CA1060907A - Process for preparing butanediols - Google Patents
Process for preparing butanediolsInfo
- Publication number
- CA1060907A CA1060907A CA234,642A CA234642A CA1060907A CA 1060907 A CA1060907 A CA 1060907A CA 234642 A CA234642 A CA 234642A CA 1060907 A CA1060907 A CA 1060907A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- reaction
- organic solvent
- butanediols
- 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.)
- Expired
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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
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
Abstract A process for preparing butanediols which comprises reacting allyl alcohol with carbon monoxide and hydrogen in an organic solvent in the presence, as a catalyst, of a carbonyl complex compound of rhodium stable to water and insoluble in it thereby to hydroformylate it, and hydrogenat-ing the resulting aldehydes. Butanediols are useful for the production of poly (butylene terephthalate) plastics used in engineering, and poly-urethanes.
Description
10609~7 ~ his invention relates to a process for pre-paring butanediols from allyl alcohol.
Butanediols are very useful as raw materials for the production of poly(butylene terephthalate) generally called "engineering plastics" and polyurethane, and their utility also extends to a variety of other chemical fields.
Commercial production of 1,4-butanediol has previously relied mainly on the Reppe process using acetylene as a raw material and a process which comprises halogenating butadiene followed by hydrolysis and hydro-genation. These methods, however, suffer from various defects such as the risk of explosion of the starting ~; material, the complexity of process steps, the necessity 15 of high pressures, and the abundance of by-products,~
and are not entirely advantageous for commercial operations. ~-. ,. : .
Because of the great importance of 1,4-butanediol as an -` intermediate, various investigations have been made in an attempt to establish a cheaper manufacturing process.
Many of these investigations have been directed to methods - using butadiene or butenes which are unsaturated compounds containing 4 carbon atoms as starting materials~ These methods have not yet gained commercial acceptance because they encounter serious difficulties in regard to the life of the catalyst, the rate of reaction, the recovery ~ of the catalyst, and the safety of operationO It has been ; desired therefore to develop a new process for preparing 1,4-butanediol free from the defects of the prior art .,, --methods.
Butanediols are very useful as raw materials for the production of poly(butylene terephthalate) generally called "engineering plastics" and polyurethane, and their utility also extends to a variety of other chemical fields.
Commercial production of 1,4-butanediol has previously relied mainly on the Reppe process using acetylene as a raw material and a process which comprises halogenating butadiene followed by hydrolysis and hydro-genation. These methods, however, suffer from various defects such as the risk of explosion of the starting ~; material, the complexity of process steps, the necessity 15 of high pressures, and the abundance of by-products,~
and are not entirely advantageous for commercial operations. ~-. ,. : .
Because of the great importance of 1,4-butanediol as an -` intermediate, various investigations have been made in an attempt to establish a cheaper manufacturing process.
Many of these investigations have been directed to methods - using butadiene or butenes which are unsaturated compounds containing 4 carbon atoms as starting materials~ These methods have not yet gained commercial acceptance because they encounter serious difficulties in regard to the life of the catalyst, the rate of reaction, the recovery ~ of the catalyst, and the safety of operationO It has been ; desired therefore to develop a new process for preparing 1,4-butanediol free from the defects of the prior art .,, --methods.
- 2 - ~ -~
':
.
. .
It is already known that allyl alcohol can be hydroformylated in the presence, as a catalyst, of a carbonyl complex compound of a metal of Group VIII of the periodic table. For example, J. AmO Chem. Soc., Vol. 78, pO 3~3 (1948) and J. Am. ChemO Soc., Vol.
79, 3051 (1949) state that when allyl alcohol is hydro-formylated using octacarbonyl dicobalt as a catalyst, 4-hydroxybutyraldehyde is formed. Furthermore, J. Chem.
Soc., (A) p. 2753 (1970) and Japanese Patent Publication ~o. 6284/74 disclose that allyl alcohol can be hydrofor-mylated when a carbonyl compound of rhodium modified with a tri-substituted phosphine is used as a catalyst.
However, the method using a cobalt-type compound typified by octacarbonyl dicobalt affords 4-hydroxy-butyraldehyde convertible to l,4-butanediol in a selec-tivity of only less than 20%, and is therefore extremely disadvantageous for commercial operations. The reports on the use of the rhodium carbonyl compound as a catalyst fail to disclose the product and its selectivityO
In the hydroformylation reaction of olefins using carbonyl complex compounds of rhodium as a cat-alyst, the complete separation and recovery of the catalyst from the reaction product and its re-use are very important problems from an economical standpoint since the catalyst ls expensive. Unless these problems are solved, the above hydroformylation reaction cannot be employed as a commercial process for preparing aldehydes.
In the conventional hydroformylation reaction using a carbonyl complex compound o:.` rhodi m as a cata yst, hodium is recovered from the reaction mixture by various known methods among which are:
(1) a method in which the reaction mixture is distilled to separate it into the product and the catalyst, ; (2) a method in which a metal, water, an acid, hydrogen, etc. are added to decompose the catalyst, and rhodium is allowed to precipitate as a metal, - (~) a method in which rhodium is separated using a cellulose membrane or silicone rubber membrane, (4) a method in which rhodium is coordinated :: with a polymeric phosphorus compound, and (5) a method in which the reaction is carried out in a heterogeneous liquid phase using a water-` 15 hydrocarbon mixture and a water-soluble catalyst, and : the catalyst is distributed to an aqueous phase and .. . .
the product, to a hydrocarbon phase, thereby to separate -;
the catalyst from the product.
~hese methods, however, are not entirely economical ~: 20 for separating the catalyst for one or more reasons, such as the poor efficiency of separating the catalyst, the consequent reduction in the rate of the hydroformylation -~
; reaction, and the loss of the catalyst ingredients because of the need for troublesome separating and activation 25 steps for the catalystO In fact, a carkonyl complex -- compound of rhodium exhibits various superior characteristics ~ :
as a catalyst for hydroformylation of olefins on a :~
laboratory-scale operation, but except some special : cases, there has been no example in which this compound .. , ~
:. - 4 -. .
:. , . , , . ~ .
