CA1150318A - Method for manufacturing ethyleneglycol - Google Patents
Method for manufacturing ethyleneglycolInfo
- Publication number
- CA1150318A CA1150318A CA000369645A CA369645A CA1150318A CA 1150318 A CA1150318 A CA 1150318A CA 000369645 A CA000369645 A CA 000369645A CA 369645 A CA369645 A CA 369645A CA 1150318 A CA1150318 A CA 1150318A
- Authority
- CA
- Canada
- Prior art keywords
- sec
- ethyleneglycol
- formaldehyde
- reaction
- alkyl
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
ABSTRACT OF THE DISCLOSURE
The invention provides a novel and very economical method for the industrial production of ethyleneglycol starting with formaldehyde and synthesis gas, i.e. a gaseous mixture of carbon monoxide and hydrogen. The method utilizes the synthetic route in which a formaldehyde di-sec-alkyl acetal, which is obtained from formaldehyde and a sec-alcohol, with carbon monoxide and hydrogen to form an ethyleneglycol mono-sec-alkyl ether which is then hydrolyzed with water into the desired ethyleneglycol.
The first step reaction of the acetal compound is catalyzed with a single component catalyst of cobalt carbonyl while the hydrolysis reaction proceeds with an acidic catalyst in a high yield unexpected from the similar reaction of ethyleneglycol mono-primary-alkyl-ethers.
The invention provides a novel and very economical method for the industrial production of ethyleneglycol starting with formaldehyde and synthesis gas, i.e. a gaseous mixture of carbon monoxide and hydrogen. The method utilizes the synthetic route in which a formaldehyde di-sec-alkyl acetal, which is obtained from formaldehyde and a sec-alcohol, with carbon monoxide and hydrogen to form an ethyleneglycol mono-sec-alkyl ether which is then hydrolyzed with water into the desired ethyleneglycol.
The first step reaction of the acetal compound is catalyzed with a single component catalyst of cobalt carbonyl while the hydrolysis reaction proceeds with an acidic catalyst in a high yield unexpected from the similar reaction of ethyleneglycol mono-primary-alkyl-ethers.
Description
~15~318 - METHOD FOR MANUFACTURING ETHYLENEGLYCOL
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing ` ethyleneglycol with high efficiency and economy. More parti-~ cularly, the invention relates to a method for manufacturing ethyleneglycol by hydrolyzing a secondary alkyl monoether of ethyleneglycol which in turn is synthesized by the reaction of a formaldehyde di-sec-alkyl acetal with hydrogen and carbon monoxide.
Ethyleneglycol is an industrially important basic compound in a wide field of chemical industry as a starting material for polyesters, as a solvent, as a non-volatile anti-freezing agent . .
or coolant and the like.
The processes for the industrial production of ethylen~lycol ~l currently on use are mostly petrochemical with ethylene as the - ~ starting material. Alternatively, several processes utilize so-called Cl compounds having a single carbon atom in a molecule such as carbon monoxide, formaldehyde and the like as the starting I material.
,~ For example, a method is known, as one of the Cl processes, by which ethyleneglycol is directly synthesized from a so-called synthesis gas, i.e. a gaseous mixture of hydrogen and carbon monoxide, in the presence of a rhodium catalyst (see, for example, Japanese Patent Disclosure 52-42809). This method is, however, ~j .
25 ¦~ not advantageous as an industrial process since the reaction must be carried out under a superatmospheric pressure of as high as 500 kg/cm2 or higher.
An alternative method as one of the Cl processes proposed ! in Japanese Patent Disclosure 54-106408 utilizes a somewhat i ;', _ . _ . .. . _ 3~8 lengthy synthetic route according to which formaldehyde is reacted with carbon monoxide to form glycolic acid which is then converted to a glycolate ester by esterification followed by the hydrogenation of the ester compound into ethyleneglycol. This method is also defective as an industrial process since the high-pressure reaction of formaldehyde with carbon monoxide must be catalyzed by a highly corrosive strong acid such as hydrofluoruc acid.
Further alternatively, a one-step method is disclosed in Japanese Patent Disclosure 51-128903 and 53-53607 in which ethyleneglycol is obtained directly by the reaction of formaldehyde and synthesis gas. One of the drawbacks of this method from the industrial standpoint is the undesirably low selectivity of ethyleneglycol among the reaction products. For example, the yield of ethylene-glycol rarely exceeds 40~ as calculated on the base of the consumed formaldehyde.
SUMMARY OF THE INVENTION
Thus, an object of the present invention is to provide a novel and improved method for the synthetic preparation of ethyleneglycol via a so-called Cl process, by which ethylene-glycol can be manufactured in a high yield and without the difficulties in the prior art processes as.
described above.
According to one aspect of the invention there is provided a method for the preparation of ethyleneglycol which comprises hydrolyzing sec-alkyl monoether of ethyleneglycol with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400C.
According to another aspect of the invention there is provided a method for the preparation of ethyleneglycol .
