CA1149419A - Preparation of polyamines from polynitriles - Google Patents
Preparation of polyamines from polynitrilesInfo
- Publication number
- CA1149419A CA1149419A CA000365419A CA365419A CA1149419A CA 1149419 A CA1149419 A CA 1149419A CA 000365419 A CA000365419 A CA 000365419A CA 365419 A CA365419 A CA 365419A CA 1149419 A CA1149419 A CA 1149419A
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- Prior art keywords
- catalyst
- hydrogenation
- cobalt
- zinc
- polynitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
PREPARATION OF POLYAMINES FROM POLYNITRILES
(D#75,787-F) ABSTRACT OF THE DISCLOSURE
Covers a process for preparing polyamines from the corresponding polynitriles via a pelleted cobalt-zinc hydrogenation catalyst which comprises contacting a polynitrile with hydrogen in presence of said catalyst, said catalyst pellet being further characterized as substantially maintaining its integral character during said hydrogenation.
I
(D#75,787-F) ABSTRACT OF THE DISCLOSURE
Covers a process for preparing polyamines from the corresponding polynitriles via a pelleted cobalt-zinc hydrogenation catalyst which comprises contacting a polynitrile with hydrogen in presence of said catalyst, said catalyst pellet being further characterized as substantially maintaining its integral character during said hydrogenation.
I
Description
BACKGROUND OF 1~ INVENTION
Field of the Invention This invention relates to a process of producing polyamines from polynitriles using a hydrogenation catalyst in pellet form.
DescriDtion of the Prior Art It has been found that many hydrogenation catalysts in pelleted form such as cobalt or nickel when used in the hydrogenation of polynitriles to corresponding polyamines tend to disintegrate. During the hydrogenation reaction the catalyst pellets are swollen or disintegrate into fine particles or both phenomenon occur. Due to loss of physical integrity, usefulness of catalyst pellets suffers somewhat in terms of proper control, particularly in a continuous process where æuch variables as space velocity, etc. must be carefully considered and controlled. Specifically, channeling occurs in the catalyst bed, so there is improper contact of nitrile with catalyst. Also fine particles sometimes plug the reactor or reactor lines.
In U. S. Patent No. 3,384,666 a method of inhibiting catalyst pellet disintegration is set out. Essentially this method involves use of a sodium, lithium or potassium hydroxide or alkoxide base. While such expedient use of caustic stabilizer has been found efficacious, nevertheless there have been found subsequently to have certain drawbacks emanating from such use. For example, it has been found that such a process to be efficiently worked must involve neutralizing the caustic and filtering off the salt. This, of course, involves a time consuming, and relatively expensive additional step. In addition, it was ~iscovered that the caustic reacts with those nitriles which additionally contain an oxy group in a manner such that the desired amine is not obtained. That is, undesirable side reactions occur.
Other means of maintaining hydrogenation catalyst pellet integrity have been discovered. In some cases this involves use of an amine type stabilizer. However, resort to such stabilizer while avoiding the above discussed problems with respect to use of caustic nevertheless still necessarily adds increased cost to the overall process in terms of necessary resort to yet another chemical additive in the catalysis.
Still other proposed solutions to the above problem are set out in U. S. Patent Nos. 3,427,356; 3,728,284; and 4,007,226.
It would therefore be a considerable advance in the art if one could discover a specific type of catalyst useful in hydrogenating polynitriles which did not undergo disintegration or breakdown during the catalysis whereby the catalyst pellet form was maintained, and yet no resort to 0 extraneous protective chemicals need be sought.
SUMMARY OF T~ INVENTION
In accordance with the invention a method of hydrogenating polynitriles to polyamines has been discovered.
In its broadest aspect, the invention involves use of a pelleted co~alt-zinc hydrogenation catalyst usually in oxide form which is characterized as substantially maintaining its integral character during said hydrogenation without resort to inorganic or organic stabilizing agents.
9~19 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In more detail, the hydrogenation technique of preparing polyamines from polynitriles via the process of the invention involves hydrogenation of the polynitrile in presence of a cobalt-zinc hydrogenation catalyst in pellet form.