~ . . . , , . -10f~1)9C)7 was used on a commercial scale as a catalyst for hydrofor-mylating olefins.
0ur investigations show that other various problems arise in addition to the above defects when the known methods are used to separate rhodium from the uniform reaction mixture obtained by hydroformyl-ation of allyl alcohol using the a~ove-mentioned rhodium catalystO For example, according to the distillation me-thod (l), hydroxybutyraldehydes as the hydroformylation product are liable to change to high-boiling compounds by, for example, aldol condensation and acetalization, and therefore, this causes a decrease in the amount of the hydroxybutyraldehydes. Also in the method (5), since the starting allyl alcohol, the hydroxybutyr-aldehydes and the catalyst are distributed mainly to anaqueous phase, a troublesome procedure is required to separate them from each otherO
Accordingly, it is an object of this invention to provide a process for preparing butanediols from allyl alcohol which is free from the defects of the conventional processes mentioned above and in particular, includes a step of separating a rhodium catalyst with good efficiency.
We have found that when allyl alcohol is hydro-formylated in a water-immiscible organic solvent and the resulting reaction mixture containing a rhodium catalyst is extracted simply with water, the catalyst can be separated from the product with very good efficiency.
~ hus, according to this invention, there is probided a process for preparing butanediols, which .,~, .
, ,. ~ , ' .
~060907 co~prises reacting allyl alcohol with carbon monoxide and hy~rogen in an organic solvent in the presence, as a catalyst, of a water-stable water-insoluble carbonyl complex compound of rhodium thereby to hydroformylate it, e~tracting the resulting reaction mixture with water to separate it into an organic solvent phase containing the catalyst and an aqueous phase containing the resulting aldehydes, recycling the organic solvent phase for re-use in the next cycle of the hydroformylation reaction, and hydrogenating the aldehydes in the aqueous phase, thereb~ to form butanediols.
The characteristics and ad~antages o the present invention are that hydroxybutyraldehydes can be obtained in high : selectivities and yields; butanediols can be obtained ~ery easily by subjecting the aqueous phase resulting from the extraction of the reacti.on mixture with water to a hydrogenation reaction ~ in the presence of a catalyst such as Raney nickel without : separating the hydroxybutyraldehydes contained in it; and that ~:
the organic solyent phase containing the catalyst which is left ater extractîon of the reaction mixture with.water can be re-2Q used in the next cycle of the hydroformylating reaction without giy~ng any act~ati.ng treatment to it. In the light of the tradi.tional ~iew that a carbonyl complex compound of rhodium is ~ery unstable to water, it is surpri.sing that in the process of thi.s inyention, the catalyst does not undergo any change in the . presence of water.
.: Theoretically, 1,4-butanediol could be pxepared by a method which comprises preparing allyl acetate rom propylene, :' : hydroformylating the re.sulting allyl acetate to fo~m 4-acetoxybutyraldehyde, hydrogenating it and then hydrolyzing the hydrogenated product. However, according to such a method, the rate of reaction would be slow and the selectivity to 4-a~ coxybutyraldehyde would be low, e~en if a rhodium catalyst or cobalt catalyst is used. Furthermore, since 4-acetoxybutyr-aldehyde is difficulty soluble in water, this method does not permit the separation of the reaction mixture easily into the catalyst and the product as in the process of this invention.
The carbonyl complex compound of rhodium used as a catalyst in the hydroformylation reaction of this invention can be expressed by the general formula LmRh (.CO) X
wherein m is: 2 or 3; X represents a hydrogen atom or a chlorine atom; and L is a tri-substituted phosphine of the formula PRR'R"
in which R, R' and R" independently represent a phenyl group, a cycloh.exyl group, a tolyl group and an alkyl group of 1 to 6 ~ caroor ato~s.
,., . . .
,, :
. . . ~
Examples of the carbonyl complex compound of rhodium ~re:
RhH(Co)lp(-c6Hs)3]3~
RhH(.CO)[P(CH3 C6H4)3]3~ ~ :
RhH(.CO) LP (n-C4Hg ) 3] 3, RhCl(CO)[P(.C6H5)3]2' and RhCl(CO) ~ P~N(C2H5)2]3} 2' These complex compounds must be stable to water and ~ . :
insoluble in it. Complex compound containing triphenoxyphosphine , 10 such as RhH(CO)[P~OC6H5)3]3 cannot be used in this invention : because they are unstable to water. :
.. When the complex compound of the abo~e formula is used :~
., as a catalyst for the hydroformylation reaction of this .`' invention, a part of L dissociates in the sol~ent, and its ~ :
-` ! ability as a catalyst som~wh.at decreases. In order to reduce ~ the dissociation of L and make up for ~ ~ .
.',~ -' ' .
i.~' J, ' .
~, ' . .
. .
"' , . , ~', ;:
'' ' ' 'i ,''..~.
, . `
, .
'. ~
' : :.
. .
. . , . , the loss of the dissociated L, a trisubstituted phosphine, trisubstituted stibine or trisubstituted arsine of the above general formula Y~R'R" can be used as an excessive ligand togethcr with the complex compound of the above formula as a catalyst.
The solvent used in the hydroformylation re-action is an organic solvent which dissolves the cat-alyst and is not miscible with waterO Preferred organic solvents are aromatic hydrocarbons which are liquid at room temperature, such as benzene, toluene or xylene.
The reaction temperat-ure in the hydroformylation reaction of this invention is 0 to 200C., preferably 10 to 100C., and especially preferably 20 to 50C.
The reaction pressure is 1 to 50 Kg/cm (absolute), preferably 1.1 to 4 Kg/cm (absolute)0 The ratio of C0/H2 in the oxo gas can be varied within the range of 1/10 to 4/1, preferably 1/5 to 1/1. The co-presence of an inert gas such as nitrogen in the reaction system is permissible.
~he concentration of the catalyst can be varied optionally, but is naturally restricted by the selectivity to the straight-chain aldehyde, the rate of reaction and the solubility of the catalyst. The preferred concentration is 1.0 to 100 millimoles/liter.
;~- The separation of the hydroformylation reaction mixture into the catalyst and the product by extraction -can be performed by any known extraction techniquesO But in order to avoid side-reactions and the degeneration of the catalyst in the extraction step, the extraction is carried out preferably in an atmosphere of an oxo gasO
~0609~'~
~he amount of water used ~or extr~ction is determined a ~; according to the coefficients o~ distribution of the resulting aldehyde to the reaction solvent and water.
Usually, it is preferred to determine the amount of water so that the concentration o~ the aldehyde in the aqueous phase becomes at least 5% by weigh-tO
~ he organic solvent phase containing the catalyst separated from the reaction mixture can be recycled directly to the react~r. If desired, however, it can be recycled after su~decting it to an activation ' treatmentO The aqueous phase is used for a hydrogenation i reaction in order to convert the hydroformylated product of all alcohol dissolved in it to butanediolsO Known h hydrogenation catalysts such as ~i, Co, Pd, Pt and Ru can ;
be used for the hydrogenation reaction. ~he use of Rarey nickel is most preferred in view of its catalytic activity and economy.
~ here is no particular restriction on the reaction conditions for the hydrogenationO Because of ;~ 20 the heat stability of the hydroxybutyraldehydes, however, - the hydrogenation reaction is carried out preferably at , .
a temperature of not more than 100C., especially 20 to 50C. ~he rate of reaction increaseswith higher hydrogen : pressures, but in view of the economy of the reaction ~ 25 apparatus, the use of hydrogen at a partial pressure of - 1.0 to 10 Kg/cm2 (absolute) is preferredO
- ~he amount of the catalyst used for the ` hydrogenation reaction is neither restricted in particular, and is determined according to the rate of reactionO An ' . ' - -- 10 _ .
. , .
106090~7 inert gas such as nitrogeIl can, of coursc, be mixed with hydrogen. For ex~mple, when Raney nickel is used as the catalyst, the pre~erre~ amount of the catalyst is 0.5 to OnOOl gram-atom per loO mole 0~ the hydroxybutyral--dehyde.
The following Examples illustrate -the present invention more specifically.
Exam~le 1 A 500 mlO stainless steel pressure r~actor was charged with 1.0 millimo]e of RhH(CO)rP(C6H5)3]3 as ~ a catalyst, 1.0 millimole of triphenylphosphine, P(C6H5)3, - as an excess ligand, and 80 mlO of benzene as a solventO
The inside of the reactor was thoroughly purged with a ; gaseous mixture consisting of carbon monoxide and hydrogen 15 in a molar ratio of 1:1, and in a stream of this gaseous -~
mixture9 20 mlO of a benzene solution containing 0.2 mole of allyl alcohol was addedO ~he stirring of the mixture was started while maintaining the inside of the reactor at a pressure of 1.5 Kg/cm2 (absolute) and a temperature of 30Co Since the absorption of the gas occurred as soon as the stirring began, the pressure of the inside of the .
reactor was maintained at 105 Kg/cm2 (absolute) by adding ; a fresh supply of the mixed gas, and the reaction was performed at 30C. for 300 hoursO
Analysis of the reaction mixture by gas-chromatography showed that all the starting allyl alcohol ~ was consumed, and 118 millimoles of 4-hydroxybutyraldehyde, -; 7002 millimoles of 2-methyl-3-hydroxy-propionaldehyde, 402 millimols propionaldehyde and 204 millimoles of ,.' ~' - 11 - , .:
.
:
. . ;:. :
1~60907 ~-propyl alcohol were formed together with traces of ethane, propane, ~-butyrolactone and high-boiling substancesO
~ he reaction mixture was then e~tracted twice with 50 ml. of water in an atmosphere of a gaseous mixture consisting of carbon monoxide and hydrogenO 98% of the product was thus extracted into the aqueous phaseO 200g of a Raney nickel catalyst was added to the extract, and hydrogenation was carried out at room temperature for 6~0 hours while maintaining the partial pressure of hydro-gen at 3.0 Kg/cm2 (absolute). Analysis of the productshowed that 114~0 millimoles of 1,4-butanediol and 69.8 millimoles of 2-methyl-1,3-propanediol were formedO
~::
~he degree of hydrogenation was therefore more than 9~/0O
~; ~xample 2 ` 15 The same reactor as used in ~xample 1 was .. . .
charged with 5.0 millimoles of RhH(CO)[P(C6H5)~]3 and 80 ml~ of toluene, and the inside of the reactor was purged thoroughly with a gaseous mixture consisting of carbon monoxide and hydrogen in a molar ratio of 1 4 In a stream of the gaseous mixture, 20 ml. of a toluene solution containing 0.2 mole of allyl alcohol was added, and the gaseous mixture was introduced into the reactor to an absolute pressure of 2.0 Kg/cm2. While mintaining the inside of the reactor at a pressure of 2.0 Kg/cm (absolute) by adding a fresh supply of a gaseous mixture of carbon monoxide and hydrogen in a molar ratio of 1:1, the reaction was performed at 30C. with stirring. It was completed in 1.0 hours.
By the same extracting procedure as in Example .
- 12 _ '', 10609C~7 1, the product was separrlted as rm aqueous solution.
':
.
. .
It is already known that allyl alcohol can be hydroformylated in the presence, as a catalyst, of a carbonyl complex compound of a metal of Group VIII of the periodic table. For example, J. AmO Chem. Soc., Vol. 78, pO 3~3 (1948) and J. Am. ChemO Soc., Vol.
79, 3051 (1949) state that when allyl alcohol is hydro-formylated using octacarbonyl dicobalt as a catalyst, 4-hydroxybutyraldehyde is formed. Furthermore, J. Chem.
Soc., (A) p. 2753 (1970) and Japanese Patent Publication ~o. 6284/74 disclose that allyl alcohol can be hydrofor-mylated when a carbonyl compound of rhodium modified with a tri-substituted phosphine is used as a catalyst.