3~8 from formaldehyde, carbon monoxide and hydrogen as the starting materials which comprises the steps of (a~
reacting formaldehyde with a sec-alcohol to form a formaldehyde di-sec-alkyl acetal, (b) reacting the formaldehyde di-sec-alkyl acetal with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst to form an ethyleneglycol mono-sec-alkyl ether and the sec-alcohol, (c) hydrolyzing the ethyleneglycol mono-sec-alkyl ether with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400C to form ethyleneglycol and the sec-alcohol, and (d) recycling the sec-alcohol formed in the above steps (b) and (c) to the reaction in the step (a).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As is mentioned above, the intermediate compound in the inventive method is a sec-alkyl monoether of ethylene-glycol. It is known in the prior art that alkyl monoethers of ethyleneglycol are prepared by the reaction of an alkyl acetal of formaldehyde with hydrogen and carbon monoxide in the presence of a binary catalyst composed of a cobalt compound and an organic compound of trivalent phosphorus (see, for example, Japanese Patent Disclosure 52-71408).
In so far as the description of the above mentioned Patent Disclosure concerns, the alkyl acetals used in the method are limited to primary-alkyl acetals so that the alkyl monoethers of ethyleneglycol are naturally limited to primary-alkyl monoethers of ethyleneglycol.
; The inventors made an attempt to obtain ethyleneglycol by the hydrolysis of such a primary-alkyl monoether only to arrive at a conclusion that this process is absolutely not suitable as an industrial process due to the extremely low yield of the desired ethyleneglycol. For example, the hydrolysis of ethyleneglycol mono-n-butyl ether tried under diversified reaction conditions gave ethyleneglycol only in a yield of 1.1% or smaller.
As is mentioned above, the inventive method comprises the steps (a) and (b), in which the intermediate compound is a sec-alkyl monoether of ethyleneglycol. These steps are expressed by the following reaction equations.
- 3a -~15~3~8 ~Rl Rl Rl CH2(OCH~ 2)2 + CO + 2H2 -~~~ HCH2CH2CH~ 2 + 2~CHH . (1) ~, Rl Rl ~ HOCH2CH2OCH~ 2 + H20 ~~~~ HOCH2CH2OH + 2~CHOH ~ (2) ¦' In the above equations, the symbols Rl and R2 are each independ-ently an alkyl group such as methyl, ethyl, propyl and butyl groups. It is a novel discovery that the hydrolysis reaction of the above equation (2) proceeds readily to give ethylene-,' glycol in a high yield when catalyzed by a suitable catalyst.
¦i The gaseous mixture to be reacted with the acetal containscarbon monoxide and hydrogen in a molar ratio of CO:H2 in the , range from 1:10 to 10:1 or, preferably, from 1:3 to 3:1. The ,l gaseous mixture may be the so-called synthesis gas produced in various known petrochemical~or gas-chemical processes. The ; reaction of the step (a) is carried out under pressurization with the above gaseous mixture in the range from 50 to 300 kg/cm2 and at a temperature in the range from 170 to 200 C.
The reaction of the step (a) ls specifically catalyzed by a catalytic amount of a cobalt compound. The most effective ¦ cobalt catalyst is cobalt carbonyl Co2(CO)8 although many cobalt ¦ compounds capable of orming the cobalt carbonyl under the ¦i reaction conditions can be used equivalently. The cobalt materials convertible to cobalt carbonyl include metallic cobalt and cobalt oxide as well as salts of cobalt such as cobalt carbonate, cobalt acetate, cobalt sulfate and the like. The amount of the cobalt catalyst used in the reaction is not parti-¦cularly limitative but an amount in the range from 0.00002 to 0.02 mole as cobalt is usually sufficient per moleof the starting acetal compound.
~ 4 ~
.,1 , .~
~5~)318 The reaction of the acetal compound with hydrogen and carbon monoxide may proceed as undiluted without any solvent but it is preferable in most cases that the acetal compound is diluted with a suitable volume of a non-polar solvent such as benzene, ,~ toluene, xylene, cyclohexane, n-hexane, n-heptane, liquid paraf-fin, alkyl ethers and the like.
The use of a solvent is not essential but preferable to prevent the undesirable side reaction between the once formed ~ monoether and the starting acetal to decrease the yield of the monoether. Therefore, it is recommended that the starting acetal is diluted with 2 -to 5 times by volume of a solvent.
The reaction is usually complete within 1 to 10 hours.
i ;~ After the end of the reaction of the step (a), the reaction , mixture is taken out of the pressurized vessel and, if desired, the sec-alkyl monoether of ethyleneglycol is isolated by distil-,. :j. . , . -- i lation or other suitable method. The reaction mixture as taken .- Ij .
- l out of the reaction vessel can be subjected to the hydrolysis reaction but the sec-alkyl monoether should be isolated when a Il higher velocity of the hydrolysis is desired. The conversion 'I of the starting acetal compound usually exceeds 99% and the yield ,i of the desired monoether compound can be as high as 75% or more based on the consumed acetal compound. The principal side ~ reaction is the hydrogenative decomposition of the acetal into ,~ the sec-alkanol and methyl ether thereof.
'~ The above described results of the cobalt-catalyzed reaction ¦ are surprising since the reaction of the primary-alkyl acetal of formaldehyde with hydrogen and carbon monoxide can proceed only in the presence of the above mentioned binary catalyst of Il cobalt and organophosphorus compounds and hardly proceeds with ¦ the single-component catalyst of the cobalt compound alone.
3~8 ; As a rough estimation, the reaction velocity of a sec-alkyl acetal of formaldehyde is approximately 10 times larger than the velocity wit~an aoetal of formaldehyde with primary-alkyl ~ groups having the same number of carbon atoms.