The hydrogenation reaction itself may be run in presence or in the absence of a solvent. When a solvent is used, it is preferred that an organic solvent such as an alcohol be employed. $ypical useful alcohols include methanol, ethanol, isopropanol, t-butanol, n-propyl alcohol, and other alcohols, particularly water-miscible alcohols.
The polynitrile to be treated in accordance with the present invention may be chosen from a wide variety of known materials of this type. Preferred are di- and tri- nitriles prepared by reacting acrylonitrile with an amine, polyamine, polyhydroxy-monoamine, polyhydroxy-polyamine, etc. such as ammonia, methylamine, piperazine, ethylenediamine, monoethanolamine, diethylenetriamine, 3-aminopropanol, methylethanolamine, aminoethylethanolamine, etc. Other preferred polynitriles are those which additionally contain an oxy group. Typically these oxynitriles include, for example, acrylonitrile adducts of polyols such as ethylene glycol, di-and tri-ethylene glycol, glycerol, trimethylol propane, butane-1,4-diol, butane-1,3-diol, etc.
The pelleted catalyst used here is a pelleted cobalt-zinc hydrogenation catalyst which usually consists of cobalt and zinc in mole ratios ranging from 98:2 to 60:40 expressed as Co and Zn. The metals are usually in oxide form.
The support or carrier used may be any one inert to process conditions such as refractory support, charcoal, silica, alumina and the like which are capable of being employed with the active hydrogenation catalysts. The methods S of preparinq such catalysts on supports are well known in the art.
The hydrogenation reaction itself may be carried out over a wide range of conditions. Typically, the polynitrile is hydrogenated in the presence of a catalyst of the class described at a temperature within the range of from about 70 to about 220C and at a pressure of about 30 to 800 atmospheres in the additional presence of hydrogen. The reaction temperature is more preferably 70-150,C with the pressure more preferably being 500-10,000 psig and most preferably 1000-3000 psig.
In a greatly preferred embodiment, ammonia is also present during the reaction. The ammonia aids the reaction in promoting better selectivity to primary amine, and prevents bimolecular coupling to produce secondary amine formation, usually unwanted in the reaction. When ammonia is present, usually there are about from 2 to about 20 moles of ammonia present per equivalent of nitrile. When hydrogen and ammonia are used together, the hydrogen partial pressure will usually amount to from about 60 to about 80 percent of the total pressure.
The particular space velocity of the hydrogenation reaction (grams nitrile/hour/cc catalyst) is not critical in the process. However, we prefer to conduct the hydrogenation reaction at a velocity of between about 0.5 to about 5 grams total liguid feed/hour/cc catalyst.
The hydrogenation reaction here can be performed in either a batch or a continous manner, with the latter being preferred. For this, suitable reactors include either a closed autoclave resulting in a batch process, or a tubular S reactor which can be operated in a continuous manner.
The desired polyamine product can then be recovered from the hydrogenation reaction media by any technique known in the art, such as by distillation. Thus, usually the polyamine product must be separated from the amine stabilizer by distillation when the latter is used in amounts such that it also acts as a solvent for the hydrogenation reaction.
It is interesting to note that only when polyamines are derived from polynitriles is the problem of catalyst instability caused during the hydrogenation step.
Mononitriles when hydrogenated are not subject to this drawback whatsoever. Even dinitriles such as adiponitrile or phthlonitrile, when converted to diamines cause only minimal catalyst problems of stability. However, when di- tri- or tetranitriles derived from reaction of acrylonitriles and compounds reactive with said acrylonitrile such as alcohols and amines are hydrogenated, most catalysts such as of the cobalt type are physically degrades during the hydrogenation reaction.
Further, as just noted and as will be more clearly seen in the examples below fixed bed cobalt catalysts alone, while useful in converting polynitriles to polyamines, are distinctly deficient in that the pellets or tablets are converted to fines when used for a substantial time in the hydrogenation process. Yet a cobalt-zinc oxide mixture is stable in terms of being able to be maintained in pellet form, even in absence of a caustic or amine stabilizing additive.
91~19 While the invention has been described in terms of using catalysts in pellet form, it is understood that the term "pellet" also is meant to include tablets with such physical forms of the cobalt-zinc containing catalyst being interchangeable for use in the invention.