However, the method using a cobalt-type compound typified by octacarbonyl dicobalt affords 4-hydroxy-butyraldehyde convertible to l,4-butanediol in a selec-tivity of only less than 20%, and is therefore extremely disadvantageous for commercial operations. The reports on the use of the rhodium carbonyl compound as a catalyst fail to disclose the product and its selectivityO
In the hydroformylation reaction of olefins using carbonyl complex compounds of rhodium as a cat-alyst, the complete separation and recovery of the catalyst from the reaction product and its re-use are very important problems from an economical standpoint since the catalyst ls expensive. Unless these problems are solved, the above hydroformylation reaction cannot be employed as a commercial process for preparing aldehydes.
In the conventional hydroformylation reaction using a carbonyl complex compound o:.` rhodi m as a cata yst, hodium is recovered from the reaction mixture by various known methods among which are:
(1) a method in which the reaction mixture is distilled to separate it into the product and the catalyst, ; (2) a method in which a metal, water, an acid, hydrogen, etc. are added to decompose the catalyst, and rhodium is allowed to precipitate as a metal, - (~) a method in which rhodium is separated using a cellulose membrane or silicone rubber membrane, (4) a method in which rhodium is coordinated :: with a polymeric phosphorus compound, and (5) a method in which the reaction is carried out in a heterogeneous liquid phase using a water-` 15 hydrocarbon mixture and a water-soluble catalyst, and : the catalyst is distributed to an aqueous phase and .. . .
the product, to a hydrocarbon phase, thereby to separate -;
the catalyst from the product.
~hese methods, however, are not entirely economical ~: 20 for separating the catalyst for one or more reasons, such as the poor efficiency of separating the catalyst, the consequent reduction in the rate of the hydroformylation -~
; reaction, and the loss of the catalyst ingredients because of the need for troublesome separating and activation 25 steps for the catalystO In fact, a carkonyl complex -- compound of rhodium exhibits various superior characteristics ~ :
as a catalyst for hydroformylation of olefins on a :~
laboratory-scale operation, but except some special : cases, there has been no example in which this compound .. , ~
:. - 4 -. .
:. , . , , . ~ .
~ . . . , , . -10f~1)9C)7 was used on a commercial scale as a catalyst for hydrofor-mylating olefins.
0ur investigations show that other various problems arise in addition to the above defects when the known methods are used to separate rhodium from the uniform reaction mixture obtained by hydroformyl-ation of allyl alcohol using the a~ove-mentioned rhodium catalystO For example, according to the distillation me-thod (l), hydroxybutyraldehydes as the hydroformylation product are liable to change to high-boiling compounds by, for example, aldol condensation and acetalization, and therefore, this causes a decrease in the amount of the hydroxybutyraldehydes. Also in the method (5), since the starting allyl alcohol, the hydroxybutyr-aldehydes and the catalyst are distributed mainly to anaqueous phase, a troublesome procedure is required to separate them from each otherO
Accordingly, it is an object of this invention to provide a process for preparing butanediols from allyl alcohol which is free from the defects of the conventional processes mentioned above and in particular, includes a step of separating a rhodium catalyst with good efficiency.
We have found that when allyl alcohol is hydro-formylated in a water-immiscible organic solvent and the resulting reaction mixture containing a rhodium catalyst is extracted simply with water, the catalyst can be separated from the product with very good efficiency.
~ hus, according to this invention, there is probided a process for preparing butanediols, which .,~, .
, ,. ~ , ' .
~060907 co~prises reacting allyl alcohol with carbon monoxide and hy~rogen in an organic solvent in the presence, as a catalyst, of a water-stable water-insoluble carbonyl complex compound of rhodium thereby to hydroformylate it, e~tracting the resulting reaction mixture with water to separate it into an organic solvent phase containing the catalyst and an aqueous phase containing the resulting aldehydes, recycling the organic solvent phase for re-use in the next cycle of the hydroformylation reaction, and hydrogenating the aldehydes in the aqueous phase, thereb~ to form butanediols.
The characteristics and ad~antages o the present invention are that hydroxybutyraldehydes can be obtained in high : selectivities and yields; butanediols can be obtained ~ery easily by subjecting the aqueous phase resulting from the extraction of the reacti.on mixture with water to a hydrogenation reaction ~ in the presence of a catalyst such as Raney nickel without : separating the hydroxybutyraldehydes contained in it; and that ~:
the organic solyent phase containing the catalyst which is left ater extractîon of the reaction mixture with.water can be re-2Q used in the next cycle of the hydroformylating reaction without giy~ng any act~ati.ng treatment to it. In the light of the tradi.tional ~iew that a carbonyl complex compound of rhodium is ~ery unstable to water, it is surpri.sing that in the process of thi.s inyention, the catalyst does not undergo any change in the . presence of water.
.: Theoretically, 1,4-butanediol could be pxepared by a method which comprises preparing allyl acetate rom propylene, :' : hydroformylating the re.sulting allyl acetate to fo~m 4-acetoxybutyraldehyde, hydrogenating it and then hydrolyzing the hydrogenated product. However, according to such a method, the rate of reaction would be slow and the selectivity to 4-a~ coxybutyraldehyde would be low, e~en if a rhodium catalyst or cobalt catalyst is used. Furthermore, since 4-acetoxybutyr-aldehyde is difficulty soluble in water, this method does not permit the separation of the reaction mixture easily into the catalyst and the product as in the process of this invention.
The carbonyl complex compound of rhodium used as a catalyst in the hydroformylation reaction of this invention can be expressed by the general formula LmRh (.CO) X
wherein m is: 2 or 3; X represents a hydrogen atom or a chlorine atom; and L is a tri-substituted phosphine of the formula PRR'R"
in which R, R' and R" independently represent a phenyl group, a cycloh.exyl group, a tolyl group and an alkyl group of 1 to 6 ~ caroor ato~s.
,., . . .
,, :
. . . ~
Examples of the carbonyl complex compound of rhodium ~re:
RhH(Co)lp(-c6Hs)3]3~
RhH(.CO)[P(CH3 C6H4)3]3~ ~ :
RhH(.CO) LP (n-C4Hg ) 3] 3, RhCl(CO)[P(.C6H5)3]2' and RhCl(CO) ~ P~N(C2H5)2]3} 2' These complex compounds must be stable to water and ~ . :
insoluble in it. Complex compound containing triphenoxyphosphine , 10 such as RhH(CO)[P~OC6H5)3]3 cannot be used in this invention : because they are unstable to water. :
.. When the complex compound of the abo~e formula is used :~
., as a catalyst for the hydroformylation reaction of this .`' invention, a part of L dissociates in the sol~ent, and its ~ :
-` ! ability as a catalyst som~wh.at decreases. In order to reduce ~ the dissociation of L and make up for ~ ~ .
.',~ -' ' .
i.~' J, ' .
~, ' . .
. .
"' , . , ~', ;:
'' ' ' 'i ,''..~.
, . `
, .
'. ~
' : :.
. .
. . , . , the loss of the dissociated L, a trisubstituted phosphine, trisubstituted stibine or trisubstituted arsine of the above general formula Y~R'R" can be used as an excessive ligand togethcr with the complex compound of the above formula as a catalyst.
The solvent used in the hydroformylation re-action is an organic solvent which dissolves the cat-alyst and is not miscible with waterO Preferred organic solvents are aromatic hydrocarbons which are liquid at room temperature, such as benzene, toluene or xylene.
The reaction temperat-ure in the hydroformylation reaction of this invention is 0 to 200C., preferably 10 to 100C., and especially preferably 20 to 50C.
The reaction pressure is 1 to 50 Kg/cm (absolute), preferably 1.1 to 4 Kg/cm (absolute)0 The ratio of C0/H2 in the oxo gas can be varied within the range of 1/10 to 4/1, preferably 1/5 to 1/1. The co-presence of an inert gas such as nitrogen in the reaction system is permissible.
~he concentration of the catalyst can be varied optionally, but is naturally restricted by the selectivity to the straight-chain aldehyde, the rate of reaction and the solubility of the catalyst. The preferred concentration is 1.0 to 100 millimoles/liter.
;~- The separation of the hydroformylation reaction mixture into the catalyst and the product by extraction -can be performed by any known extraction techniquesO But in order to avoid side-reactions and the degeneration of the catalyst in the extraction step, the extraction is carried out preferably in an atmosphere of an oxo gasO
~0609~'~
~he amount of water used ~or extr~ction is determined a ~; according to the coefficients o~ distribution of the resulting aldehyde to the reaction solvent and water.
Usually, it is preferred to determine the amount of water so that the concentration o~ the aldehyde in the aqueous phase becomes at least 5% by weigh-tO
~ he organic solvent phase containing the catalyst separated from the reaction mixture can be recycled directly to the react~r. If desired, however, it can be recycled after su~decting it to an activation ' treatmentO The aqueous phase is used for a hydrogenation i reaction in order to convert the hydroformylated product of all alcohol dissolved in it to butanediolsO Known h hydrogenation catalysts such as ~i, Co, Pd, Pt and Ru can ;
be used for the hydrogenation reaction. ~he use of Rarey nickel is most preferred in view of its catalytic activity and economy.
~ here is no particular restriction on the reaction conditions for the hydrogenationO Because of ;~ 20 the heat stability of the hydroxybutyraldehydes, however, - the hydrogenation reaction is carried out preferably at , .
a temperature of not more than 100C., especially 20 to 50C. ~he rate of reaction increaseswith higher hydrogen : pressures, but in view of the economy of the reaction ~ 25 apparatus, the use of hydrogen at a partial pressure of - 1.0 to 10 Kg/cm2 (absolute) is preferredO
- ~he amount of the catalyst used for the ` hydrogenation reaction is neither restricted in particular, and is determined according to the rate of reactionO An ' . ' - -- 10 _ .
. , .
106090~7 inert gas such as nitrogeIl can, of coursc, be mixed with hydrogen. For ex~mple, when Raney nickel is used as the catalyst, the pre~erre~ amount of the catalyst is 0.5 to OnOOl gram-atom per loO mole 0~ the hydroxybutyral--dehyde.
The following Examples illustrate -the present invention more specifically.
Exam~le 1 A 500 mlO stainless steel pressure r~actor was charged with 1.0 millimo]e of RhH(CO)rP(C6H5)3]3 as ~ a catalyst, 1.0 millimole of triphenylphosphine, P(C6H5)3, - as an excess ligand, and 80 mlO of benzene as a solventO
The inside of the reactor was thoroughly purged with a ; gaseous mixture consisting of carbon monoxide and hydrogen 15 in a molar ratio of 1:1, and in a stream of this gaseous -~
mixture9 20 mlO of a benzene solution containing 0.2 mole of allyl alcohol was addedO ~he stirring of the mixture was started while maintaining the inside of the reactor at a pressure of 1.5 Kg/cm2 (absolute) and a temperature of 30Co Since the absorption of the gas occurred as soon as the stirring began, the pressure of the inside of the .
reactor was maintained at 105 Kg/cm2 (absolute) by adding ; a fresh supply of the mixed gas, and the reaction was performed at 30C. for 300 hoursO
Analysis of the reaction mixture by gas-chromatography showed that all the starting allyl alcohol ~ was consumed, and 118 millimoles of 4-hydroxybutyraldehyde, -; 7002 millimoles of 2-methyl-3-hydroxy-propionaldehyde, 402 millimols propionaldehyde and 204 millimoles of ,.' ~' - 11 - , .:
.
:
. . ;:. :
1~60907 ~-propyl alcohol were formed together with traces of ethane, propane, ~-butyrolactone and high-boiling substancesO
~ he reaction mixture was then e~tracted twice with 50 ml. of water in an atmosphere of a gaseous mixture consisting of carbon monoxide and hydrogenO 98% of the product was thus extracted into the aqueous phaseO 200g of a Raney nickel catalyst was added to the extract, and hydrogenation was carried out at room temperature for 6~0 hours while maintaining the partial pressure of hydro-gen at 3.0 Kg/cm2 (absolute). Analysis of the productshowed that 114~0 millimoles of 1,4-butanediol and 69.8 millimoles of 2-methyl-1,3-propanediol were formedO
~::
~he degree of hydrogenation was therefore more than 9~/0O
~; ~xample 2 ` 15 The same reactor as used in ~xample 1 was .. . .
charged with 5.0 millimoles of RhH(CO)[P(C6H5)~]3 and 80 ml~ of toluene, and the inside of the reactor was purged thoroughly with a gaseous mixture consisting of carbon monoxide and hydrogen in a molar ratio of 1 4 In a stream of the gaseous mixture, 20 ml. of a toluene solution containing 0.2 mole of allyl alcohol was added, and the gaseous mixture was introduced into the reactor to an absolute pressure of 2.0 Kg/cm2. While mintaining the inside of the reactor at a pressure of 2.0 Kg/cm (absolute) by adding a fresh supply of a gaseous mixture of carbon monoxide and hydrogen in a molar ratio of 1:1, the reaction was performed at 30C. with stirring. It was completed in 1.0 hours.
By the same extracting procedure as in Example .
- 12 _ '', 10609C~7 1, the product was separrlted as rm aqueous solution.
3.0g of Raney nickel was added to the aqueous solution, and hydrogenation was performed at a reaction te~perature - of 40C. while maintaining the partial p~essure of hydrogen at 105 Kg/cm2 (absolute)O The reaction was completed in 4.0 hours, and 15402 millimoles of 1,4-butanediol and 39.0 millimoles of 2-methyl-1,3-propanediol were formedO
Exam~le 3 20 ml. of a toluene solution containing 0.2 ; mole of allyl alcohol was added to the catalyst-contain-ing toluene solution which remained after the extraction of the hydroformylated product in Exampke 2. Under the same conditions as in Example 2, the mixture was hydroformylated, followed by extraction and hydrogenationO
There was obtained 15703 millimoles of 1,4-butanediolO
In this process~ the rate of the hydroformylation reaction was almost t~e same as that in Example 20 When the same procedure was repeated and the recovered catalyst was reused, the reaction ended within an hour at least up to the 10th cycle, and the selectivity to 1,4-butanediol was 75 to 80% based on the reacted allyl alcoholO No reduction in activity as a result of the repeated used was observed in the catalystO
Example 4 ~ he hydroformylation reaction was carried out under the same conditions as in ~xample 1 except that 3.0 ml. of water was addedO ~he rate of reaction and the selectivity corresponded with those in Example 1~
i:~
, ~ .
106090~
This demonstrates that the presence of water does not substantially affect the present reaction.
Exam~les 5 to 7 The same reaction as in Example 1 was performed except that each of the carbonyl complex compounds of rhodium shown i.n the following table was usedO 'rhe results are also shown in the following tableO
In all of these Examples, the reaction products obtained by the hydroformylation reaction were 4-hydroxy-butyraldehyde and 2-methyl-3-hydroxypropionaldehydeO
When the catalyst-containing benzene solution ~ which remained after the extraction of the hydroformyla-: tion reaction product was reused, changes in catalytic activity as a result of its repeated use were only slighto ;~ Ex_ Catalyst Con- Amount of ample ver- 1,4-sion butane-of diQl allyl formed alcoho' (mmole~
_ _.
RhH(CO)[P(n-C~Hg)3]3 63 112 6 RhH(C0CP(cyclo-C6Hll)3]3 75 95 , . 7 RhH(C0)[p(cH3 C6 4)3 3 70 123 Comparative Example 1 :
'rhe same reaction as in Example 1 was performed except that 0.2 mole of allvl acetate was used as a starting material. 'rhe conversion of allyl acetate was less than 2%~
Comparative Example 2 : .
- 14 _ ,, .
106090 '~
Th~ same reaction as in Example 1 was performed except that 1.0 millimole of Co2(C0)8 was used as a cat-alyst More than 95% of the allyl alcohol remained un-reacted.
Comparativ Examp]e 3 ~ he same reaction as in Comparative Example 2 was carried out except that 0O2 mole of allyl acetate - was used as a starting material. The conversion of allyl acetate was less than 1%.
10The results of Comparative ~xamples 1 to 3 de-monstrate that when the starting material or catalyst in these Comparative Examples is used, the application of the same reaction conditions as in the present ` invention scarcely induces the reactionO
15 Comparative ~xample 4 -A 100 mlO satinless steel electromagnetically stirred autoclave was charged with 2.0 millimoles of RhH(C0)[P(C6H5)3]3, 10 ml. of allyl acetate and 100 ml. ~;
~ of benzene. After purging the inside of the autoclave ; 20 with hydrogen, C0 was introduced to a pressure of 60 Kg/cm2.
Then, hydrogen was introduced under pressure to adjust the pressure of the inside to 120 Kg/cm2~ Then, the autoclave was immersed in an oil bath at 1350CD ~ and -~
the solution was stirred to initiate the reactionO
25 The temperature of the inside of the autoclave was raised to 120C. in the course of about 30 minutesD During this time, the pressure rose to 123 Kg/cm2. The reaction was completed in about 2 D 5 hours.
The autoclave was cooled to room temperature i - 15 -, . , , .-. . .. .. .
.:
.-, . . . .
10609~t7 (at this time, the residual pressure was 88 Kg/cm2).After releasing the pressllre, the reaction product was anal~zed by gas-chromatographyO ~s a result, it was found that allyl acetate was all consumed, and 4-acetoxy-butyraldehyde, 2-methyl-propionaldehyde and acetic acid were formed at a selectivity o 45.0% and 48.3%, respectively. In other words 9 the selectivity to 1,4-; butanediol based on the allyl acetate was less than 47~5%.
Comparative Example 5 ~ he same reaction as in Comparative ~xample4 was performed except that 2.0 millimoles of Co2(C0)8 was used as a catalystO Analysis of the reaction mixture by gas-chromatography showed that all the allyl acetate was consumed, and 4-acetoxy-butyraldehyde, 1,4-diAcetoxy-~ butane, 2-methyl-3-acetoxy-rpopionaldehyde, 2-methyl-- 1,3-propanediol monoacetate, 2-acetoxy-butyraldeh~de, 1,2--~ butanediol monoacetate, n-propyl acetate and isobutyraldehyde were formed in an amount of 47.9, 0.7, 901, 1.5, 1904, 4089 lol and 208 millimoles, respectively. The selectivity to the 1,4-butanediol precursor based on the consumed allyl acetate was 52 .6%O
~ he results in Comparative Example 4 and 5 show that when the starting material or catalyst in these comparative examples is used, 1,4-butanediol can be obtained in a fairly acceptable yield, but on the other hand, large quantities of many kinds of by-products are formedO
"
~' ~06090l~
,omparativ~ Exampl~ 6 ~ he same reaction as :in Comparative Example 5 was perfo~ned except that 10 ml~ of allyl alcohol was used as a starting material. All the all~yl alcohol was consumed, bu-t the selectivities to the 1,4-butanediol and its precursor were less than 15% in total.
' :
. ~ ~
::
, '.
Exam~le 3 20 ml. of a toluene solution containing 0.2 ; mole of allyl alcohol was added to the catalyst-contain-ing toluene solution which remained after the extraction of the hydroformylated product in Exampke 2. Under the same conditions as in Example 2, the mixture was hydroformylated, followed by extraction and hydrogenationO
There was obtained 15703 millimoles of 1,4-butanediolO
In this process~ the rate of the hydroformylation reaction was almost t~e same as that in Example 20 When the same procedure was repeated and the recovered catalyst was reused, the reaction ended within an hour at least up to the 10th cycle, and the selectivity to 1,4-butanediol was 75 to 80% based on the reacted allyl alcoholO No reduction in activity as a result of the repeated used was observed in the catalystO
Example 4 ~ he hydroformylation reaction was carried out under the same conditions as in ~xample 1 except that 3.0 ml. of water was addedO ~he rate of reaction and the selectivity corresponded with those in Example 1~
i:~
, ~ .
106090~
This demonstrates that the presence of water does not substantially affect the present reaction.
Exam~les 5 to 7 The same reaction as in Example 1 was performed except that each of the carbonyl complex compounds of rhodium shown i.n the following table was usedO 'rhe results are also shown in the following tableO
In all of these Examples, the reaction products obtained by the hydroformylation reaction were 4-hydroxy-butyraldehyde and 2-methyl-3-hydroxypropionaldehydeO
When the catalyst-containing benzene solution ~ which remained after the extraction of the hydroformyla-: tion reaction product was reused, changes in catalytic activity as a result of its repeated use were only slighto ;~ Ex_ Catalyst Con- Amount of ample ver- 1,4-sion butane-of diQl allyl formed alcoho' (mmole~
_ _.
RhH(CO)[P(n-C~Hg)3]3 63 112 6 RhH(C0CP(cyclo-C6Hll)3]3 75 95 , . 7 RhH(C0)[p(cH3 C6 4)3 3 70 123 Comparative Example 1 :
'rhe same reaction as in Example 1 was performed except that 0.2 mole of allvl acetate was used as a starting material. 'rhe conversion of allyl acetate was less than 2%~
Comparative Example 2 : .
- 14 _ ,, .
106090 '~
Th~ same reaction as in Example 1 was performed except that 1.0 millimole of Co2(C0)8 was used as a cat-alyst More than 95% of the allyl alcohol remained un-reacted.
Comparativ Examp]e 3 ~ he same reaction as in Comparative Example 2 was carried out except that 0O2 mole of allyl acetate - was used as a starting material. The conversion of allyl acetate was less than 1%.
10The results of Comparative ~xamples 1 to 3 de-monstrate that when the starting material or catalyst in these Comparative Examples is used, the application of the same reaction conditions as in the present ` invention scarcely induces the reactionO
15 Comparative ~xample 4 -A 100 mlO satinless steel electromagnetically stirred autoclave was charged with 2.0 millimoles of RhH(C0)[P(C6H5)3]3, 10 ml. of allyl acetate and 100 ml. ~;
~ of benzene. After purging the inside of the autoclave ; 20 with hydrogen, C0 was introduced to a pressure of 60 Kg/cm2.
Then, hydrogen was introduced under pressure to adjust the pressure of the inside to 120 Kg/cm2~ Then, the autoclave was immersed in an oil bath at 1350CD ~ and -~
the solution was stirred to initiate the reactionO
25 The temperature of the inside of the autoclave was raised to 120C. in the course of about 30 minutesD During this time, the pressure rose to 123 Kg/cm2. The reaction was completed in about 2 D 5 hours.
The autoclave was cooled to room temperature i - 15 -, . , , .-. . .. .. .
.:
.-, . . . .
10609~t7 (at this time, the residual pressure was 88 Kg/cm2).After releasing the pressllre, the reaction product was anal~zed by gas-chromatographyO ~s a result, it was found that allyl acetate was all consumed, and 4-acetoxy-butyraldehyde, 2-methyl-propionaldehyde and acetic acid were formed at a selectivity o 45.0% and 48.3%, respectively. In other words 9 the selectivity to 1,4-; butanediol based on the allyl acetate was less than 47~5%.
Comparative Example 5 ~ he same reaction as in Comparative ~xample4 was performed except that 2.0 millimoles of Co2(C0)8 was used as a catalystO Analysis of the reaction mixture by gas-chromatography showed that all the allyl acetate was consumed, and 4-acetoxy-butyraldehyde, 1,4-diAcetoxy-~ butane, 2-methyl-3-acetoxy-rpopionaldehyde, 2-methyl-- 1,3-propanediol monoacetate, 2-acetoxy-butyraldeh~de, 1,2--~ butanediol monoacetate, n-propyl acetate and isobutyraldehyde were formed in an amount of 47.9, 0.7, 901, 1.5, 1904, 4089 lol and 208 millimoles, respectively. The selectivity to the 1,4-butanediol precursor based on the consumed allyl acetate was 52 .6%O
~ he results in Comparative Example 4 and 5 show that when the starting material or catalyst in these comparative examples is used, 1,4-butanediol can be obtained in a fairly acceptable yield, but on the other hand, large quantities of many kinds of by-products are formedO
"
~' ~06090l~
,omparativ~ Exampl~ 6 ~ he same reaction as :in Comparative Example 5 was perfo~ned except that 10 ml~ of allyl alcohol was used as a starting material. All the all~yl alcohol was consumed, bu-t the selectivities to the 1,4-butanediol and its precursor were less than 15% in total.