Accordingly, the amount of the cobalt catalyst in the reaction of the equation (1) above can be much smaller than in the similar reaction with a primary alkyl acetal instead of secondary. For example, the above recited Japanese Patent Disclosure 52-71408 recommends an amount of about 2% by moles of cobalt carbonyl based on the amount of the starting primary ' alkyl acetal or 1.5~ by weight of the carbonyl in the reaction mixture while the amount of the cobalt carbonyl in the inventive reaction of the equation (l? is in the range from 0.16.to 0.80%
by moles based on the amount of the secondary alkyl acetal ~ corresponding to a concentration of 0.07 to 0.35% by weight ;~of the cobalt carbonyl ln the reaction mixture.
; For Example, the reaction of di-n-propylacetal of formalde-hyde gave the desired monoether compound in a yield of 9.7%
while the reaction with the di-isopropylacetal of formaldehyde , carried out under the same reaction conditions gave 70% or more ,, of the desired monoether compound when the catalyst was a single-component cobalt carbonyl without the addition of an organophos-phorus compound. Further, the reaction of diethylacetal of , formaldehyde carried out in a similar manner gave the desired ~, ethyleneglycol monoethyl ether in a yield of only 4.0%. Thus, the reaction of the step (a) is unique in the absence of any 1, organophosphorus compound in the catalyst system which has been ¦I considered to be indispensable in order to obtain a yield of I¦ the monoether higher than 70%.
~15~318 The second step of the inventive method, i.e. the step (b), is the hydrolysis of the sec-alkyl monoether of ethyleneglycol with water. It is also surprising that the hydrolysis conversion of the sec-alkyl monoether readily reaches 90% or higher while, ; as is mentioned above, a similar hydrolysis reaction of a primary-alkyl monoether is extremely difficult under the same conditions.
, The reaction of the hydrolysis readily proceeds when water is admixed to the monoether in an equimolar amount or larger and the reaction mixture is heated at a temperature in the range from 200 to 400 C in the presence of a suitable acidic catalyst , such as sulfuric acid, zinc chloride and the like soluble in the reaction mixture as well as certain solid acidic catalysts such as silica-alumina or aluminosilicates.
The method of the present invention may be carried out either as a batch-wise process or as a continuous process accord-~'~ing to need. The isolation or recovery of the desired product, - the by-products and the catalyst can be performed by one or a combination of known techniques such as distillation with no particular difficulties. The principal by-product of the , inventive method is the secondary alcohol of the formula R2`CHOH
produced in both of the step (a) and step (b) and it is readily recycled to the acetal com~ound of formaldehyde. Therefore the invention provides a very efficient means for the industrial il production of ethyleneglycol starting from formaldehyde and ~ synthesis gas with high selectivity and in a good yield.
Following are the examples to illustrate the inventive il method in further detail but not to limit the scope of the invention in any way.
I
Il ;
~ - 7 -"
1:15V318 Example 1.
Into a stainless steel-made autoclave of 300 ml capacity equipped with an electromagnetically driven vertical stirrer were introduced 16.5 g of formaldehyde diisopropylacetal . ~CH3)2CHO-CH2-OCH(CH3)2 (0.125 mole), 80 g of toluene and cobalt ,~ carbonyl Co2(CO)B in an amount indicated in Table 1 below and ` the air inside the autoclave was replaced with a 1:1 by volume gaseous mixture of carbon monoxide and hydrogen. Thereafter, the autoclave was pressurized with the same gaseous mixture with simultaneous temperature elevation reaching the temperature , indicated in Table 1 when the pressure inside the autoclave was equal to 200 kg/cm2, the temperature and the pressure being ~¦ maintained throughout the reaction by continous supply of the gaseous mixture. After the end of the reaction time of the ,, duration as indicated in Table~l, the reaction mixture was taken out of thé cooled autoclave and analyzed to give the results ll of the conversion of the acetal compound and the yield of the i!
desired monoether compound based on the consumed starting acetal compound as shown in Table 1.
....Table 1 il .
.~ Experi- Cobalt Reaction Reaction Conversion Yield of ment carbonyl temper- time, of acetal monoether No. .taken, ature, hours compound, compound, ... m moles C %
1 1.0 180 1.5 98.8 59.6
BACKGROUND OF THE INVENTION
The present invention relates to a method for manufacturing ` ethyleneglycol with high efficiency and economy. More parti-~ cularly, the invention relates to a method for manufacturing ethyleneglycol by hydrolyzing a secondary alkyl monoether of ethyleneglycol which in turn is synthesized by the reaction of a formaldehyde di-sec-alkyl acetal with hydrogen and carbon monoxide.
Ethyleneglycol is an industrially important basic compound in a wide field of chemical industry as a starting material for polyesters, as a solvent, as a non-volatile anti-freezing agent . .
or coolant and the like.
The processes for the industrial production of ethylen~lycol ~l currently on use are mostly petrochemical with ethylene as the - ~ starting material. Alternatively, several processes utilize so-called Cl compounds having a single carbon atom in a molecule such as carbon monoxide, formaldehyde and the like as the starting I material.
