobalt-containing catalyst precursors may take many different forms. For instance, the cobalt may be added to the reaction mixture in an oxide form, as in the case of, for example, cobalt(II) oxide (CoO~ or cobalt (II, III) oxide (Co3O4). Alternatively, it may be added as the salt of a mineral acid, as in the case of cobalt(II) chloride (CoC12), cobalt(II) chloride hydrate (CoCl2 6~2O~, cobalt(II) bromide (CoBr2), cobalt(II) iodide (CoI2) and cobalt(II) nitrate hydrate (Co(NO3)2.6E2O), etc., or as the salt of a suitable organic carboxylic acid, for example, cobalt(II) formate, cobalt(II~ acetate, cobalt(II) propionate, cobalt naphthenate, cobalt acetylacetonate, etc. The cobalt may also be added to the reaction zone as a carbonyl or hydro-carbonyl derivative. Here, suitable examples include dicobalt octacarbonyl (Co2(CO)8), cobalt hydrocarbonyl (HCo(CO)4) and substituted carbonyl species.
Preferred cobalt-containing compounds include oxides of cobalt, cobalt salts of a mineral acid, cobalt salts of organic carboxylic acids and cobalt carbonyl or hydrocarbonyl derivatives. Among these, particularly preferred are cobalt(II) chloride, cobalt acetylacetonate, cobalt(II) acetate, cobalt(II) propionate, and dicobalt octacarbonyl.
In the process of thi~ invention the reaction is conducted in the presence of a catalyst comprising a cobalt--containing compound and a cyclopentadienyl ligand. The '' cobalt-containing compound employed may be a cobalt carbonyl or a compound capable of ~orming a cobalt carbonyl under reaction conditions. The catalyst may be introduced into -the reaction system as a preformed complex by combining the cobalt-containing compound with the cyclopentadienyl ligand to form a complex where the cyclopentadiene is coordinated to the cobalt as a "pentahapto" ligand. This preformed complex is then introduced into the reaction mixture.
Alternatively, the cyclopentadienyl ligand and the cobalt-containing compound may be separately introduc~d into thereaction system where the complex is formed under reaction conditions.
Cyclopendienyl ligands which may be utilized with the cobalt-containing compounds in this process include cyclopentadiene and cyclopentadiene derivatives such as methylcyclopentadiene, pentamethylcyclopentadiene, tert-amylcyclopentadiene, _-butylcyclopentadiene, cyclopenta-dienyl methyl ketone, phenyl cyclopentadienyl ketone, chlor-ocarbonylcyclopentadiene, N,N-dimethylaminomethylcyclo-~0 pentadiene, cyclopentadienyl acetonitrile, cyclopentadienylcarboxylic acid, cyclopendienyl acetic acid and cyclopenta-dienyl methyl carbinol, etc. When cyclopentadiene, for example, is coordinated with a metal s~ch as cobalt to form a cyclopendienyl-metal species ~he resulting compound falls within the general category of being a "pentahapto" ligand, i.e., pentahapto cyclopentadienyl cobalt.
A preferred clas of the cyclopentadienyl ligands includes cyclopentadiene, methylcyclopentadiene, peneta-methylcyclopentadiene, tert-amylcyclopentadiene and n butyl cyclopentadiene.
~ :~ 6~38~ ~
A preferred class of preformed cobalt catalysts includes the cyclopentadienylcobalt carbonyl complexes exemplified by cyclopentadienylcobalt dicarbonayl.
The number of gram moles of ligand employed per gram atom of cobalt can be varied widely and is generally in the range of 0.1 to 100 and preferably from 0.5 to 5.
Alcohols useful as starting materials in the process of this invention have the formula:
R'OH
where R' is alkyl of from 1 to 10 carbon atoms. Suitable alcohols include methanol, ethanol, propanol, butanol, heptanol, decanol, etc. and isomers thereof.
Aldehydes which may be utilized in the process of this invention include compounds of formula:
RCHO
where R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms as exemplified by methyl, ethyl, butyl, hexyl, nonyl, ekc. and isomers thereof.
Compounds capable of releasing an aldehyde under reaction conditions such as aldehyde polymers including paraform-aldehyde and trioxane may be utilized in the process of this invention~ The preerred aldehydes are formaldehyde and paraformaldehyde.