' :
. ~ ~
::
, '.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for preparing butanediols which comprises reacting allyl alcohol with carbon monoxide and hydrogen in an organic solvent in the presence, as a catalyst, of a carbonyl complex compound of rhodium of the general formula wherein m is 2 or 3; X represents a hydrogen atom or a chlorine atom, and L is a tri-substituted phosphine of the formula PRR'R" in which R, R' and R" independently represent a phenyl group, a cyclohexyl group, a tolyl group and an alkyl group of 1 to 6 carbon atoms, to hydroformylate it to the corresponding aldehydes, extracting the resulting hydroformylation mixture with water to separate it into an organic solvent phase containing said catalyst and an aqueous phase containing the aldehydes, the separated organic solvent phase containing said catalyst being recycled for re-use in the next cycle of the hydroformylation reaction, and hydrogenating the said aldehydes in the said aqueous phase thereby to form butanediols.
2. The process of claim 1 wherein the concentration of the catalyst is 1.0 to 100 millimoles per liter of the organic solvent.
3. The process of claim 1 wherein the hydroformylation reaction is carried out a temperature of 0 to 200°C and a pressure of 1 to 50 Kg/cm2 (absolute).
4. The process of claim 1 wherein the hydrogenation reaction is carried out at a temperature of not more than 100°C and a pressure of 1 to 10 Kg/cm2 (absolute).
5. The process of claim 1 wherein in the rhodium carbonyl complex of formula LmRh(CO)X, X represents hydrogen; L represents a phosphine of formula R3P wherein R represents a phenyl group, an n-butyl group, a cyclohexyl group, or a tolyl group, and m is 2 or 3.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP49099668A JPS5129412A (en) | 1974-08-30 | 1974-08-30 | Butanjioorurui no seizohoho |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060907A true CA1060907A (en) | 1979-08-21 |
Family
ID=14253400
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,642A Expired CA1060907A (en) | 1974-08-30 | 1975-08-29 | Process for preparing butanediols |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5129412A (en) |
| CA (1) | CA1060907A (en) |
| DE (1) | DE2538364B2 (en) |
| FR (1) | FR2283114A1 (en) |
| GB (1) | GB1493154A (en) |
| IT (1) | IT1042173B (en) |
Families Citing this family (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1565719A (en) * | 1976-12-30 | 1980-04-23 | Gen Electric | Process for preparing butanediols |
| US4139542A (en) | 1977-11-07 | 1979-02-13 | General Electric Company | Process for the preparation of 2-alkoxytetrahydrofurans via hydroformylation of allylic alcohols |
| JPS5849532B2 (en) * | 1977-12-15 | 1983-11-05 | 株式会社クラレ | Method for producing butanediols |
| JPS5545646A (en) * | 1978-09-29 | 1980-03-31 | Toyo Soda Mfg Co Ltd | Preparation of hydroxybutylaldehyde |
| JPS55151521A (en) * | 1979-05-15 | 1980-11-26 | Toyo Soda Mfg Co Ltd | Preparation of alcohol |
| NL8002342A (en) * | 1980-04-23 | 1981-11-16 | Stamicarbon | PREPARATION OF 2-HYDROXYTETRAHYDROFURANE. |
| JPS606630A (en) * | 1983-06-24 | 1985-01-14 | Kuraray Co Ltd | Continuous hydroformylation of allyl alcohol |
| US4590311A (en) * | 1983-12-29 | 1986-05-20 | Shell Oil Company | Process for the preparation of 1,4-butanediol |
| JPS60202835A (en) * | 1984-03-14 | 1985-10-14 | Kuraray Co Ltd | Preparation of 3-methylpentane-1,5-diol |
| US4625068A (en) * | 1985-03-20 | 1986-11-25 | Exxon Chemical Patents Inc. | Rhodium catalyzed hydroformylation of internal olefins |
| US4642388A (en) * | 1985-08-30 | 1987-02-10 | Exxon Chemical Patents Inc. | Rhodium catalyzed hydroformylation of alpha-substituted alpha-olefins |
| US4678857A (en) * | 1986-03-31 | 1987-07-07 | Texaco Inc. | Process for separation of product resulting from hydroformylation |
| US5180854A (en) * | 1988-07-14 | 1993-01-19 | Union Carbide Chemicals & Plastics Technology Corporation | Process for catalyst aldehyde product separation |
| CA2314771C (en) | 1999-08-03 | 2010-09-14 | Kuraray Co., Ltd. | Method for manufacturing aminoalcohol |
| WO2009035838A2 (en) * | 2007-09-07 | 2009-03-19 | Dow Global Technologies Inc. | Hydrogenation of aliphatic dialdehydes to aliphatic diols |
| AU2009258344B2 (en) | 2008-06-09 | 2013-11-07 | Lanzatech Nz, Inc. | Production of butanediol by anaerobic microbial fermentation |
| US8124805B2 (en) | 2009-11-25 | 2012-02-28 | Lyondell Chemical Technology, L.P. | Allyl acetate hydroformylation process |
| CN114522740B (en) * | 2020-11-23 | 2023-10-13 | 中国科学院大连化学物理研究所 | Method for preparing 3-acetoxypropanol from vinyl acetate |
-
1974
- 1974-08-30 JP JP49099668A patent/JPS5129412A/en active Granted
-
1975
- 1975-08-27 GB GB35360/75A patent/GB1493154A/en not_active Expired
- 1975-08-28 DE DE19752538364 patent/DE2538364B2/en not_active Ceased
- 1975-08-29 IT IT26737/75A patent/IT1042173B/en active
- 1975-08-29 FR FR7526620A patent/FR2283114A1/en not_active Withdrawn
- 1975-08-29 CA CA234,642A patent/CA1060907A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5319563B2 (en) | 1978-06-21 |
| DE2538364B2 (en) | 1978-02-23 |
| GB1493154A (en) | 1977-11-23 |
| FR2283114A1 (en) | 1976-03-26 |
| DE2538364A1 (en) | 1976-03-18 |
| IT1042173B (en) | 1980-01-30 |
| JPS5129412A (en) | 1976-03-12 |
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