CA1043813A - Treatment of adiponitrile with weak-acid cation exchange resins - Google Patents
Treatment of adiponitrile with weak-acid cation exchange resinsInfo
- Publication number
- CA1043813A CA1043813A CA234,359A CA234359A CA1043813A CA 1043813 A CA1043813 A CA 1043813A CA 234359 A CA234359 A CA 234359A CA 1043813 A CA1043813 A CA 1043813A
- Authority
- CA
- Canada
- Prior art keywords
- adiponitrile
- resin
- cation exchange
- treated
- water
- 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
- C07C255/00—Carboxylic acid nitriles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process for reducing the amount of basic impurities, especially N-heterocyclic compounds, in adiponitrile is disclosed.
The process comprises treating adiponitrile with a weak-acid cation exchange resin in the presence of water. The cation exchange resin is used in its hydrogen form. The process is particularly useful in the purification of adiponitrile manu-factured from adipic acid and ammonia.
A process for reducing the amount of basic impurities, especially N-heterocyclic compounds, in adiponitrile is disclosed.
The process comprises treating adiponitrile with a weak-acid cation exchange resin in the presence of water. The cation exchange resin is used in its hydrogen form. The process is particularly useful in the purification of adiponitrile manu-factured from adipic acid and ammonia.
Description
_ ~4 ~
The present invention relates to the treatment of adiponitrile with weak-acid cation exchange resins and in par- -ticular to a process for reducing the amount of basic impuri-ties in crude adiponitrile in which the crude adiponitrile is - treated with a weak-acid cation exchange resin in the presence of water.
One of the more important uses o~ adiponitrile at the present time is in the manufacture o~ hexamethylene diamine.
Thiæ diamine may be used aæ a detergent, as an emulsi~ying agent or, in particular, as an intermediate in the manufacture of polymers. A catalytic hydrogenation reaction is usually employed to con~ert adiponitrile to hexamethylene diamine.
There are several method~ for synthesizing adiponitrile.
In paxticular, adiponitrile may be obtainea by reacting adipic acld with ammonia in the presence Or a dehydrating catalyst, for example, by the techniques disclosed in U. S. Patent 2,200,734 ~ ;
- Or Arnold and Lazier which issued May 14, 1940 and in U.S. Patent
The present invention relates to the treatment of adiponitrile with weak-acid cation exchange resins and in par- -ticular to a process for reducing the amount of basic impuri-ties in crude adiponitrile in which the crude adiponitrile is - treated with a weak-acid cation exchange resin in the presence of water.
One of the more important uses o~ adiponitrile at the present time is in the manufacture o~ hexamethylene diamine.
Thiæ diamine may be used aæ a detergent, as an emulsi~ying agent or, in particular, as an intermediate in the manufacture of polymers. A catalytic hydrogenation reaction is usually employed to con~ert adiponitrile to hexamethylene diamine.
There are several method~ for synthesizing adiponitrile.
In paxticular, adiponitrile may be obtainea by reacting adipic acld with ammonia in the presence Or a dehydrating catalyst, for example, by the techniques disclosed in U. S. Patent 2,200,734 ~ ;
- Or Arnold and Lazier which issued May 14, 1940 and in U.S. Patent
2,273,633 of M. ~. A. Fluchaire which issued February 17, 1942.
Adiponltrlle, especially adiponitrile obtained rrom adipic acid, ; 20 contains impurlties, ~ome Or which boil at temperatures close to the boiling point o~ adiponitrile. 2-Cyanocyclopentylidene-imine, hereinafter ~ometimes rererred to as CPI, i~ an example ;
such ~n impurity. Close boiling impuritie~ fre~uently cannot be removed erriciently in indu~trial scale di~tillation columns.
Impurltie~ in the adiponitrilc may lead to impuritie~ in sub-~ ~oquont derivatlve~, in partlcular in hexamethylene dlamine, - that are dirrlcult to remove. Failurc to remove these latter impuritie~ may ro~ult in inrerior and variable propertles, e~-.; ,....... . . .
pecially in polymer~ manuractured u5ing ~uch impure hexamethyl~
ene di~mine. Tcchnique8 for the purirication Or adiponitrile are known in the axt. ~or example, adiponitrlle may be treated ~.
., . ~ .