,~ For example, a method is known, as one of the Cl processes, by which ethyleneglycol is directly synthesized from a so-called synthesis gas, i.e. a gaseous mixture of hydrogen and carbon monoxide, in the presence of a rhodium catalyst (see, for example, Japanese Patent Disclosure 52-42809). This method is, however, ~j .
25 ¦~ not advantageous as an industrial process since the reaction must be carried out under a superatmospheric pressure of as high as 500 kg/cm2 or higher.
An alternative method as one of the Cl processes proposed ! in Japanese Patent Disclosure 54-106408 utilizes a somewhat i ;', _ . _ . .. . _ 3~8 lengthy synthetic route according to which formaldehyde is reacted with carbon monoxide to form glycolic acid which is then converted to a glycolate ester by esterification followed by the hydrogenation of the ester compound into ethyleneglycol. This method is also defective as an industrial process since the high-pressure reaction of formaldehyde with carbon monoxide must be catalyzed by a highly corrosive strong acid such as hydrofluoruc acid.
Further alternatively, a one-step method is disclosed in Japanese Patent Disclosure 51-128903 and 53-53607 in which ethyleneglycol is obtained directly by the reaction of formaldehyde and synthesis gas. One of the drawbacks of this method from the industrial standpoint is the undesirably low selectivity of ethyleneglycol among the reaction products. For example, the yield of ethylene-glycol rarely exceeds 40~ as calculated on the base of the consumed formaldehyde.
SUMMARY OF THE INVENTION
Thus, an object of the present invention is to provide a novel and improved method for the synthetic preparation of ethyleneglycol via a so-called Cl process, by which ethylene-glycol can be manufactured in a high yield and without the difficulties in the prior art processes as.
described above.
According to one aspect of the invention there is provided a method for the preparation of ethyleneglycol which comprises hydrolyzing sec-alkyl monoether of ethyleneglycol with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400C.
According to another aspect of the invention there is provided a method for the preparation of ethyleneglycol .
3~8 from formaldehyde, carbon monoxide and hydrogen as the starting materials which comprises the steps of (a~
reacting formaldehyde with a sec-alcohol to form a formaldehyde di-sec-alkyl acetal, (b) reacting the formaldehyde di-sec-alkyl acetal with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst to form an ethyleneglycol mono-sec-alkyl ether and the sec-alcohol, (c) hydrolyzing the ethyleneglycol mono-sec-alkyl ether with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400C to form ethyleneglycol and the sec-alcohol, and (d) recycling the sec-alcohol formed in the above steps (b) and (c) to the reaction in the step (a).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As is mentioned above, the intermediate compound in the inventive method is a sec-alkyl monoether of ethylene-glycol. It is known in the prior art that alkyl monoethers of ethyleneglycol are prepared by the reaction of an alkyl acetal of formaldehyde with hydrogen and carbon monoxide in the presence of a binary catalyst composed of a cobalt compound and an organic compound of trivalent phosphorus (see, for example, Japanese Patent Disclosure 52-71408).
In so far as the description of the above mentioned Patent Disclosure concerns, the alkyl acetals used in the method are limited to primary-alkyl acetals so that the alkyl monoethers of ethyleneglycol are naturally limited to primary-alkyl monoethers of ethyleneglycol.
; The inventors made an attempt to obtain ethyleneglycol by the hydrolysis of such a primary-alkyl monoether only to arrive at a conclusion that this process is absolutely not suitable as an industrial process due to the extremely low yield of the desired ethyleneglycol. For example, the hydrolysis of ethyleneglycol mono-n-butyl ether tried under diversified reaction conditions gave ethyleneglycol only in a yield of 1.1% or smaller.
As is mentioned above, the inventive method comprises the steps (a) and (b), in which the intermediate compound is a sec-alkyl monoether of ethyleneglycol. These steps are expressed by the following reaction equations.
- 3a -~15~3~8 ~Rl Rl Rl CH2(OCH~ 2)2 + CO + 2H2 -~~~ HCH2CH2CH~ 2 + 2~CHH . (1) ~, Rl Rl ~ HOCH2CH2OCH~ 2 + H20 ~~~~ HOCH2CH2OH + 2~CHOH ~ (2) ¦' In the above equations, the symbols Rl and R2 are each independ-ently an alkyl group such as methyl, ethyl, propyl and butyl groups. It is a novel discovery that the hydrolysis reaction of the above equation (2) proceeds readily to give ethylene-,' glycol in a high yield when catalyzed by a suitable catalyst.
¦i The gaseous mixture to be reacted with the acetal containscarbon monoxide and hydrogen in a molar ratio of CO:H2 in the , range from 1:10 to 10:1 or, preferably, from 1:3 to 3:1. The ,l gaseous mixture may be the so-called synthesis gas produced in various known petrochemical~or gas-chemical processes. The ; reaction of the step (a) is carried out under pressurization with the above gaseous mixture in the range from 50 to 300 kg/cm2 and at a temperature in the range from 170 to 200 C.
The reaction of the step (a) ls specifically catalyzed by a catalytic amount of a cobalt compound. The most effective ¦ cobalt catalyst is cobalt carbonyl Co2(CO)8 although many cobalt ¦ compounds capable of orming the cobalt carbonyl under the ¦i reaction conditions can be used equivalently. The cobalt materials convertible to cobalt carbonyl include metallic cobalt and cobalt oxide as well as salts of cobalt such as cobalt carbonate, cobalt acetate, cobalt sulfate and the like. The amount of the cobalt catalyst used in the reaction is not parti-¦cularly limitative but an amount in the range from 0.00002 to 0.02 mole as cobalt is usually sufficient per moleof the starting acetal compound.