EXAMPLE
A solution of 488 g. (1.68 moles) of cobalt nitrate hexahydrate and 36 g. of zinc nitrate hexahydrate (0.12 mole) in two liters of distilled water was heated to 75C. This solution was added slowly with stirring to 197 g (1.85 moles) of sodium carbonate in three liters of distilled water, also at 75C. After addition was complete, the slurry was stirred one hour longer at 80C, then filtered. Collected solids were washed eight times with two liters of hot lS distilled water, dried at 110C and calcined for two hours at 400C. The mixed cobalt and zinc oxides, wt. 142 g., contained 66.5% Co, 5.1% Zn and 513 ppm. of sodium. This product was charged to a glass tube and prereduced at 325C
with hydrogen until no moisture could be detected in the exit gases. After the catalyst was cooled to room temperature in situ ~nder nitrogen, it was back-oxidized carefully with dilute oxygen in nitrogen. The stabilized cobalt-zinc oxide catalyst was blended with 0.5% graphite before being formed into 1/8" diameter cylindrical pellets.
To a three liter flask containing 600 g. (10.0 moles) of ethylenediamine was added 1855 g. (35.0 moles) of acrylonitrile at 35-50C with external cooling. After addition was complete, the solution was placed in a stirred autoclave with 60 g. of a commercial silica, alumina catalyst (Aerocat Silica Alumina TA, American Cyanamid Company) and heated at 160C for four hours. This mixture of cyanoethylated ethylenediamines was used as a feed in the experiments described here and in Example II.
Twenty-five ml. of pellets of the cobalt-zinc oxide catalyst whose preparation is described above was placed in a small fixed bed reactor. A liquid feed composed of egual weights of liquid ammonia, methanol and the 3.5/1 mole ratio cyanoethylated ethylenediamine was passed up through the catalyst at a rate of 24 m./hour. ~ydrogen was also introduced at 12 liters/hour STP. ~ressure was maintained at 2500 psig and reactor temperature at 115C. Samples of liquid product were collected periodically and analyzed for completeness of reaction by infrared nitrile determination.
After 53 hours of operation, the catalyst was removed from the reactor and the pellets were observed to be unchanged in appearance. A sample of liquid product was passed through a wiped film evaporator before analysis by gas chromatography and contained 54% tris(aminopropyl)ethylenediamine and 9%
bis(aminopropyl)ethylenediamine.
EXANPLE II
A commercially manufactured catalyst prepared from a 75:23:2 atomic ratio of cobalt, copper and chromia was used in this experiment. To the same fixed bed reactor used in Example I was charged 25 ml. of 1/8" tablets. Using the same feed, hydrogen flow, pressure and temperature as in Example I, the run was terminated after 20 hours because the catalyst pellets had completely disintegrated and plugged the reactor.
EXAMPLE ~II
Commercially produced cobalt, 1/8" pellets was charged to a 25 ml. capacity fixed bed catalytic reactor. A
9'~19 3.5/1 mole ratio acrylonitrile-ethylenediamine reaction product in a 1:1:1 weight ratio methanol-liquid ammonia-polynitrile solution was passed over the catalyst with hydrogen and gave relatively high conversion in the S hydrogenation except near the end of the 55 hour run. ~owever, the catalyst, when removed from the reactor, was found to be composed of broken pieces of the tablet, no longer capable of being used.
EXAMPLE IV
To a solution of 197 g. (1.85 moles) of sodium carbonate in three liters of distilled water was added 430 g.
(1.48 moles) of cobalt nitrate hexahydrate and 101 g. (0.34 mole) of zinc nitrate hexahydrate in two liters of distilied water at 75C. Stirring was continued for an hour at that temperature followed by filtration and washing eight times with hot distilled water. The oxides were dried at 110C and calcined for two hours at 400C to provide 144g. of product, 56.9% Co, 12.8% Zn, 142 ppm of sodium. It was prereduced with hydrogen at 325C, stabilized with dilute oxygen in nitrogen and pelleted with 0.5% graphite. The tablets were put in the 25 ml. fixed bed reactor and subjected to a 1~1 hour continuous run. The nitrile employed was made by reaction of acrylonitrile with ethylenediamine in a 1.5:1 molar ratio. It was passed over the catalyst in a solution composed of equal parts by ~eight of nitrile, methanol and anhydrous ammonia at a rate of 24 ml. per hour accompanied by 12 liters ~STP) per hour of hydrogen. Gas chromatographic analysis of the product, free of methanol and ammonia, gave values of 64%
bis(aminopropyl)ethylenediamine and 33%
aminopropylethylenediamine. The catalyst pellets were physically unchanged.