~4 3 ~ ~ ~
with a solid acidic catalyst in the presence o~ water and at a temperature of at least 140C to remove 2-cyanocycl~pentylidene-imine. The solid acidic cataly~ts may be sllica-alu~ina catalysts, cryst~lline aluminosilicate~, boron phosphate or titania-alumina.
Such treatmcnt is deæcribed in Canad~an Patent 912,036 o~ B. J.
Kershaw which issued October 10, 1972.
Adiponitrile, especially adiponitrile obtained ~rom the reaction o~ adlpic acid with ammonia, may also contain impurities in the form of cyclic amines, especially N-hetero-cyclic compounds. Examples of such impurities are 2-methyl-4-amino-5,6-trimethylene pyrimidine, hereinafter sometimes re-ferred to as MAP, 2-Pm~no-3,4,5,6 bis(trimethylene) pyridine, .~ hereinafter so_etimes referred to as ABP, and 2-cyclopentyl-4-amino-5,6-trimethylene pyr~m~dine, hereinafter sometimes re-~erred to as VAP. Such N-heterocyclic compounds may cauae prob-lems in the hydrogenation of adiponitrile to hexamethylene diamine or in the subsequent purification o~ he~amethylene diamine.
It has now been ~ound that basic impurities, e~pecially N-heterocycllc compound~, may bo removed from crude adiponitrile ~y treating the adiponitrile with a weak-acid cation exchange resin, ~uch ro~ins being discu~sed hereinafter.
Accordingly, the pre~ent invention provide~ a procee~
for reducing the amount of basic impurities in crude adiponitrile, said process comprlsing the steps of treating crude adiponitrile with a weak-acid cation exchange resin in the presence of water and at a temperature in the range of from 20C up to the temper- - ~-ature ~t which degradation o~ the weak-acid catlon exchange resin becomes slgnl~lcant, said resin being in its hydrogen form, and ~-~
separating adiponitrile there~rom.
In a pre~erred embodiment of the process o~ the present . . .
;~0438~3 invention the temperature is in the range 20 C to 140 C and especially in the range 25C to 100 C.
In a further embodiment the adiponitrile is adipo-nitrile manufactured ~rom adipic acid and ammonia.
In another embodiment the adiponitrile being treated contains at least 1% by weight o~ water.
Cation exchange resins are usually classi~ied as being of three general types. Strong-acid cation exchange resins have a che lcal activity similar to sulphuric acid and commercially are usually nuclear sulphonic acid or methylene sulphonic acid resins. Intermediate-acid cation exchange resins have a che_ical activity ~m~lar to phosphoric acid and commercially are usually phosphonic acid, phosphonous acid or phosphoric acid resins.
Weak-acid cation exchange resins, which are used in the process ;
o~ the pre6ent invention, have a chemio~l activity similar to acetlc acid and commercially are usually carboxylic acid or phenolic resins. me classes of lon exchange resins are dis-cussed in greater detail in "DUOLITE* Ion-Exchange Manual" ob-tainable from Diamond Shamrock Chemical Company.
In the process of the present inventlon crude adipo-nitrile is treated with a weak-acid cation exchange resin.
In the process the adiponitrile may be treated by contacting the adiponitrile and re~in in a continuous proces6 or in a batch .:
process, the ~ormer being pre~erred. Preferably, the adiponitrile ~ ~-is passed throu6h a ~ixed bed o~ weak-acid cation exchange resln.
` In a preferred embodiment the adiponitrile i8 adiponitrlle manu-~actured ~rom adipic acid and ammonia, *denotes trade mark ~'
Adiponltrlle, especially adiponitrile obtained rrom adipic acid, ; 20 contains impurlties, ~ome Or which boil at temperatures close to the boiling point o~ adiponitrile. 2-Cyanocyclopentylidene-imine, hereinafter ~ometimes rererred to as CPI, i~ an example ;
such ~n impurity. Close boiling impuritie~ fre~uently cannot be removed erriciently in indu~trial scale di~tillation columns.
Impurltie~ in the adiponitrilc may lead to impuritie~ in sub-~ ~oquont derivatlve~, in partlcular in hexamethylene dlamine, - that are dirrlcult to remove. Failurc to remove these latter impuritie~ may ro~ult in inrerior and variable propertles, e~-.; ,....... . . .
pecially in polymer~ manuractured u5ing ~uch impure hexamethyl~
ene di~mine. Tcchnique8 for the purirication Or adiponitrile are known in the axt. ~or example, adiponitrlle may be treated ~.