~ 4 ~
.,1 , .~
~5~)318 The reaction of the acetal compound with hydrogen and carbon monoxide may proceed as undiluted without any solvent but it is preferable in most cases that the acetal compound is diluted with a suitable volume of a non-polar solvent such as benzene, ,~ toluene, xylene, cyclohexane, n-hexane, n-heptane, liquid paraf-fin, alkyl ethers and the like.
The use of a solvent is not essential but preferable to prevent the undesirable side reaction between the once formed ~ monoether and the starting acetal to decrease the yield of the monoether. Therefore, it is recommended that the starting acetal is diluted with 2 -to 5 times by volume of a solvent.
The reaction is usually complete within 1 to 10 hours.
i ;~ After the end of the reaction of the step (a), the reaction , mixture is taken out of the pressurized vessel and, if desired, the sec-alkyl monoether of ethyleneglycol is isolated by distil-,. :j. . , . -- i lation or other suitable method. The reaction mixture as taken .- Ij .
- l out of the reaction vessel can be subjected to the hydrolysis reaction but the sec-alkyl monoether should be isolated when a Il higher velocity of the hydrolysis is desired. The conversion 'I of the starting acetal compound usually exceeds 99% and the yield ,i of the desired monoether compound can be as high as 75% or more based on the consumed acetal compound. The principal side ~ reaction is the hydrogenative decomposition of the acetal into ,~ the sec-alkanol and methyl ether thereof.
'~ The above described results of the cobalt-catalyzed reaction ¦ are surprising since the reaction of the primary-alkyl acetal of formaldehyde with hydrogen and carbon monoxide can proceed only in the presence of the above mentioned binary catalyst of Il cobalt and organophosphorus compounds and hardly proceeds with ¦ the single-component catalyst of the cobalt compound alone.
3~8 ; As a rough estimation, the reaction velocity of a sec-alkyl acetal of formaldehyde is approximately 10 times larger than the velocity wit~an aoetal of formaldehyde with primary-alkyl ~ groups having the same number of carbon atoms.
Accordingly, the amount of the cobalt catalyst in the reaction of the equation (1) above can be much smaller than in the similar reaction with a primary alkyl acetal instead of secondary. For example, the above recited Japanese Patent Disclosure 52-71408 recommends an amount of about 2% by moles of cobalt carbonyl based on the amount of the starting primary ' alkyl acetal or 1.5~ by weight of the carbonyl in the reaction mixture while the amount of the cobalt carbonyl in the inventive reaction of the equation (l? is in the range from 0.16.to 0.80%
by moles based on the amount of the secondary alkyl acetal ~ corresponding to a concentration of 0.07 to 0.35% by weight ;~of the cobalt carbonyl ln the reaction mixture.
; For Example, the reaction of di-n-propylacetal of formalde-hyde gave the desired monoether compound in a yield of 9.7%
while the reaction with the di-isopropylacetal of formaldehyde , carried out under the same reaction conditions gave 70% or more ,, of the desired monoether compound when the catalyst was a single-component cobalt carbonyl without the addition of an organophos-phorus compound. Further, the reaction of diethylacetal of , formaldehyde carried out in a similar manner gave the desired ~, ethyleneglycol monoethyl ether in a yield of only 4.0%. Thus, the reaction of the step (a) is unique in the absence of any 1, organophosphorus compound in the catalyst system which has been ¦I considered to be indispensable in order to obtain a yield of I¦ the monoether higher than 70%.
~15~318 The second step of the inventive method, i.e. the step (b), is the hydrolysis of the sec-alkyl monoether of ethyleneglycol with water. It is also surprising that the hydrolysis conversion of the sec-alkyl monoether readily reaches 90% or higher while, ; as is mentioned above, a similar hydrolysis reaction of a primary-alkyl monoether is extremely difficult under the same conditions.
, The reaction of the hydrolysis readily proceeds when water is admixed to the monoether in an equimolar amount or larger and the reaction mixture is heated at a temperature in the range from 200 to 400 C in the presence of a suitable acidic catalyst , such as sulfuric acid, zinc chloride and the like soluble in the reaction mixture as well as certain solid acidic catalysts such as silica-alumina or aluminosilicates.
The method of the present invention may be carried out either as a batch-wise process or as a continuous process accord-~'~ing to need. The isolation or recovery of the desired product, - the by-products and the catalyst can be performed by one or a combination of known techniques such as distillation with no particular difficulties. The principal by-product of the , inventive method is the secondary alcohol of the formula R2`CHOH
produced in both of the step (a) and step (b) and it is readily recycled to the acetal com~ound of formaldehyde. Therefore the invention provides a very efficient means for the industrial il production of ethyleneglycol starting from formaldehyde and ~ synthesis gas with high selectivity and in a good yield.
Following are the examples to illustrate the inventive il method in further detail but not to limit the scope of the invention in any way.
I
Il ;
~ - 7 -"
1:15V318 Example 1.