9~19 EXA~LE V
Here an experiment was carried out, using the commercial nitrile hydrogenation catalyst described in Example II and the same l.S:l mole ratio acrylonitrile-ethylenediamine addition product feed of Example IV. Normally, the lower the acrylonitrile-ethylenediamine ratio feed used, the less the tendency for catalyst tablets to disintegrate. Under the same conditions as used in Example IV, the cobalt-copper-chromia catalyst was used for 85 hours, becoming almost completely converted to a finely divided mud by the termination of the experiment.
EXAMPLE VI
Two liters of distilled water containing 22.6 g. of synthetic calcium silicate was heated to 70C. This was stirred while 244 g. of Co(N03)2.6H20 and 18 g. Zn (N03)2.6~20 in two liters of distilled water was run slowly in simultaneously with 155 g. of sodium carbonate in another two liters of distilled water. All solutions were kept at 7~C, with the additions adjusted to maintain the pH of the reaction solution at %0. Following an hour digestion period, solids were collected by filtration, washed eight times, dried at 110C and calcined an hour at 400C. Analysis of the catalyst before prereduction was Co 51.3%, Zn 4.1%, Ca 3.7%, Si 4.8%
and Na 532 ppm. Following prereduction at 325C and sta~ilization, pellets were made with the aid of 0.5%
graphite.
The feed for the fixed bed hydrogenation was prepared by reaction of 1.88 moles of acrylonitrile per mole of ethylenediamine. The continuous run was made at the same rates and conditions as were used for Example I. After 22 _g_ ~1~9'~19 hours, the gas chromatographic analysis of the product (free of ammonia and methanol) was 15% aminopropyl-ethylenediamine, 69% bis(aminopropyl)ethylenediamine and 7.6%
tris(aminopropyl)ethylenediamine. The run was terminated after 251 hours at which time the corresponding analyses were 15%, 69% and 7.3%. The catalyst pellets did not form finely divided material although a few of the pellets were split.
From the foregoing description and examples of this invention, those of ordinary skill in the art may make many modifications and variations therefrom without departing from the scope of the invention as hereinafter claimed.
Field of the Invention This invention relates to a process of producing polyamines from polynitriles using a hydrogenation catalyst in pellet form.
DescriDtion of the Prior Art It has been found that many hydrogenation catalysts in pelleted form such as cobalt or nickel when used in the hydrogenation of polynitriles to corresponding polyamines tend to disintegrate. During the hydrogenation reaction the catalyst pellets are swollen or disintegrate into fine particles or both phenomenon occur. Due to loss of physical integrity, usefulness of catalyst pellets suffers somewhat in terms of proper control, particularly in a continuous process where æuch variables as space velocity, etc. must be carefully considered and controlled. Specifically, channeling occurs in the catalyst bed, so there is improper contact of nitrile with catalyst. Also fine particles sometimes plug the reactor or reactor lines.
In U. S. Patent No. 3,384,666 a method of inhibiting catalyst pellet disintegration is set out. Essentially this method involves use of a sodium, lithium or potassium hydroxide or alkoxide base. While such expedient use of caustic stabilizer has been found efficacious, nevertheless there have been found subsequently to have certain drawbacks emanating from such use. For example, it has been found that such a process to be efficiently worked must involve neutralizing the caustic and filtering off the salt. This, of course, involves a time consuming, and relatively expensive additional step. In addition, it was ~iscovered that the caustic reacts with those nitriles which additionally contain an oxy group in a manner such that the desired amine is not obtained. That is, undesirable side reactions occur.
Other means of maintaining hydrogenation catalyst pellet integrity have been discovered. In some cases this involves use of an amine type stabilizer. However, resort to such stabilizer while avoiding the above discussed problems with respect to use of caustic nevertheless still necessarily adds increased cost to the overall process in terms of necessary resort to yet another chemical additive in the catalysis.
Still other proposed solutions to the above problem are set out in U. S. Patent Nos. 3,427,356; 3,728,284; and 4,007,226.
It would therefore be a considerable advance in the art if one could discover a specific type of catalyst useful in hydrogenating polynitriles which did not undergo disintegration or breakdown during the catalysis whereby the catalyst pellet form was maintained, and yet no resort to 0 extraneous protective chemicals need be sought.
SUMMARY OF T~ INVENTION
In accordance with the invention a method of hydrogenating polynitriles to polyamines has been discovered.
In its broadest aspect, the invention involves use of a pelleted co~alt-zinc hydrogenation catalyst usually in oxide form which is characterized as substantially maintaining its integral character during said hydrogenation without resort to inorganic or organic stabilizing agents.
9~19 DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In more detail, the hydrogenation technique of preparing polyamines from polynitriles via the process of the invention involves hydrogenation of the polynitrile in presence of a cobalt-zinc hydrogenation catalyst in pellet form.
The hydrogenation reaction itself may be run in presence or in the absence of a solvent. When a solvent is used, it is preferred that an organic solvent such as an alcohol be employed. $ypical useful alcohols include methanol, ethanol, isopropanol, t-butanol, n-propyl alcohol, and other alcohols, particularly water-miscible alcohols.
The polynitrile to be treated in accordance with the present invention may be chosen from a wide variety of known materials of this type. Preferred are di- and tri- nitriles prepared by reacting acrylonitrile with an amine, polyamine, polyhydroxy-monoamine, polyhydroxy-polyamine, etc. such as ammonia, methylamine, piperazine, ethylenediamine, monoethanolamine, diethylenetriamine, 3-aminopropanol, methylethanolamine, aminoethylethanolamine, etc. Other preferred polynitriles are those which additionally contain an oxy group. Typically these oxynitriles include, for example, acrylonitrile adducts of polyols such as ethylene glycol, di-and tri-ethylene glycol, glycerol, trimethylol propane, butane-1,4-diol, butane-1,3-diol, etc.
The pelleted catalyst used here is a pelleted cobalt-zinc hydrogenation catalyst which usually consists of cobalt and zinc in mole ratios ranging from 98:2 to 60:40 expressed as Co and Zn. The metals are usually in oxide form.
The support or carrier used may be any one inert to process conditions such as refractory support, charcoal, silica, alumina and the like which are capable of being employed with the active hydrogenation catalysts. The methods S of preparinq such catalysts on supports are well known in the art.
The hydrogenation reaction itself may be carried out over a wide range of conditions. Typically, the polynitrile is hydrogenated in the presence of a catalyst of the class described at a temperature within the range of from about 70 to about 220C and at a pressure of about 30 to 800 atmospheres in the additional presence of hydrogen. The reaction temperature is more preferably 70-150,C with the pressure more preferably being 500-10,000 psig and most preferably 1000-3000 psig.
In a greatly preferred embodiment, ammonia is also present during the reaction. The ammonia aids the reaction in promoting better selectivity to primary amine, and prevents bimolecular coupling to produce secondary amine formation, usually unwanted in the reaction. When ammonia is present, usually there are about from 2 to about 20 moles of ammonia present per equivalent of nitrile. When hydrogen and ammonia are used together, the hydrogen partial pressure will usually amount to from about 60 to about 80 percent of the total pressure.
The particular space velocity of the hydrogenation reaction (grams nitrile/hour/cc catalyst) is not critical in the process. However, we prefer to conduct the hydrogenation reaction at a velocity of between about 0.5 to about 5 grams total liguid feed/hour/cc catalyst.
The hydrogenation reaction here can be performed in either a batch or a continous manner, with the latter being preferred. For this, suitable reactors include either a closed autoclave resulting in a batch process, or a tubular S reactor which can be operated in a continuous manner.
The desired polyamine product can then be recovered from the hydrogenation reaction media by any technique known in the art, such as by distillation. Thus, usually the polyamine product must be separated from the amine stabilizer by distillation when the latter is used in amounts such that it also acts as a solvent for the hydrogenation reaction.
It is interesting to note that only when polyamines are derived from polynitriles is the problem of catalyst instability caused during the hydrogenation step.
Mononitriles when hydrogenated are not subject to this drawback whatsoever. Even dinitriles such as adiponitrile or phthlonitrile, when converted to diamines cause only minimal catalyst problems of stability. However, when di- tri- or tetranitriles derived from reaction of acrylonitriles and compounds reactive with said acrylonitrile such as alcohols and amines are hydrogenated, most catalysts such as of the cobalt type are physically degrades during the hydrogenation reaction.
Further, as just noted and as will be more clearly seen in the examples below fixed bed cobalt catalysts alone, while useful in converting polynitriles to polyamines, are distinctly deficient in that the pellets or tablets are converted to fines when used for a substantial time in the hydrogenation process. Yet a cobalt-zinc oxide mixture is stable in terms of being able to be maintained in pellet form, even in absence of a caustic or amine stabilizing additive.
91~19 While the invention has been described in terms of using catalysts in pellet form, it is understood that the term "pellet" also is meant to include tablets with such physical forms of the cobalt-zinc containing catalyst being interchangeable for use in the invention.
EXAMPLE
A solution of 488 g. (1.68 moles) of cobalt nitrate hexahydrate and 36 g. of zinc nitrate hexahydrate (0.12 mole) in two liters of distilled water was heated to 75C. This solution was added slowly with stirring to 197 g (1.85 moles) of sodium carbonate in three liters of distilled water, also at 75C. After addition was complete, the slurry was stirred one hour longer at 80C, then filtered. Collected solids were washed eight times with two liters of hot lS distilled water, dried at 110C and calcined for two hours at 400C. The mixed cobalt and zinc oxides, wt. 142 g., contained 66.5% Co, 5.1% Zn and 513 ppm. of sodium. This product was charged to a glass tube and prereduced at 325C
with hydrogen until no moisture could be detected in the exit gases. After the catalyst was cooled to room temperature in situ ~nder nitrogen, it was back-oxidized carefully with dilute oxygen in nitrogen. The stabilized cobalt-zinc oxide catalyst was blended with 0.5% graphite before being formed into 1/8" diameter cylindrical pellets.
To a three liter flask containing 600 g. (10.0 moles) of ethylenediamine was added 1855 g. (35.0 moles) of acrylonitrile at 35-50C with external cooling. After addition was complete, the solution was placed in a stirred autoclave with 60 g. of a commercial silica, alumina catalyst (Aerocat Silica Alumina TA, American Cyanamid Company) and heated at 160C for four hours. This mixture of cyanoethylated ethylenediamines was used as a feed in the experiments described here and in Example II.
Twenty-five ml. of pellets of the cobalt-zinc oxide catalyst whose preparation is described above was placed in a small fixed bed reactor. A liquid feed composed of egual weights of liquid ammonia, methanol and the 3.5/1 mole ratio cyanoethylated ethylenediamine was passed up through the catalyst at a rate of 24 m./hour. ~ydrogen was also introduced at 12 liters/hour STP. ~ressure was maintained at 2500 psig and reactor temperature at 115C. Samples of liquid product were collected periodically and analyzed for completeness of reaction by infrared nitrile determination.
After 53 hours of operation, the catalyst was removed from the reactor and the pellets were observed to be unchanged in appearance. A sample of liquid product was passed through a wiped film evaporator before analysis by gas chromatography and contained 54% tris(aminopropyl)ethylenediamine and 9%
bis(aminopropyl)ethylenediamine.
EXANPLE II
A commercially manufactured catalyst prepared from a 75:23:2 atomic ratio of cobalt, copper and chromia was used in this experiment. To the same fixed bed reactor used in Example I was charged 25 ml. of 1/8" tablets. Using the same feed, hydrogen flow, pressure and temperature as in Example I, the run was terminated after 20 hours because the catalyst pellets had completely disintegrated and plugged the reactor.
EXAMPLE ~II
Commercially produced cobalt, 1/8" pellets was charged to a 25 ml. capacity fixed bed catalytic reactor. A
9'~19 3.5/1 mole ratio acrylonitrile-ethylenediamine reaction product in a 1:1:1 weight ratio methanol-liquid ammonia-polynitrile solution was passed over the catalyst with hydrogen and gave relatively high conversion in the S hydrogenation except near the end of the 55 hour run. ~owever, the catalyst, when removed from the reactor, was found to be composed of broken pieces of the tablet, no longer capable of being used.