., . ~ .
~4 3 ~ ~ ~
with a solid acidic catalyst in the presence o~ water and at a temperature of at least 140C to remove 2-cyanocycl~pentylidene-imine. The solid acidic cataly~ts may be sllica-alu~ina catalysts, cryst~lline aluminosilicate~, boron phosphate or titania-alumina.
Such treatmcnt is deæcribed in Canad~an Patent 912,036 o~ B. J.
Kershaw which issued October 10, 1972.
Adiponitrile, especially adiponitrile obtained ~rom the reaction o~ adlpic acid with ammonia, may also contain impurities in the form of cyclic amines, especially N-hetero-cyclic compounds. Examples of such impurities are 2-methyl-4-amino-5,6-trimethylene pyrimidine, hereinafter sometimes re-ferred to as MAP, 2-Pm~no-3,4,5,6 bis(trimethylene) pyridine, .~ hereinafter so_etimes referred to as ABP, and 2-cyclopentyl-4-amino-5,6-trimethylene pyr~m~dine, hereinafter sometimes re-~erred to as VAP. Such N-heterocyclic compounds may cauae prob-lems in the hydrogenation of adiponitrile to hexamethylene diamine or in the subsequent purification o~ he~amethylene diamine.
It has now been ~ound that basic impurities, e~pecially N-heterocycllc compound~, may bo removed from crude adiponitrile ~y treating the adiponitrile with a weak-acid cation exchange resin, ~uch ro~ins being discu~sed hereinafter.
Accordingly, the pre~ent invention provide~ a procee~
for reducing the amount of basic impurities in crude adiponitrile, said process comprlsing the steps of treating crude adiponitrile with a weak-acid cation exchange resin in the presence of water and at a temperature in the range of from 20C up to the temper- - ~-ature ~t which degradation o~ the weak-acid catlon exchange resin becomes slgnl~lcant, said resin being in its hydrogen form, and ~-~
separating adiponitrile there~rom.
In a pre~erred embodiment of the process o~ the present . . .
;~0438~3 invention the temperature is in the range 20 C to 140 C and especially in the range 25C to 100 C.
In a further embodiment the adiponitrile is adipo-nitrile manufactured ~rom adipic acid and ammonia.
In another embodiment the adiponitrile being treated contains at least 1% by weight o~ water.
Cation exchange resins are usually classi~ied as being of three general types. Strong-acid cation exchange resins have a che lcal activity similar to sulphuric acid and commercially are usually nuclear sulphonic acid or methylene sulphonic acid resins. Intermediate-acid cation exchange resins have a che_ical activity ~m~lar to phosphoric acid and commercially are usually phosphonic acid, phosphonous acid or phosphoric acid resins.
Weak-acid cation exchange resins, which are used in the process ;
o~ the pre6ent invention, have a chemio~l activity similar to acetlc acid and commercially are usually carboxylic acid or phenolic resins. me classes of lon exchange resins are dis-cussed in greater detail in "DUOLITE* Ion-Exchange Manual" ob-tainable from Diamond Shamrock Chemical Company.
In the process of the present inventlon crude adipo-nitrile is treated with a weak-acid cation exchange resin.
In the process the adiponitrile may be treated by contacting the adiponitrile and re~in in a continuous proces6 or in a batch .:
process, the ~ormer being pre~erred. Preferably, the adiponitrile ~ ~-is passed throu6h a ~ixed bed o~ weak-acid cation exchange resln.
` In a preferred embodiment the adiponitrile i8 adiponitrlle manu-~actured ~rom adipic acid and ammonia, *denotes trade mark ~'
- 3 -.
:
. -- .. .. ..... . ., ~ - - .