Into a stainless steel-made autoclave of 300 ml capacity equipped with an electromagnetically driven vertical stirrer were introduced 16.5 g of formaldehyde diisopropylacetal . ~CH3)2CHO-CH2-OCH(CH3)2 (0.125 mole), 80 g of toluene and cobalt ,~ carbonyl Co2(CO)B in an amount indicated in Table 1 below and ` the air inside the autoclave was replaced with a 1:1 by volume gaseous mixture of carbon monoxide and hydrogen. Thereafter, the autoclave was pressurized with the same gaseous mixture with simultaneous temperature elevation reaching the temperature , indicated in Table 1 when the pressure inside the autoclave was equal to 200 kg/cm2, the temperature and the pressure being ~¦ maintained throughout the reaction by continous supply of the gaseous mixture. After the end of the reaction time of the ,, duration as indicated in Table~l, the reaction mixture was taken out of thé cooled autoclave and analyzed to give the results ll of the conversion of the acetal compound and the yield of the i!
desired monoether compound based on the consumed starting acetal compound as shown in Table 1.
....Table 1 il .
.~ Experi- Cobalt Reaction Reaction Conversion Yield of ment carbonyl temper- time, of acetal monoether No. .taken, ature, hours compound, compound, ... m moles C %
1 1.0 180 1.5 98.8 59.6
2 0 5 . 180 4 0 98.9 71.4
3 1 0.2 I 190 7-0 1 99-2 1 74-1 . I
The hydrolysis reaction of the above obtained mono-isopropyl ; ether of ethyleneglycol was carried out by introducing 26 g (0.25 mole) of the monoether compound, 9 g (0.5 mole) of water and a catalyst of the kind and in an amount as indicated in . Table 2 below into a stainless steel-made autoclave of lO0 ml capacity followed by purging the air in the vessel with nitrogen i'~ and temperature elevation up to 300 C, the temperature being ; maintained throughout the reaction of the duration as indicated . ', in Table 2.
.~ After the end of the reaction time, the reaction mixture was taken out of the cooled autoclave and analyzed for the ' content of the desired ethyleneglycol to give the results shown ,j in Table 2 in % yield based on the monoether compound taken.
In Experiment No. 6 where a solid catalyst was used, the catalyst ~'i was washed with acetone to be freed from any.reaction ~ixture ~. and thç washing was added to the reaction mixture before analysis.
.~
~i Table 2 ,i . ~
¦~ Experi- .. Reaction Yield of , ment Catalyst, taken (g) time, ethylene-No. hours glycol, %
,. ,, .... _ .... _ . 4 Sulfuric acid (l)l 90.8 Zinc chloride (l). 3 86.6 ; Silica-alumina* ~20) lO 96.0 *) 10% Sio2-90% Al23 ¦¦ Example:2..
The reaction of formaldehyde di-sec-butylacetal of the formula CH2(OCH~C H )2 with:carbo.n monoxide and h~drogen was ¦l undertaken substantially in the same manner as in Experiment !l 9 li ., 115~ 18 No. 3 of Example 1 by introducing 20 g (0.125 mole) of the acetal compound, 80 g of toluene and 0.2 m mole of cobalt carbonyl into the 300 ml autoclave. The conversion of the acetal compound ~ was 92.8% and the yield of the monoether compound, i.e. ethylene-glycol mono-sec-butyl ether, was 76.4% based on the amount of the consumed acetal compound.
The hydrolysis reaction of the above obtained monoether compound was carried out substantially in the same manner as in Experiment No. 6 of Example 1 by introducing 10 g (0.078 mole) of the monoether compound, 4.5 g (0.25 mole) of water and 10 g of the same silica-alumina catalyst into the 100 ml autoclave.
The yield of the ethyleneglycol was 70.5% based on the amount of the monoether compound taken.
Example 3.
.~ ........................................ ..
~ Into the same lOO ml autoclave as used in Example 1 were ', taken 19 g (25 ml) of silica-alumina catalyst and 36 g (2 moles) ', of water and the air in the vessel was replaced with nitrogen.
The autoclave was heated up to 265 C when the pressure inside ' the vessel reached about 24 kg/cm2.
l Then 13 g (0.125 mole) of the ethyleneglycol mono-isopropyl ~ ether were introduced into the autoclave by pressurization with `l a pump and the reaction was continued at the same temperature for 1 hour. The pressure inside the vessel was increased to l 37 kg/cm2 at the end of the reaction time. The reaction mixture ~ was withdrawn from the bottom of the autoclave by opening the ,¦ valve and analyzed gas chromatographically. The conversion of the monoether and the yields of ethyleneglycol and isopropyl , alcohol on the base of the reacted monoether were 53%, 99% and ~ I -- 1 0 . . ~
5~318 60%, respectively. The low yield of the isopropyl alcohol indicated the dehydration of the alcohol into propylene.
Distillation of the reaction mixture gave 4 g of ethylene-glycol remaining after distilling out of the azeotropic mixtures ~ of isopropyl alcohol and water at 80 C and then of the unreacted ! monoether and water at 98 C.
, Example 4.
The experimental procedure was substantially the same ' as in Experiment No. l of Example 1 except that the gaseous ' feed was a 1:2 by moles mixture of carbon monoxide and hydrogen under a pressure of 300 kg/cm2 and the reaction time was extended to 3 hours. The results were: conversion of the acetal compound 100%; yield of the monoether compound 76.4%; and yield of i methylisopropyl ether 11.5%.