The ~uantity of cobalt catalyst employed in the instant invention is not critical and may vary over a wide range. In general, the novel process is desirably conducted in the presence of a catalytically effective quantity of one or more of the active cobalt species together with one or more of the cyclopentadienyl ligands which gives the desired products in reasonable yields. The reaction proceeds when employing as little as about 1 x 10 6 weigh-t percent and even lesser amounts of cobalt, 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, etc.
A cobalt catalyst concentration of ~rom about l x lO 5 to about lO weight percent cobalt, based on the total weight of reaction mixture, is generally desirable in the practice of this invention.
The temperature range which can usefully be employed in these syntheses is a variable dependent upon other experi-mental factors, including the choice of the aldehyde, the alcohol, the pressure, and the concentration and choice of particular species of the cobalt-containing compound and the cyclopentadienyl ligand among other things. The range of operability is from about 50 to about 300~C when super-atmospheric pressures of syngas are employed. A narrower range of about 100 to about 250C represents the preferred temperature range.
Superatmospheric pressures of 500 psi or greater lead to s~stantial yields of desirable glycol ethers by the process of this invention. A preferred operating range is from about lO00 psi to about 5000 psi, although pressures above 5000 psi also provide useful yields of the desired acid. The pressures referred to here repr~sent the total pressure generated by all the reactants, although they are substantialiy due to the carbon monoxide and hydrogen fractions in these examples.
The relative amounts of carbon monoxide and hydro-gen which may be initially present in the syngas mixture are variable, and these amounts may be varied over a wide range.
1 1 698~ ~
In general, the mole ratio of CO:H2 is in the range from about 20:1 up to about 1:20, preferably from about 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 ~e used in conjunction with up to 50% by volume of one or more other gases. These other gases may include one or more inert gases such as nitrogen, argon, neon and the like, or they may include gases that may, or may not, undergo reaction under CO hydrogenation conditions, such as carbon dioxide, hydrocarbons such as methane, ethane, propane and the like, ethers such as dimethyl ether, methylethyl ether and diethyl ethex.
In all these syntheses in order to achieve a high degree of sel~ctivity the amount of carbon monoxide, hydrogen, aldehyde and alcohol present in the reaction mixture should be sufficient to at least satisfy the stoichiometry of eq (l) or (2) depending upon the desired glycol alkylether.
Excess carbon monoxide and/or hydrogen or any of the reactants over the stoichiometric amounts may be present, i desired.
As far as can be determined, without limiting the invention thereby, the cobalt-catalyst one-step process disclosed herein leads primarily to the formation of glycol alkylether products. In the case then where formaldehyde and methanol are the co-reactants, the principal products axe ethylene glycol monomethylether and ethylene glycol dimethylether. By-products such as wa~er and dimetho~y-methane are also datected in the liguid product fraction.
The novel process of this invention can be conducted in a batch, semi-continuous or continuous fashion.
~ ~ 69~
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 syn-the-sis reaction. Operating conditions can be adjusted to optimize the formation of the desired ester product, and said material may be recovered by methods well known in the art, such as distillation, fractionation, extraction and the like. A fraction rich in cobalt catalyst components may then be recycled to the reaction zone, if desired, and additional products generated.
The products 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 techni~ues. Analyses have, for the rnost part, been by parts in weight; all -tem-; peratures are in degrees centigrade and all pressures in pounds per square inch gauge (psi).
The following examples which illustrate various embodiments of the invention are to be considerd not limi-tative.
- E X A M P L E
To a 450 ml glass-lined pressure reactor was charged a mixture of dicobalt octacarbonyl (2 mmole Co), pentamethylcyclopentadiene (2 mmole) and paraformaldehyde ~0.1 mole) in 37.1 g of n-butanol (0.5 mole). After flushing with nitrogen, the reactor was sealed and flushed with a gaseous mixture containing equal molar amounts of carbon mono~ide and hydrogen following which it was pressured to 2700 psi with a gaseous mixture containing 2 moles of hydro-gen per mole of carbon monoxide and finally heated to 160C
9_ ~ ~ 6 9 ~
with agitation. After 4 hours at 160C the reactor was allowed to cool, the excess gas was sampled and vented and a deep-red liquid product (42.7 g) was recovered.
Analysis by glc of the liquid product showed the presence of:
13.2 wt % ethylene glycol monobutyl ether 1.2 wt % ethylene glycol dibutyl ether 5.7 wt % water 78.3 wt % unreacted n-butanol Estimated yield of ethylene glycol monobutyl ether (basis paraformaldehyde charged) was 48 mole percent. Total glycol monobutyl and dibutyl ether yield was 51 mole per-cent.
Cobalt recovery in the liquid product solution is > 95%.
Typical off-gas samples showed the presence of:
33.9% carbon monoxide 59.6% hydrogen
4.8% carbon dioxide The glycol monobutyl ether was recovered by distillation in vacuo.
Following the general procedure of Example 1, additional catalysts were employed in Example~ 2-5.
Specifically:
a) Examples 2 and 3 demonstrate the effective use o cyclopentadienylcobalt dicarbonyl as the catalyst for the synthesis of glycol hutyl ethers.
b) Example 4 demonstrates the efective use of the cobalt(II) acetate-pentamethylcyclopentadiene combina-tion as catalyst for the sy~thesis ol glycol butyl ethers.
c) Cyclopentadienylcobalt dicarbonyl was successfully employed as the soluble catalyst while the alcohol utilized was methanol in Example 5.
Results are summarized in Table ~ which follows.
~ 1 6988 ~
o ~
oo oo ,, ~ ,, ~, ~ ~ ~ .,. ~
~`~
I 0 ~
1~
3 ;~1c~l r~
U~ ~ ~ o ~ o o ~a ~ ~ ~ o ~q ~ ~ ,1 ~ ,~
O
U~ ~ ~ ~o oo oo oo ol c~ O
~1 o o c~J o ~ ~
s~ o I 1` ~ o o o o H ~ ~ I ,r, ~ C~i ~S~ ~ t ~ ~ C10 r~ ~
~q ~1 ~ ~U
~ ~ C~i U ~
_i .
'C ~ o o o o o o f~
E-~ O `D ~O O ~O O C~ ~ ~d u a~
P o ~ ~ ~
C~ ~ ~ ~ O
3) _I o d ~ ~ o o 4 ~ ~ ~ ~ e 2 ~
~- d o ~Y
O ~^
:C
,1 U p.
O ~ ~1 . ._ u ~ a~
¢ ~ ~ m m O O O J~
o U) r~
l ~ P
o ~ a ~
:1 o ~ u d ~ d E3 ~ ~ t3 ~3 O O U") O O ~I S,l ~
E3 u~ ~ ~ X ~ Pi E~ --I
~O~
~
P O ~u~ ~ u qU~ ~ U^ a~
-~ ~ d ,~d d c ~ ~ ~ ~ ~ O O ~
~ ~ o ~ o ~ ~ ~ 8 ~
~j ~ ~ ,Q ~ ~ d ~ 169~8:~
Following the general procedure of Examples 1-5 inclusive, the 450 ml glass~lined pressure reactor was charged with 0.1 mole of paraformaldehyde, cyclopentadienyl-cobalt dicarbonyl (2.0 mmole Co), and 0.5 mole of _-butanol.
After flushing with syngas (CO/E2 mixture), the reactor was pressured to 2700 psi with a gaseous mixture containing 2 moles of hydrogen per mole of carbon monoxide, and heated to 160~C with agitation. After 4 hours at temperature, the reactor was cooled and vented and the clear red liquid product recovered and analyzed by glc and Karl Fischer Titration. There were no residual solids at this stage.
The product liquid was distilled ln vacuo, and ethylene glycol monobutyl ether was recovered as a distillate fraction at 48-52C (l mm Hg pressure). The residual catalyst remained behind as a deep-red colored liquid (2.5 g) and this residual catalyst liquid was returned to the 450 ml glass-lined by washing with additional n-butanol (0.5 mole). Fresh paraformaldehyde tO.l mole) was also added at this stage, the reactor sealed, flushed with syngas, pressured to 2700 psi with CO/~2 (1:2) and heated to 160C
with agitation for 4 hours. In this manner the synthesis of ethylene glycol monobutyl e~her was repeated successfully, a~d the later recovered fxom the crude liquid product (42.5 g) by vacuum distillation as outlined above.
The residual catalyst solution (2.5 g) from this second cycle was again returned to the reactor for further glycol ether synthesis. The yields of glycol monobutyl ether (basis para~ormaldehyde charged~ for this three cycle experiment are shown in Table II.
1 1 69~
TABLE II
Ethylene Gly~ol Butyl Ethçrs From Syngas-Catalyst Recycling Number of Yield of
Following the general procedure of Example 1, additional catalysts were employed in Example~ 2-5.
Specifically:
a) Examples 2 and 3 demonstrate the effective use o cyclopentadienylcobalt dicarbonyl as the catalyst for the synthesis of glycol hutyl ethers.
b) Example 4 demonstrates the efective use of the cobalt(II) acetate-pentamethylcyclopentadiene combina-tion as catalyst for the sy~thesis ol glycol butyl ethers.
c) Cyclopentadienylcobalt dicarbonyl was successfully employed as the soluble catalyst while the alcohol utilized was methanol in Example 5.
Results are summarized in Table ~ which follows.
~ 1 6988 ~
o ~
oo oo ,, ~ ,, ~, ~ ~ ~ .,. ~
~`~
I 0 ~
1~
3 ;~1c~l r~
U~ ~ ~ o ~ o o ~a ~ ~ ~ o ~q ~ ~ ,1 ~ ,~
O
U~ ~ ~ ~o oo oo oo ol c~ O
~1 o o c~J o ~ ~
s~ o I 1` ~ o o o o H ~ ~ I ,r, ~ C~i ~S~ ~ t ~ ~ C10 r~ ~
~q ~1 ~ ~U
~ ~ C~i U ~
_i .
'C ~ o o o o o o f~
E-~ O `D ~O O ~O O C~ ~ ~d u a~
P o ~ ~ ~
C~ ~ ~ ~ O
3) _I o d ~ ~ o o 4 ~ ~ ~ ~ e 2 ~
~- d o ~Y
O ~^
:C
,1 U p.
O ~ ~1 . ._ u ~ a~
¢ ~ ~ m m O O O J~
o U) r~
l ~ P
o ~ a ~
:1 o ~ u d ~ d E3 ~ ~ t3 ~3 O O U") O O ~I S,l ~
E3 u~ ~ ~ X ~ Pi E~ --I
~O~
~
P O ~u~ ~ u qU~ ~ U^ a~
-~ ~ d ,~d d c ~ ~ ~ ~ ~ O O ~
~ ~ o ~ o ~ ~ ~ 8 ~
~j ~ ~ ,Q ~ ~ d ~ 169~8:~
Following the general procedure of Examples 1-5 inclusive, the 450 ml glass~lined pressure reactor was charged with 0.1 mole of paraformaldehyde, cyclopentadienyl-cobalt dicarbonyl (2.0 mmole Co), and 0.5 mole of _-butanol.
After flushing with syngas (CO/E2 mixture), the reactor was pressured to 2700 psi with a gaseous mixture containing 2 moles of hydrogen per mole of carbon monoxide, and heated to 160~C with agitation. After 4 hours at temperature, the reactor was cooled and vented and the clear red liquid product recovered and analyzed by glc and Karl Fischer Titration. There were no residual solids at this stage.
The product liquid was distilled ln vacuo, and ethylene glycol monobutyl ether was recovered as a distillate fraction at 48-52C (l mm Hg pressure). The residual catalyst remained behind as a deep-red colored liquid (2.5 g) and this residual catalyst liquid was returned to the 450 ml glass-lined by washing with additional n-butanol (0.5 mole). Fresh paraformaldehyde tO.l mole) was also added at this stage, the reactor sealed, flushed with syngas, pressured to 2700 psi with CO/~2 (1:2) and heated to 160C
with agitation for 4 hours. In this manner the synthesis of ethylene glycol monobutyl e~her was repeated successfully, a~d the later recovered fxom the crude liquid product (42.5 g) by vacuum distillation as outlined above.
The residual catalyst solution (2.5 g) from this second cycle was again returned to the reactor for further glycol ether synthesis. The yields of glycol monobutyl ether (basis para~ormaldehyde charged~ for this three cycle experiment are shown in Table II.
1 1 69~
TABLE II
Ethylene Gly~ol Butyl Ethçrs From Syngas-Catalyst Recycling Number of Yield of
5 Example Catalyst Cycles BuocH2cH2oH(%)
6 1 38 a Yield basis paraformaldehyde charged (0.1 mole) at the start of each catalyst cycle.
~13-
~13-
Claims (22)
1. A process for preparing glycol monoalkyl-ethers and dialkylethers which comprises reacting a mixture of hydrogen, carbon monoxide, an aldehyde of the formula:
RCHO, wherein R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms and an alcohol of the formula:
R'OH, wherein R' is alkyl of from 1 to 10 carbon atoms, in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadienyl ligand at super-atmospheric pressures of 500 psi or greater until substantial formation of the said glycol monoalkylethers and dialkylethers has been achieved and recovering the said ethers from the reaction mixture.
RCHO, wherein R is selected from the group consisting of hydrogen and alkyl of from 1 to 10 carbon atoms and an alcohol of the formula:
R'OH, wherein R' is alkyl of from 1 to 10 carbon atoms, in the presence of a catalyst comprising a cobalt-containing compound and at least one cyclopentadienyl ligand at super-atmospheric pressures of 500 psi or greater until substantial formation of the said glycol monoalkylethers and dialkylethers has been achieved and recovering the said ethers from the reaction mixture.
2. The process of Claim 1 wherein the said reaction mixture is heated at a temperature of from about 50 to about 300°C.
3. The process of Claim 1 wherein the said reaction mixture is heated at a temperature of about 100 to about 250°C.
4. The process of Claim 1 wherein the process is conducted at a pressure of about 1000 psi to about 5000 psi.
5. The process of Claim 1 wherein the said cobalt-containing compound is selected from the group consisting of one or more oxides of cobalt, cobalt salts of a mineral acid, cobalt salts of an organic carboxylic acid and cobalt carbonyl or hydrocarbonyl derivatives.
6. The process of Claim 5 wherein the said cobalt-containing compound is selected from the group consisting of cobalt oxide, cobalt chloride, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt propionate, cobalt acetylacetonate, and dicobalt octacarbonyl.
7. The process of Claim 6 wherein said cobalt compound is cobalt(II) acetate.
8. The process of Claim 6 wherein said cobalt compound is dicobalt octacarbonyl.
9. The method of Claim 1 wherein said aldehyde is selected from the group consisting of formaldehyde and paraformaldehyde.
10. The process of Claim 9 wherein the said aldehyde is formaldehyde.
11. The process of Claim 9 wherein the said aldehyde is paraformaldehyde.
12. The process of Claim 1 wherein the said alcohol is selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol and isomers thereof.
13. The process of Claim 12 wherein the said alcohol is methanol.
14. The process of Claim 12 wherein the said alcohol is ethanol.
15. The process of Claim 12 wherein the said alcohol is n-butanol.
16. The process of Claim 1 wherein the said cyclopentadienyl ligand is a compound selected from the group consisting of cyclopentadiene, methylcyclopentadiene, pentamethylcyclopentadiene, tert-amylcyclopentadiene and n-butylcyclopentadiene.
17. The process of Claim 16 wherein the said cyclopentadienyl ligand is cyclopentadiene.
18. The process of Claim 16 wherein the said cyclopentadienyl ligand is pentamethylcyclopentadiene.
19. The process of Claim 16 wherein the said cyclopentadienyl ligand is methylcyclopentadiene.
20. The process of Claim 1 wherein the said aldehyde is formaldehyde, the said alcohol is methanol, the said cobalt-containing compound is dicobalt octacarbonyl and the said cyclopendienyl ligand is cyclopentadiene.
21. The process of Claim 1 wherein the said aldehyde is formaldehyde, the said alcohol is n-butanol and the said cobalt-containing compound is cyclopentadienyl-cobalt dicarbonyl.
22. The process of Claim 1 wherein the said aldehyde is formaldehyde, the said alcohol is n-butanol, the said cobalt-containing compound is dicobalt octacarbonyl and the said cyclopentadienyl ligand is pentamethylcyclopentadiene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US186,933 | 1980-09-12 | ||
| US06/186,933 US4317943A (en) | 1980-09-12 | 1980-09-12 | Process for preparing glycol ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1169881A true CA1169881A (en) | 1984-06-26 |
Family
ID=22686897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000384691A Expired CA1169881A (en) | 1980-09-12 | 1981-08-27 | Process for preparing glycol ethers |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4317943A (en) |
| JP (1) | JPS5932454B2 (en) |
| BE (1) | BE890305A (en) |
| BR (1) | BR8104919A (en) |
| CA (1) | CA1169881A (en) |
| DE (1) | DE3135192A1 (en) |
| FR (1) | FR2490216A1 (en) |
| GB (1) | GB2083466B (en) |
| IT (1) | IT1139969B (en) |
| NL (1) | NL8104097A (en) |
| ZA (1) | ZA815889B (en) |
Families Citing this family (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4356327A (en) * | 1981-10-29 | 1982-10-26 | Texaco Inc. | Process for preparing propylene glycol monoalkyl ethers and alkoxyacetones |
| US4692426A (en) * | 1984-06-21 | 1987-09-08 | Sun Refining And Marketing Company | Phosphite-promoted ruthenium-cobalt catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers |
| US4617287A (en) * | 1984-06-21 | 1986-10-14 | Sun Refining And Marketing Company | Ruthenium-cobalt carbonyl catalysts for the dealkoxyhydroxymethylation of aldehyde acetals to form glycol ethers |
| US4652542A (en) * | 1984-06-21 | 1987-03-24 | Sun Refining And Marketing Company | Ruthenium-cobalt carbonyl catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers |
| US4895987A (en) * | 1986-06-06 | 1990-01-23 | Sun Refining And Marketing Company | Phosphonite-and phosphonite-promoted ruthenium - cobalt catalysts for the dealkoxyhydroxymethylation of acetals to form glycol ethers |
| USD434876S (en) | 1999-11-09 | 2000-12-05 | Titus Chukwuemeka Ife | Hair piece design |
| US7838708B2 (en) | 2001-06-20 | 2010-11-23 | Grt, Inc. | Hydrocarbon conversion process improvements |
| US20050171393A1 (en) | 2003-07-15 | 2005-08-04 | Lorkovic Ivan M. | Hydrocarbon synthesis |
| RU2366642C2 (en) | 2003-07-15 | 2009-09-10 | Джи Ар Ти, Инк. | Hydrocarbons synthesis |
| US7244867B2 (en) | 2004-04-16 | 2007-07-17 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| US20060100469A1 (en) | 2004-04-16 | 2006-05-11 | Waycuilis John J | Process for converting gaseous alkanes to olefins and liquid hydrocarbons |
| US8173851B2 (en) | 2004-04-16 | 2012-05-08 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US8642822B2 (en) | 2004-04-16 | 2014-02-04 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons using microchannel reactor |
| US7674941B2 (en) | 2004-04-16 | 2010-03-09 | Marathon Gtf Technology, Ltd. | Processes for converting gaseous alkanes to liquid hydrocarbons |
| US20080275284A1 (en) | 2004-04-16 | 2008-11-06 | Marathon Oil Company | Process for converting gaseous alkanes to liquid hydrocarbons |
| KR101335397B1 (en) | 2006-02-03 | 2013-12-02 | 지알티, 인코포레이티드 | Separation of light gases from halogens |
| CA2641348C (en) | 2006-02-03 | 2014-12-23 | Grt, Inc. | Continuous process for converting natural gas to liquid hydrocarbons |
| JP2010528054A (en) * | 2007-05-24 | 2010-08-19 | ジーアールティー インコーポレイテッド | Zone reactor incorporating reversible hydrogen halide capture and release |
| US8282810B2 (en) | 2008-06-13 | 2012-10-09 | Marathon Gtf Technology, Ltd. | Bromine-based method and system for converting gaseous alkanes to liquid hydrocarbons using electrolysis for bromine recovery |
| KR101740419B1 (en) | 2008-07-18 | 2017-05-26 | 지알티, 인코포레이티드 | Continuous process for converting natural gas to liquid hydrocarbons |
| US8367884B2 (en) | 2010-03-02 | 2013-02-05 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8198495B2 (en) | 2010-03-02 | 2012-06-12 | Marathon Gtf Technology, Ltd. | Processes and systems for the staged synthesis of alkyl bromides |
| US8815050B2 (en) | 2011-03-22 | 2014-08-26 | Marathon Gtf Technology, Ltd. | Processes and systems for drying liquid bromine |
| US8436220B2 (en) | 2011-06-10 | 2013-05-07 | Marathon Gtf Technology, Ltd. | Processes and systems for demethanization of brominated hydrocarbons |
| US8829206B2 (en) | 2011-06-24 | 2014-09-09 | Eastman Chemical Company | Production of cyclic acetals or ketals using solid acid catalysts |
| US9000229B2 (en) | 2011-06-24 | 2015-04-07 | Eastman Chemical Company | Production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals |
| US9056313B2 (en) | 2011-06-24 | 2015-06-16 | Eastman Chemical Company | Catalysts for the production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals |
| US9388105B2 (en) | 2011-06-24 | 2016-07-12 | Eastman Chemical Company | Production of hydroxy ether hydrocarbons by liquid phase hydrogenolysis of cyclic acetals or cyclic ketals |
| US8969598B2 (en) | 2011-06-24 | 2015-03-03 | Eastman Chemical Company | Production of cyclic acetals or ketals using liquid-phase acid catalysts |
| US8829207B2 (en) | 2011-06-24 | 2014-09-09 | Eastman Chemical Company | Production of cyclic acetals by reactive distillation |
| US8785697B2 (en) | 2011-06-24 | 2014-07-22 | Eastman Chemical Company | Nickel modified catalyst for the production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals |
| US8829256B2 (en) | 2011-06-30 | 2014-09-09 | Gtc Technology Us, Llc | Processes and systems for fractionation of brominated hydrocarbons in the conversion of natural gas to liquid hydrocarbons |
| US8802908B2 (en) | 2011-10-21 | 2014-08-12 | Marathon Gtf Technology, Ltd. | Processes and systems for separate, parallel methane and higher alkanes' bromination |
| US9193641B2 (en) | 2011-12-16 | 2015-11-24 | Gtc Technology Us, Llc | Processes and systems for conversion of alkyl bromides to higher molecular weight hydrocarbons in circulating catalyst reactor-regenerator systems |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE875802C (en) * | 1941-03-07 | 1953-05-07 | Basf Ag | Process for the production of organic compounds containing oxygen |
| US4071568A (en) * | 1975-12-12 | 1978-01-31 | Mitsubishi Chemical Industries Limited | Process for producing glycol monoether |
-
1980
- 1980-09-12 US US06/186,933 patent/US4317943A/en not_active Expired - Lifetime
-
1981
- 1981-07-28 JP JP56117212A patent/JPS5932454B2/en not_active Expired
- 1981-07-30 BR BR8104919A patent/BR8104919A/en unknown
- 1981-08-21 GB GB8125653A patent/GB2083466B/en not_active Expired
- 1981-08-25 ZA ZA815889A patent/ZA815889B/en unknown
- 1981-08-27 CA CA000384691A patent/CA1169881A/en not_active Expired
- 1981-09-04 NL NL8104097A patent/NL8104097A/en not_active Application Discontinuation
- 1981-09-05 DE DE19813135192 patent/DE3135192A1/en not_active Withdrawn
- 1981-09-10 BE BE0/205928A patent/BE890305A/en not_active IP Right Cessation
- 1981-09-11 IT IT23925/81A patent/IT1139969B/en active
- 1981-09-11 FR FR8117224A patent/FR2490216A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BR8104919A (en) | 1982-04-13 |
| JPS5932454B2 (en) | 1984-08-09 |
| GB2083466A (en) | 1982-03-24 |
| FR2490216B1 (en) | 1983-11-04 |
| FR2490216A1 (en) | 1982-03-19 |
| GB2083466B (en) | 1984-06-13 |
| IT1139969B (en) | 1986-09-24 |
| BE890305A (en) | 1982-03-10 |
| IT8123925A0 (en) | 1981-09-11 |
| NL8104097A (en) | 1982-04-01 |
| JPS5754134A (en) | 1982-03-31 |
| DE3135192A1 (en) | 1982-04-29 |
| US4317943A (en) | 1982-03-02 |
| ZA815889B (en) | 1983-01-26 |
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