While the adiponitrile treated by the process of the present invention is de~cribed as "crude adiponitrile" the adiponitrile being treated is preferably adiponitrile that has been subjected to partial puri~ication, e.g., by distill-ation.
me treatment of adiponitrile according to the pro-cess of the present invention is carried out in the presence of water. me temperature at which the adiponitrile is treated may be in the range of from about 20C up to the temperature at which the weak-acid cation exchange resin exhibit~ si~nificant degradation. Such degradation may affect the properties of the catlon exchange resin and/or the properties and especially the impurities in the adiponitrile after treatment. In par-ticular, the adiponitrile after treatment mQy contain decomp-osition products of the cation exchange resin. me temperature at which decomposition of the cation e~change re~in may become significant will depend on the actual resin being used and, in part, on the process conditiona. Pre~erably the upper temper-ature limit is not in excess of 140C. Pre~erred temperatures are in the range 20 to 100C and in particular 25 to 50C.
As stated above the treatment of the adiponitrile is carried out in the presence Or water. The water content oP the adiponitrile is preferably in the range from about 1% to a ratio o~ water to adiponitrile of about 2:1, on a weight basi~. me upper limit o~ water is determined primarily by practical con-~ideratlons. In an embodiment of the proceæs oP the pregent in-ven 40n the treatment o~ adiponitrile is carried out in the pres-ence o~ at least 5% by weight of water. A particularly prePerred range of water is 5-10% by weight.
me pre~sure used in the process of the present in- ~-vention is not critical. The pre~sure will depend primarily ' ' ' - ~.
:
. -- .. .. ..... . ., ~ - - .
While the adiponitrile treated by the process of the present invention is de~cribed as "crude adiponitrile" the adiponitrile being treated is preferably adiponitrile that has been subjected to partial puri~ication, e.g., by distill-ation.
me treatment of adiponitrile according to the pro-cess of the present invention is carried out in the presence of water. me temperature at which the adiponitrile is treated may be in the range of from about 20C up to the temperature at which the weak-acid cation exchange resin exhibit~ si~nificant degradation. Such degradation may affect the properties of the catlon exchange resin and/or the properties and especially the impurities in the adiponitrile after treatment. In par-ticular, the adiponitrile after treatment mQy contain decomp-osition products of the cation exchange resin. me temperature at which decomposition of the cation e~change re~in may become significant will depend on the actual resin being used and, in part, on the process conditiona. Pre~erably the upper temper-ature limit is not in excess of 140C. Pre~erred temperatures are in the range 20 to 100C and in particular 25 to 50C.
As stated above the treatment of the adiponitrile is carried out in the presence Or water. The water content oP the adiponitrile is preferably in the range from about 1% to a ratio o~ water to adiponitrile of about 2:1, on a weight basi~. me upper limit o~ water is determined primarily by practical con-~ideratlons. In an embodiment of the proceæs oP the pregent in-ven 40n the treatment o~ adiponitrile is carried out in the pres-ence o~ at least 5% by weight of water. A particularly prePerred range of water is 5-10% by weight.
me pre~sure used in the process of the present in- ~-vention is not critical. The pre~sure will depend primarily ' ' ' - ~.
- 4 -~; '-;
~ .
. . .
~ 3 ~ 1 ~
on other process variables, for example, temperature and the water content o~ the adiponitrile.
In a pre~erred embodiment of the process o~ the present invention the adiponitrile is substantially ~ree of ammonia.
In the process of the present invention amines es- ~
pecially the aforementioned cyclic amines are removed ~rom ~ ;
the adiponitrile by retention on the weak-acid cation ex-- change resin. After a period of time it may become desirable to remove said amines from the weak-acid cation exchange resin and thereby regenerate the resin for further use. The res~n may be regenerated by contacting with an amount of a strong acid, for example, hydrochloric or sulphuric acid, that is slightly in excess of the stoichiometric amount of acid ~ f required to con~ert the resin to its acid or hydrogen form.
The resin i8 used in the process of the present invention in its acid or hydrogen form. Preferably the resin is regener-- ated at about ambient temperature~. The relatively low amount ~f acid required ~or regeneration o~ weak-acid cation exchange 20 resins, as compared with strong-acid cation exchange resins, may hare advantages with respect to the control of polluti~n from the proce~s.
Adiponitrile purified by the process described herein i8 particularly useful in the manufacture of hexamethylene diamine u8ing an iron catalyst as is di~closed in Canadian patent application 234 356 Or B. J. Kershaw filed on the s&me d&te as the present application.
A~ iB exemplifi~d hereina~ter the treatment of adlpo-~ nitrile with a weak-acid cation exchange resin in the presence 30 of water results in e~sentially no hydroly~is of 2-cyanocyclo-pent~lideneimine. ~uch hydrolysis would result in the ~orm-ation o~ ammonla, which would be adsorbed by the resin thereby _ 5 _ - ~. ,. - ::
" ~
- ,. ~ ... ,, . . ~ . . . . ...
.1043t~
reducing the capacity of the resin for removing other amines. The process of the present invention may, therefore, offer advantages over the treatment of adiponitrile with a strong-acid cation exchange resin in the presence of water, 2-cyanocyclopentyl-ideneimine being hydrolyzed by strong-acid cation exchange resins in the presence of water.
me process of the present invention is illustrated by the following examples. The adiponitrile used in the examples had been manufactured ~rom adipic acid and ammonia.
All analyses are on a weight basis.
EXAMPLE I
To 50 ml o~ a crude adiponitrile referred to herein-after as adiponitrile #1, the composition of which is given `
in Table I hereinafter, were added 3 ml of water and 2 g of DUOLITE CC-3, a weak-acid cation exchange resin obtainable from Diamond Shamrock Chemical Company. The resulting mixture was stirred for 30 minutes~at ambient temperature and then filtered.
The filtrate of treatea adiponttrile ~o obtained was analyzed by gas chromatography. The results were as follows:
Before Treatment* After Treatment* Removal of _omponent with Resin (%) with Resin (%) Impurity (%) MAP - 0.040 0.0079 80 ABP 0.071 0.019 75 CPI 0.35 0.35 0 *Analy~es are on a solution ba~is, i.e., adiponitrile plus water.
EXAMPLE II `
To show the effect of water, Example I was repeated except th~t no water was added to the adiponitrile. The re-sults were as follows: -Be~ore Tre~tment A~ter Treatment Removal of Impurity _with Re~in (%) with Re~in (%~ Impurity (%) : .-... .
o o40 o.o38 5 .~. . . ..
, , .
, ..
EXAMPLE III
:. -: . .
To 50 ml o~ a crude adi~onitrile re~erred to herein-after as adiponitrile #2, the composition o~ which is gi~en -in Table I hereinafter, were added water and DUOLITE CC-3 cation exchange resin. The resulting mixture was stirred ~or 30 minutes and a sample of the adiponitrile was analyzed by gas chromatography. A ~urther analysis was made after a total o~ 60 minutes treatment. me results are given in Table II.
me hydrolysis product of CPI, 2-cyanocyclopentanone, was not detected in any of the samples.
EXAMPLE IV
, Approxlmately 37 g of DUOLITE CC-3 cation exchange resin were placed in a glass column o~ approximately 2.5 cm internal diameter. 60 ml of water were mixed with one litre of adiponitrile #l and the resulting solution was pa~sed down through the glass column. The contact time of adiponitrile with the cation exchange resin was approximately 2.5 minutes.
Samples of the treated adiponitrile eluting from the glass column were taken periodically and analyzea by gas chromato-graphy. The results were as follows:
Sample~ MAP(%) Removal of ABP (%) Removal o~
' MAP (%) ABP (%) .
Treated #1 0.0055 86 0.012 83 Treated #2 0.0085 79 0.012 83 Treated #3 0.015 63 0.023 68 *Treated #l - after 100 ml of treated mixture had eluted from ~-the column, the next 100 ml was collectea and thl~
sample taken therefrom. -~
Treated #2 - after 400 ml Or treated mixture had eluted from the column, the next 200 ml was collected and this sa~ple taken therefrom.
Treated #3 - sample taken from the f~nal 70 ml eluted from the column.
- 7 ~
,,.:, .:
.. , . . . , . - :
~, - ~ . ,. . . .- . ; ,, , :~438~3 After treatment of the adiponitrile the cation ex-change re~in ln the column was treated with 40 ml o~ 15%
hydro~hloric acid and then washed with distilled water until the eluent was free of acid. A solution o~ 30 ml of water in 500 ml o~ adiponitrile #1 was then passed down through the cation exchange resin as described above. The result~
were:
Sample* MAP (~) Removal of ABP (~) Removal of MAP (%) , ABP (%) 10Treated #1 0.0026 94 0.023 67 Treated #2 o.oo63 84 0.022 69 Treated #3 0.0078 81 0.025 65 *Treated #l - ~ample taken from the fir~t 100 ml o~ eluent.
Treated #2 - after 100 ml of treated mixture had eluted from the column, the next 300 ml was collected and thiB sample taken thererrom.
Treated #3 - sample taken ~rom the last 100 ml of eluent.
TABLE I
Impurlty*~ Adiponitrile #1 Adiponitrile #2 ; 20 MAP 0.042 0.028 ABP 0.075 0.062 VAP 0.075 CPI o.35 0.15 -cyanovalerlc acld 1.0 ~ -cyanovaleramlde 0.5 0.13 : adipl m~ de 0.6 N.B. all analyses expre8sed as percentages on a weight/volume ba~is, remaining component essentlally adiponitrile.
** MAP - 2-methyl-4-amino-5,6-trimethylene pyrimidine ;;~
ABP ~ 2-amino-3,4,5,6-bis (tr~mPthylene) pyridine VAP - 2-cyclopentyl-4-amino-5,6-trimethylene pyrimidine CPI _ 2-cyanocyclopentylideneim~ne '- ' . :' .
. -. - - . ~ . - . . . - . . - . ~
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9 ~:
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on other process variables, for example, temperature and the water content o~ the adiponitrile.
In a pre~erred embodiment of the process o~ the present invention the adiponitrile is substantially ~ree of ammonia.
In the process of the present invention amines es- ~
pecially the aforementioned cyclic amines are removed ~rom ~ ;
the adiponitrile by retention on the weak-acid cation ex-- change resin. After a period of time it may become desirable to remove said amines from the weak-acid cation exchange resin and thereby regenerate the resin for further use. The res~n may be regenerated by contacting with an amount of a strong acid, for example, hydrochloric or sulphuric acid, that is slightly in excess of the stoichiometric amount of acid ~ f required to con~ert the resin to its acid or hydrogen form.
The resin i8 used in the process of the present invention in its acid or hydrogen form. Preferably the resin is regener-- ated at about ambient temperature~. The relatively low amount ~f acid required ~or regeneration o~ weak-acid cation exchange 20 resins, as compared with strong-acid cation exchange resins, may hare advantages with respect to the control of polluti~n from the proce~s.
Adiponitrile purified by the process described herein i8 particularly useful in the manufacture of hexamethylene diamine u8ing an iron catalyst as is di~closed in Canadian patent application 234 356 Or B. J. Kershaw filed on the s&me d&te as the present application.
A~ iB exemplifi~d hereina~ter the treatment of adlpo-~ nitrile with a weak-acid cation exchange resin in the presence 30 of water results in e~sentially no hydroly~is of 2-cyanocyclo-pent~lideneimine. ~uch hydrolysis would result in the ~orm-ation o~ ammonla, which would be adsorbed by the resin thereby _ 5 _ - ~. ,. - ::
" ~
- ,. ~ ... ,, . . ~ . . . . ...
.1043t~
reducing the capacity of the resin for removing other amines. The process of the present invention may, therefore, offer advantages over the treatment of adiponitrile with a strong-acid cation exchange resin in the presence of water, 2-cyanocyclopentyl-ideneimine being hydrolyzed by strong-acid cation exchange resins in the presence of water.
me process of the present invention is illustrated by the following examples. The adiponitrile used in the examples had been manufactured ~rom adipic acid and ammonia.
All analyses are on a weight basis.
EXAMPLE I
To 50 ml o~ a crude adiponitrile referred to herein-after as adiponitrile #1, the composition of which is given `
in Table I hereinafter, were added 3 ml of water and 2 g of DUOLITE CC-3, a weak-acid cation exchange resin obtainable from Diamond Shamrock Chemical Company. The resulting mixture was stirred for 30 minutes~at ambient temperature and then filtered.
The filtrate of treatea adiponttrile ~o obtained was analyzed by gas chromatography. The results were as follows:
Before Treatment* After Treatment* Removal of _omponent with Resin (%) with Resin (%) Impurity (%) MAP - 0.040 0.0079 80 ABP 0.071 0.019 75 CPI 0.35 0.35 0 *Analy~es are on a solution ba~is, i.e., adiponitrile plus water.
EXAMPLE II `
To show the effect of water, Example I was repeated except th~t no water was added to the adiponitrile. The re-sults were as follows: -Be~ore Tre~tment A~ter Treatment Removal of Impurity _with Re~in (%) with Re~in (%~ Impurity (%) : .-... .
o o40 o.o38 5 .~. . . ..
, , .
, ..
EXAMPLE III
:. -: . .
To 50 ml o~ a crude adi~onitrile re~erred to herein-after as adiponitrile #2, the composition o~ which is gi~en -in Table I hereinafter, were added water and DUOLITE CC-3 cation exchange resin. The resulting mixture was stirred ~or 30 minutes and a sample of the adiponitrile was analyzed by gas chromatography. A ~urther analysis was made after a total o~ 60 minutes treatment. me results are given in Table II.
me hydrolysis product of CPI, 2-cyanocyclopentanone, was not detected in any of the samples.
EXAMPLE IV
, Approxlmately 37 g of DUOLITE CC-3 cation exchange resin were placed in a glass column o~ approximately 2.5 cm internal diameter. 60 ml of water were mixed with one litre of adiponitrile #l and the resulting solution was pa~sed down through the glass column. The contact time of adiponitrile with the cation exchange resin was approximately 2.5 minutes.
Samples of the treated adiponitrile eluting from the glass column were taken periodically and analyzea by gas chromato-graphy. The results were as follows:
Sample~ MAP(%) Removal of ABP (%) Removal o~
' MAP (%) ABP (%) .
Treated #1 0.0055 86 0.012 83 Treated #2 0.0085 79 0.012 83 Treated #3 0.015 63 0.023 68 *Treated #l - after 100 ml of treated mixture had eluted from ~-the column, the next 100 ml was collectea and thl~
sample taken therefrom. -~
Treated #2 - after 400 ml Or treated mixture had eluted from the column, the next 200 ml was collected and this sa~ple taken therefrom.
Treated #3 - sample taken from the f~nal 70 ml eluted from the column.
- 7 ~
,,.:, .:
.. , . . . , . - :
~, - ~ . ,. . . .- . ; ,, , :~438~3 After treatment of the adiponitrile the cation ex-change re~in ln the column was treated with 40 ml o~ 15%
hydro~hloric acid and then washed with distilled water until the eluent was free of acid. A solution o~ 30 ml of water in 500 ml o~ adiponitrile #1 was then passed down through the cation exchange resin as described above. The result~
were:
Sample* MAP (~) Removal of ABP (~) Removal of MAP (%) , ABP (%) 10Treated #1 0.0026 94 0.023 67 Treated #2 o.oo63 84 0.022 69 Treated #3 0.0078 81 0.025 65 *Treated #l - ~ample taken from the fir~t 100 ml o~ eluent.
Treated #2 - after 100 ml of treated mixture had eluted from the column, the next 300 ml was collected and thiB sample taken thererrom.
Treated #3 - sample taken ~rom the last 100 ml of eluent.
TABLE I
Impurlty*~ Adiponitrile #1 Adiponitrile #2 ; 20 MAP 0.042 0.028 ABP 0.075 0.062 VAP 0.075 CPI o.35 0.15 -cyanovalerlc acld 1.0 ~ -cyanovaleramlde 0.5 0.13 : adipl m~ de 0.6 N.B. all analyses expre8sed as percentages on a weight/volume ba~is, remaining component essentlally adiponitrile.
** MAP - 2-methyl-4-amino-5,6-trimethylene pyrimidine ;;~
ABP ~ 2-amino-3,4,5,6-bis (tr~mPthylene) pyridine VAP - 2-cyclopentyl-4-amino-5,6-trimethylene pyrimidine CPI _ 2-cyanocyclopentylideneim~ne '- ' . :' .
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Claims (11)
1. A process for reducing the amount of basic impuri-ties in crude adiponitrile, said process comprising the steps of treating crude adiponitrile with a weak-acid cation exchange resin in the presence of water and at a temperature in the range of from 20°C up to the temperature at which degradation of the weak-acid cation exchange resin becomes significant, said resin being in its hydrogen form, and separating adiponitrile therefrom.
2. The process of Claim 1 in which the adiponitrile is treated with the resin in the presence of at least 1%, by weight of adiponitrile, of water.