,j ~' As may be concluded from the above results, the combination ,l of the best reaction conditions in both of the step (a) and step (b), i.e. the conditions in Example 4 for the step (a) ' and the conditions in Example 3 for the step (b), results in i an overall yield of the ethyleneglycol amounting to 76% based ~j on the consumed starting acetal compound with the acetal compound, '~ carbon monoxide, hydrogen and water as the reactants or the starting materials.
The hydrolysis reaction of the above obtained mono-isopropyl ; ether of ethyleneglycol was carried out by introducing 26 g (0.25 mole) of the monoether compound, 9 g (0.5 mole) of water and a catalyst of the kind and in an amount as indicated in . Table 2 below into a stainless steel-made autoclave of lO0 ml capacity followed by purging the air in the vessel with nitrogen i'~ and temperature elevation up to 300 C, the temperature being ; maintained throughout the reaction of the duration as indicated . ', in Table 2.
.~ After the end of the reaction time, the reaction mixture was taken out of the cooled autoclave and analyzed for the ' content of the desired ethyleneglycol to give the results shown ,j in Table 2 in % yield based on the monoether compound taken.
In Experiment No. 6 where a solid catalyst was used, the catalyst ~'i was washed with acetone to be freed from any.reaction ~ixture ~. and thç washing was added to the reaction mixture before analysis.
.~
~i Table 2 ,i . ~
¦~ Experi- .. Reaction Yield of , ment Catalyst, taken (g) time, ethylene-No. hours glycol, %
,. ,, .... _ .... _ . 4 Sulfuric acid (l)l 90.8 Zinc chloride (l). 3 86.6 ; Silica-alumina* ~20) lO 96.0 *) 10% Sio2-90% Al23 ¦¦ Example:2..
The reaction of formaldehyde di-sec-butylacetal of the formula CH2(OCH~C H )2 with:carbo.n monoxide and h~drogen was ¦l undertaken substantially in the same manner as in Experiment !l 9 li ., 115~ 18 No. 3 of Example 1 by introducing 20 g (0.125 mole) of the acetal compound, 80 g of toluene and 0.2 m mole of cobalt carbonyl into the 300 ml autoclave. The conversion of the acetal compound ~ was 92.8% and the yield of the monoether compound, i.e. ethylene-glycol mono-sec-butyl ether, was 76.4% based on the amount of the consumed acetal compound.
The hydrolysis reaction of the above obtained monoether compound was carried out substantially in the same manner as in Experiment No. 6 of Example 1 by introducing 10 g (0.078 mole) of the monoether compound, 4.5 g (0.25 mole) of water and 10 g of the same silica-alumina catalyst into the 100 ml autoclave.
The yield of the ethyleneglycol was 70.5% based on the amount of the monoether compound taken.
Example 3.
.~ ........................................ ..
~ Into the same lOO ml autoclave as used in Example 1 were ', taken 19 g (25 ml) of silica-alumina catalyst and 36 g (2 moles) ', of water and the air in the vessel was replaced with nitrogen.
The autoclave was heated up to 265 C when the pressure inside ' the vessel reached about 24 kg/cm2.
l Then 13 g (0.125 mole) of the ethyleneglycol mono-isopropyl ~ ether were introduced into the autoclave by pressurization with `l a pump and the reaction was continued at the same temperature for 1 hour. The pressure inside the vessel was increased to l 37 kg/cm2 at the end of the reaction time. The reaction mixture ~ was withdrawn from the bottom of the autoclave by opening the ,¦ valve and analyzed gas chromatographically. The conversion of the monoether and the yields of ethyleneglycol and isopropyl , alcohol on the base of the reacted monoether were 53%, 99% and ~ I -- 1 0 . . ~
5~318 60%, respectively. The low yield of the isopropyl alcohol indicated the dehydration of the alcohol into propylene.
Distillation of the reaction mixture gave 4 g of ethylene-glycol remaining after distilling out of the azeotropic mixtures ~ of isopropyl alcohol and water at 80 C and then of the unreacted ! monoether and water at 98 C.
, Example 4.
The experimental procedure was substantially the same ' as in Experiment No. l of Example 1 except that the gaseous ' feed was a 1:2 by moles mixture of carbon monoxide and hydrogen under a pressure of 300 kg/cm2 and the reaction time was extended to 3 hours. The results were: conversion of the acetal compound 100%; yield of the monoether compound 76.4%; and yield of i methylisopropyl ether 11.5%.
,j ~' As may be concluded from the above results, the combination ,l of the best reaction conditions in both of the step (a) and step (b), i.e. the conditions in Example 4 for the step (a) ' and the conditions in Example 3 for the step (b), results in i an overall yield of the ethyleneglycol amounting to 76% based ~j on the consumed starting acetal compound with the acetal compound, '~ carbon monoxide, hydrogen and water as the reactants or the starting materials.
Claims (6)
1. A method for the preparation of ethyleneglycol which comprises hydrolyzing sec-alkyl monoether of ethyleneglycol with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400 °C.