EXAMPLE IV
To a solution of 197 g. (1.85 moles) of sodium carbonate in three liters of distilled water was added 430 g.
(1.48 moles) of cobalt nitrate hexahydrate and 101 g. (0.34 mole) of zinc nitrate hexahydrate in two liters of distilied water at 75C. Stirring was continued for an hour at that temperature followed by filtration and washing eight times with hot distilled water. The oxides were dried at 110C and calcined for two hours at 400C to provide 144g. of product, 56.9% Co, 12.8% Zn, 142 ppm of sodium. It was prereduced with hydrogen at 325C, stabilized with dilute oxygen in nitrogen and pelleted with 0.5% graphite. The tablets were put in the 25 ml. fixed bed reactor and subjected to a 1~1 hour continuous run. The nitrile employed was made by reaction of acrylonitrile with ethylenediamine in a 1.5:1 molar ratio. It was passed over the catalyst in a solution composed of equal parts by ~eight of nitrile, methanol and anhydrous ammonia at a rate of 24 ml. per hour accompanied by 12 liters ~STP) per hour of hydrogen. Gas chromatographic analysis of the product, free of methanol and ammonia, gave values of 64%
bis(aminopropyl)ethylenediamine and 33%
aminopropylethylenediamine. The catalyst pellets were physically unchanged.
9~19 EXA~LE V
Here an experiment was carried out, using the commercial nitrile hydrogenation catalyst described in Example II and the same l.S:l mole ratio acrylonitrile-ethylenediamine addition product feed of Example IV. Normally, the lower the acrylonitrile-ethylenediamine ratio feed used, the less the tendency for catalyst tablets to disintegrate. Under the same conditions as used in Example IV, the cobalt-copper-chromia catalyst was used for 85 hours, becoming almost completely converted to a finely divided mud by the termination of the experiment.
EXAMPLE VI
Two liters of distilled water containing 22.6 g. of synthetic calcium silicate was heated to 70C. This was stirred while 244 g. of Co(N03)2.6H20 and 18 g. Zn (N03)2.6~20 in two liters of distilled water was run slowly in simultaneously with 155 g. of sodium carbonate in another two liters of distilled water. All solutions were kept at 7~C, with the additions adjusted to maintain the pH of the reaction solution at %0. Following an hour digestion period, solids were collected by filtration, washed eight times, dried at 110C and calcined an hour at 400C. Analysis of the catalyst before prereduction was Co 51.3%, Zn 4.1%, Ca 3.7%, Si 4.8%
and Na 532 ppm. Following prereduction at 325C and sta~ilization, pellets were made with the aid of 0.5%
graphite.
The feed for the fixed bed hydrogenation was prepared by reaction of 1.88 moles of acrylonitrile per mole of ethylenediamine. The continuous run was made at the same rates and conditions as were used for Example I. After 22 _g_ ~1~9'~19 hours, the gas chromatographic analysis of the product (free of ammonia and methanol) was 15% aminopropyl-ethylenediamine, 69% bis(aminopropyl)ethylenediamine and 7.6%
tris(aminopropyl)ethylenediamine. The run was terminated after 251 hours at which time the corresponding analyses were 15%, 69% and 7.3%. The catalyst pellets did not form finely divided material although a few of the pellets were split.
From the foregoing description and examples of this invention, those of ordinary skill in the art may make many modifications and variations therefrom without departing from the scope of the invention as hereinafter claimed.
Claims (10)
1. A hydrogenation method for preparing pollyamines from the corresponding polynitriles which comprises using a pelleted cobalt-zinc hydrogenation catalyst, whereby said catalyst pellet is further characterized as substantially maintaining its integral character during said hydrogenation.
2. The method of Claim 1 wherein said hydrogenation is effected in presence of a solvent.
3. The method of Claim 2 wherein said solvent is an organic solvent.
4. The method of Claim 3 wherein said organic solvent is an alcohol.
5. The method of Claim 4 wherein said alcohol is methanol.
6. The method of Claim 1 wherein said hydrogenation is carried out in the presence of ammonia.
7. The method of Claim 6 carried out in liquid phase under reaction conditions including a temperature within the range of from about 70° to about 220°C and a pressure of about 30 to 800 atmospheres and from about 2 to about 20 moles of ammonia per mole equivalent of nitrile.
8. The method of Claim 1 wherein said catalyst comprises cobalt and zinc metal in oxide form.
9. The method of Claim 1 wherein said cobalt-zinc catalyst has a molar ratio of Co:Zn varying from 98:2 to 60:40.
10. The method of Claim 1 wherein said polynitrile to be hydrogenated is derived from reaction with acrylonitrile.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11096680A | 1980-01-10 | 1980-01-10 | |
| US110,966 | 1987-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1149419A true CA1149419A (en) | 1983-07-05 |
Family
ID=22335894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000365419A Expired CA1149419A (en) | 1980-01-10 | 1980-11-25 | Preparation of polyamines from polynitriles |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5914457B2 (en) |
| BE (1) | BE886968A (en) |
| CA (1) | CA1149419A (en) |
| DE (1) | DE3048836A1 (en) |
| FR (1) | FR2473511A1 (en) |
| GB (1) | GB2067191B (en) |
| NL (1) | NL8100034A (en) |
| SE (1) | SE8100069L (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135725B1 (en) * | 1983-08-02 | 1989-03-08 | Tosoh Corporation | Process for producing polyamines |
| US4721811A (en) * | 1985-08-26 | 1988-01-26 | W. R. Grace & Co. | Synthesis of aliphatic polyamines |
| US5039436A (en) * | 1986-04-18 | 1991-08-13 | The Lubrizol Corporation | Coupled polyamine lubricant additives derived from hydrocarbyl polynitriles and polyamines |
| US4906392A (en) * | 1986-04-18 | 1990-03-06 | The Lubrizol Corporation | Coupled polyamine lubricant additives derived from hydrocarbyl polynitriles and polyamines |
| US5811584A (en) * | 1997-07-29 | 1998-09-22 | Hampshire Chemical Corp. | Preparation of tetramethylethylenediamine |
| US20080194857A1 (en) | 2007-02-12 | 2008-08-14 | Air Products And Chemicals, Inc. | Selective Manufacture of N,N'-BIS(Cyanoethyl)-1,2-Ethylenediamine and N, N'-BIS(3-aminopropyl)-1,2-Ethylenediamine |
| TWI565686B (en) * | 2015-11-26 | 2017-01-11 | 南亞塑膠工業股份有限公司 | Preparation method of n,n'-bis(3-aminopropyl)ethylenediamine |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR971429A (en) * | 1940-05-30 | 1951-01-17 | Prod De Chimie Organique De La | Reduction or hydrogenation process using metal couples |
| US2701263A (en) * | 1952-05-06 | 1955-02-01 | American Viscose Corp | Method of making bis (3-aminopropyl) ether |
| US4003933A (en) * | 1975-07-16 | 1977-01-18 | Phillips Petroleum Company | Hydrogenation of nitriles in absence of secondary reaction suppressant |
-
1980
- 1980-09-25 JP JP13242880A patent/JPS5914457B2/en not_active Expired
- 1980-11-25 CA CA000365419A patent/CA1149419A/en not_active Expired
- 1980-12-23 DE DE19803048836 patent/DE3048836A1/en not_active Withdrawn
-
1981
- 1981-01-05 GB GB8100121A patent/GB2067191B/en not_active Expired
- 1981-01-06 BE BE0/203404A patent/BE886968A/en not_active IP Right Cessation
- 1981-01-07 NL NL8100034A patent/NL8100034A/en not_active Application Discontinuation
- 1981-01-08 SE SE8100069A patent/SE8100069L/en not_active Application Discontinuation
- 1981-01-09 FR FR8100329A patent/FR2473511A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| BE886968A (en) | 1981-05-04 |
| DE3048836A1 (en) | 1981-10-08 |
| GB2067191A (en) | 1981-07-22 |
| JPS56100743A (en) | 1981-08-12 |
| SE8100069L (en) | 1981-07-11 |
| NL8100034A (en) | 1981-08-03 |
| GB2067191B (en) | 1984-04-04 |
| FR2473511A1 (en) | 1981-07-17 |
| JPS5914457B2 (en) | 1984-04-04 |
| FR2473511B1 (en) | 1985-04-26 |
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Legal Events
| Date | Code | Title | Description |
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| MKEX | Expiry |