3. The process of Claim 2 in which the adiponitrile is treated with the resin in the substantial absence of ammonia.
4. The process of Claim 3 in which the adiponitrile is adiponitrile manufactured from adipic acid and ammonia.
5. The process of Claim 4 in which the temperature is in the range 20°C to 100°C.
6. The process of Claim 4 in which the temperature is in the range 25°C to 50°C.
7. The process of any one of Claim 4, Claim 5 and Claim 6 in which the ratio of water to adiponitrile when the adiponitrile is treated with the resin is less than 2:1 by weight.
8. The process of any one of Claim 4, Claim 5 and Claim 6 in which the adiponitrile is treated with the resin in the presence of at least 5%, by weight of adiponitrile, of water.
9. The process of any one of Claim 4, Claim 5 and Claim 6 in which the adiponitrile is treated with the resin in the presence of 5 to 10%, by weight of adiponitrile, of water.
10. The process of any one of Claim 1, Claim 5 and Claim 6 in which the adiponitrile contains 2-cyanocyclopentyl-ideneimine and in which there is essentially no hydrolysis of the 2-cyanocyclopentylideneimine.
11. The process of any one of Claim 1, Claim 5 and Claim 6 in which the crude adiponitrile has been subjected to distillation prior to treatment with the resin.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA234,359A CA1043813A (en) | 1975-08-26 | 1975-08-26 | Treatment of adiponitrile with weak-acid cation exchange resins |
| IT2584376A IT1065070B (en) | 1975-08-26 | 1976-07-29 | PROCESS FOR THE PRODUCTION OF HEXAMETHYLENE DIAMINE |
| GB2643777A GB1539436A (en) | 1975-08-26 | 1976-08-17 | Process for purifying adiponitrile |
| GB3427076A GB1539435A (en) | 1975-08-26 | 1976-08-17 | Process for the manufacture of hexamethylene diamine |
| FR7625712A FR2322127A1 (en) | 1975-08-26 | 1976-08-25 | PERFECTED PROCESS FOR THE PRODUCTION OF HEXAMETHYLENE DIAMINE FROM CRUDE ADIPONITRILE |
| DE19762638510 DE2638510A1 (en) | 1975-08-26 | 1976-08-26 | IMPROVED PROCESS FOR THE PREPARATION OF HEXAMETHYLENEDIAMINE |
| FR7706940A FR2334664A1 (en) | 1975-08-26 | 1977-03-09 | METHOD FOR REDUCING THE QUANTITY OF N-HETEROCYCLIC AMINE IN CRUDE ADIPONITRILE |
| US05/858,663 US4147717A (en) | 1975-08-26 | 1977-12-08 | Process for purifying adiponitrile |
| US05/858,661 US4146555A (en) | 1975-08-26 | 1977-12-08 | Process for purifying adiponitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA234,359A CA1043813A (en) | 1975-08-26 | 1975-08-26 | Treatment of adiponitrile with weak-acid cation exchange resins |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1043813A true CA1043813A (en) | 1978-12-05 |
Family
ID=4103917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,359A Expired CA1043813A (en) | 1975-08-26 | 1975-08-26 | Treatment of adiponitrile with weak-acid cation exchange resins |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1043813A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017040583A1 (en) | 2015-09-03 | 2017-03-09 | Invista North America S.A R.L. | Inhibiting cpi formation from adiponitrile |
| US11028045B2 (en) | 2016-05-02 | 2021-06-08 | Inv Nylon Chemicals Americas, Llc | Process for reducing CPI in a dinitrile stream |
| WO2021152564A1 (en) | 2020-01-31 | 2021-08-05 | Invista Textiles (U.K.) Limited | Impurity formation reduction during product refining |
-
1975
- 1975-08-26 CA CA234,359A patent/CA1043813A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017040583A1 (en) | 2015-09-03 | 2017-03-09 | Invista North America S.A R.L. | Inhibiting cpi formation from adiponitrile |
| US10640459B2 (en) | 2015-09-03 | 2020-05-05 | Invista North America S.A.R.L. | Inhibiting CPI formation from adiponitrile |
| US11028045B2 (en) | 2016-05-02 | 2021-06-08 | Inv Nylon Chemicals Americas, Llc | Process for reducing CPI in a dinitrile stream |
| WO2021152564A1 (en) | 2020-01-31 | 2021-08-05 | Invista Textiles (U.K.) Limited | Impurity formation reduction during product refining |
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