2. A method for the preparation of ethyleneglycol which comprises the steps of (a) reacting a formaldehyde di-sec-alkylacetal with carbon monoxide and hydrogen in the presence of a catalytic amount of cobalt carbonyl to form a sec-alkyl monoether of ethyleneglycol, and (b) hydrolyzing the sec-alkyl monoether of ethyleneglycol with water in the presence of an acidic catalyst at a temperature .
in the range from 200 to 400 °C.
in the range from 200 to 400 °C.
3. The method as claimed in claim 2 wherein the reaciton of the step (a) is carried out under a pressure in the range from 50 to 300 kg/cm2 as pressurized with a gaseous mixture of carbon monoxide and hydrogen and at a temperature in the range from 170 to 200 °C.
4. The method as claimed in claim 3 wherein the gaseous mixture of carbon monoxide and hydrogen contains carbon monoxide and hydrogen in a volume ratio from 1:10 to 10:1.
5. The method as claimed in claim 2 wherein the formaldehyde di-sec-alkylacetal is formaldehyde di-isopropylacetal or form-aldehyde di-sec-butylacetal.
6. A method for the preparation of ethyleneglycol from formaldehyde, carbon monoxide and hydrogen as the starting materials which comprises the steps of (a) reacting formaldehyde with a sec-alcohol to form a formaldehyde di-sec-alkyl acetal, (b) reacting the formaldehyde di-sec-alkyl acetal with carbon monoxide and hydrogen in the presence of a cobalt carbonyl catalyst to form an ethyleneglycol mono-sec-alkyl ether and the sec-alcohol, (c) hydrolyzing the ethyleneglycol mono-sec-alkyl ether with water in the presence of an acidic catalyst at a temperature in the range from 200 to 400°C to form ethyleneglycol and the sec-alcohol, and (d) recycling the sec-alcohol formed in the above steps (b) and (c) to the reaction in the step (a).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55021168A JPS593451B2 (en) | 1980-02-21 | 1980-02-21 | Manufacturing method of ethylene glycol |
| JP21168/1980 | 1980-02-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1150318A true CA1150318A (en) | 1983-07-19 |
Family
ID=12047381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000369645A Expired CA1150318A (en) | 1980-02-21 | 1981-01-29 | Method for manufacturing ethyleneglycol |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS593451B2 (en) |
| CA (1) | CA1150318A (en) |
| DE (1) | DE3104033C2 (en) |
| GB (1) | GB2070002B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554250B (en) * | 2015-09-30 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of method that glycol monoethyl ether hydrolysis prepares ethylene glycol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE890945C (en) * | 1942-07-11 | 1953-10-29 | Basf Ag | Process for the production of ethylene glycol |
-
1980
- 1980-02-21 JP JP55021168A patent/JPS593451B2/en not_active Expired
-
1981
- 1981-01-28 GB GB8102597A patent/GB2070002B/en not_active Expired
- 1981-01-29 CA CA000369645A patent/CA1150318A/en not_active Expired
- 1981-02-05 DE DE3104033A patent/DE3104033C2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3104033C2 (en) | 1984-10-31 |
| GB2070002A (en) | 1981-09-03 |
| DE3104033A1 (en) | 1981-12-10 |
| JPS56118026A (en) | 1981-09-16 |
| GB2070002B (en) | 1983-12-21 |
| JPS593451B2 (en) | 1984-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4317943A (en) | Process for preparing glycol ethers | |
| US5489702A (en) | Process for the production of dialkyl carbonate | |
| US4476326A (en) | Process for the synthesis of ethanol and acetaldehyde using cobalt compounds with novel promoters | |
| EP0130058B1 (en) | Catalytic conversion of ethers to esters and alcohols | |
| US4691048A (en) | Process for reducing carbonylation of aldehydes, uses as hemiacetalesters, catalyzed by cobalt carbonyl complexes | |
| EP0069339B1 (en) | Process for producing 7-octen-1-al and derivatives thereof | |
| US4874900A (en) | Preparation of pseudoionones | |
| US5053556A (en) | Process for producing alkenyl ethers | |
| CA1150318A (en) | Method for manufacturing ethyleneglycol | |
| US4235744A (en) | Carbonylation of olefinically unsaturated compounds | |
| US6541414B2 (en) | Catalyst for preparing 1,3-alkanediol from epoxide derivative | |
| US6348632B1 (en) | Process for preparing 1,3-alkanediol from epoxide derivative | |
| US3513189A (en) | Preparation of acetoacetic esters | |
| KR910006002B1 (en) | Hydrolysis process of dialkyl carbonate | |
| US4585891A (en) | Process for the production of dihydrocarbyl oxalates | |
| US3277187A (en) | Hochz ch | |
| US4318860A (en) | Preparation of unsaturated monester precursor for pelargonic acid | |
| JP3756537B2 (en) | Dimethyldecandial and process for producing the same | |
| JP2675156B2 (en) | Process for producing 1,1,2-trialkoxyethane | |
| US6600065B2 (en) | Process for preparing 3-hydroxyesters from epoxide derivatives | |
| KR100440872B1 (en) | Process for Preparing 1,3-alkanediol from Epoxide Derivatives | |
| JP3228485B2 (en) | Method for producing 2-formyl-4-acyloxy-1-butene | |
| US4511743A (en) | Process for homologating alcohols through the intermediate production of ketals with cobalt carbonyl complexes as catalysts | |
| EP0101223B1 (en) | process for producing phenylacetones | |
| CA1179375A (en) | Process for improving ethylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |