CA1302434C - Process for recovery of bis(hexamethylene)triamine - Google Patents
Process for recovery of bis(hexamethylene)triamineInfo
- Publication number
- CA1302434C CA1302434C CA000563856A CA563856A CA1302434C CA 1302434 C CA1302434 C CA 1302434C CA 000563856 A CA000563856 A CA 000563856A CA 563856 A CA563856 A CA 563856A CA 1302434 C CA1302434 C CA 1302434C
- Authority
- CA
- Canada
- Prior art keywords
- triamine
- bis
- aliphatic hydrocarbon
- hexamethylene
- bhmt
- 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 - Lifetime
Links
- MRNZSTMRDWRNNR-UHFFFAOYSA-N bis(hexamethylene)triamine Chemical compound NCCCCCCNCCCCCCN MRNZSTMRDWRNNR-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 9
- 238000011084 recovery Methods 0.000 title claims abstract description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 21
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000009835 boiling Methods 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 3
- 102100025991 Betaine-homocysteine S-methyltransferase 1 Human genes 0.000 description 16
- 101000933413 Homo sapiens Betaine-homocysteine S-methyltransferase 1 Proteins 0.000 description 16
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- HWJPHQNEWARZLH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5-decafluoro-6,6-bis(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F HWJPHQNEWARZLH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100176165 Mus musculus Shmt1 gene Proteins 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- -1 poly(hexamethylene) Polymers 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- KBMSFJFLSXLIDJ-UHFFFAOYSA-N 6-aminohexanenitrile Chemical compound NCCCCCC#N KBMSFJFLSXLIDJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RQZPVTJKRKQPGB-UHFFFAOYSA-N [4-(aminomethyl)-4-ethylcyclohexyl]methanamine Chemical compound CCC1(CN)CCC(CN)CC1 RQZPVTJKRKQPGB-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
TITLE
Process For Recovery Of Bis(hexamethylene)triamine Abstract Recovery of bis(hexamethylene)triamine from still heels of hexamethylenediamine by extraction using an aliphatic hydrocarbon having a boiling point between about 34°C and 210°C.
Process For Recovery Of Bis(hexamethylene)triamine Abstract Recovery of bis(hexamethylene)triamine from still heels of hexamethylenediamine by extraction using an aliphatic hydrocarbon having a boiling point between about 34°C and 210°C.
Description
3~
T I TLE
Process For Recovery Of Bi s ( hexamethylene~triamine Field of The Invention This invention relates to a process for the isolation and purification of bis(hexamethylene~triamine, hereinafter sometimes referred to as "BHMT". BHMT has the chemical structure:
T I TLE
Process For Recovery Of Bi s ( hexamethylene~triamine Field of The Invention This invention relates to a process for the isolation and purification of bis(hexamethylene~triamine, hereinafter sometimes referred to as "BHMT". BHMT has the chemical structure:
2 NCH2 CH2 CH2 CH2 CH2 CH2 NHC~32 CH2 CH2 CH2 CH2 CH2 NH2 .
~ackground Of The Invention BHMT is a byproduct from the manufacture of hexamethylenediamine. Large quantities of hexamethylene-diamine are manufactured for use in the production of 6,6-nylon. It is conventional to ~eparate the hexa-methylenediamine from other reaction products by distillation. The distillation residue, ~till heels, contains varying amounts of BHM~, depending on how the plant is running. According to U.S. Patent 4,115,304 to Chadwick, the distillation re~idue from one hexamethylene-diamine plant contained the following amounts of the listed components: -bis(hexamethylene)triamine 5 to 40% by wt C-10 diamine Iprlmarily 1,4-di(aminomethyl)-1-ethyl cyclohexane)10 to 35~ by wt hexamethylene diamine and adiponitrile2 to 10% by wt poly(hexamethylene)-polyamines and unknown compounds30 to 75~ by wt water trace ammonia trace BHMT has been reported to have been recovered I-0440 35 from such a residue by distillation: see U.S. Patent 3,523,973 to Evans~ However, because ~he ~MT has a high .. . .... . .. .. . .
boiling point, attempts to separate it by distillation often l~ad to degradation and tar formation.
BHMT is useful as an additive in the ~anufacture of 6,6-nylon. It acts as a "branching agent"/ and accordinq to U.S. Patent 4,596,742 to Selivansky et al., in a sheath-core nylon yarn, wherein the sheath contains BHMT, the yarn has higher crimp development.
~HMT is also useful as an additive in 6,6-nylon polymers as a dye-receptor, can be added to asphalt to improve the bonding of the qravel to the other components, can be used in paper products, i.e., paper toweling, where it can replace diethylene triamine which acts to improve the wet 6trsngth of the paper product~.
Summary O The Invention The present invention provides a proc~ss ~or the recovery of BHMT from hexamethylenediamine still heels, and comprises (1) contacting the still heels with an aliphatic hydrocarbon having a boiliny point between about 34C and about 210C, whereby the BHnT is extracted from the still heels and dissolved in the aliphatic hydrocarbon, (2) ~eparating the aliphatic hydrocarbon containing the dissolved BHMT from the r~main~ng components of the still heels, and then (3) separating the BHMT from the aliphatic hydrocarbon.
The step of contacting the aliphatic hydrocarbon with the still heels can be carried out ~t ~ temperature range below room temperature to the boil~ng polnt of the aliphatic hydrocarbon. Preferably the temperature i~
above about 20C, with mixing to ~peed the extraction.
The ~tep of separating the aliphatic hydrocarbon containing the dissolved BHMT is be~t accompli~hed by decantation.
The st~p of separating the BHMT from the aliphatic hydrocarbon can be carried out by distilling tho aliphatic hydrocarbon, or by cooling the aliphatio hydrocarbon containing the dissolved sHMT until the sHMT
3 ~3~ 34 crystallizes from the solution, or the BHMT may be separated by extracting it from the aliphatic hydrocarbon with water, and subsequently evaporating the water.
Detail ~
Many suitable aliphatic hydrocarbons may be used to extract the BHMT from the hexamethylenediamine still heels, some are shown in the table below:
Distillation ~an~e at 760 mm Hq Heptane 94-98 Hexane 66-71 Cyclohexane 80-81 Lacquer Diluent L 97-107 15 Mineral Spirits lS8-195 Odorless Mineral Spirits 179-198 Pentane 34-39 Petroleum Ether 35-60 Example Three hundred ~eventy grams of still heels of a commercial hexamethylenediamine plant containing 64~ BHMT
were continuously extracted with one liter of hexane for 6 hours, using an ether extraction apparatus, at room temperature. After 6 hours 240 grams of the still heels had gone into the hexane leaving 130 grams of BHMT-depleted residue.
The hexane-extract was distilled off at atmospheric pressure at about 71C, and then the BHMT-rich residue was distilled through a short Oldershaw* column at about 1 mm pressure. The initial product distilled ~the foreshot) was about 42 grams. The foreshot was primarily 6-aminocapronitrile. The heart cuts were distilled at 50 to 152C -- 90 grams were collected which solidified on .
cooling. The product was analy~ed and found to be *denotes trademark .,~''~
~3~2~L3~L
q bis(hexamethylene)triamine. rhe product had a melting point of 34 to 35C.
sHM~ can be recrystallized from hexane, or 8HMT
can be converted into a pourable white powder by melting distilled aHMT and pouring it slowly, with stirring, into cold hexane. The precipitate can then be filtered off and dried under vacuum.
~ackground Of The Invention BHMT is a byproduct from the manufacture of hexamethylenediamine. Large quantities of hexamethylene-diamine are manufactured for use in the production of 6,6-nylon. It is conventional to ~eparate the hexa-methylenediamine from other reaction products by distillation. The distillation residue, ~till heels, contains varying amounts of BHM~, depending on how the plant is running. According to U.S. Patent 4,115,304 to Chadwick, the distillation re~idue from one hexamethylene-diamine plant contained the following amounts of the listed components: -bis(hexamethylene)triamine 5 to 40% by wt C-10 diamine Iprlmarily 1,4-di(aminomethyl)-1-ethyl cyclohexane)10 to 35~ by wt hexamethylene diamine and adiponitrile2 to 10% by wt poly(hexamethylene)-polyamines and unknown compounds30 to 75~ by wt water trace ammonia trace BHMT has been reported to have been recovered I-0440 35 from such a residue by distillation: see U.S. Patent 3,523,973 to Evans~ However, because ~he ~MT has a high .. . .... . .. .. . .
boiling point, attempts to separate it by distillation often l~ad to degradation and tar formation.
BHMT is useful as an additive in the ~anufacture of 6,6-nylon. It acts as a "branching agent"/ and accordinq to U.S. Patent 4,596,742 to Selivansky et al., in a sheath-core nylon yarn, wherein the sheath contains BHMT, the yarn has higher crimp development.
~HMT is also useful as an additive in 6,6-nylon polymers as a dye-receptor, can be added to asphalt to improve the bonding of the qravel to the other components, can be used in paper products, i.e., paper toweling, where it can replace diethylene triamine which acts to improve the wet 6trsngth of the paper product~.
Summary O The Invention The present invention provides a proc~ss ~or the recovery of BHMT from hexamethylenediamine still heels, and comprises (1) contacting the still heels with an aliphatic hydrocarbon having a boiliny point between about 34C and about 210C, whereby the BHnT is extracted from the still heels and dissolved in the aliphatic hydrocarbon, (2) ~eparating the aliphatic hydrocarbon containing the dissolved BHMT from the r~main~ng components of the still heels, and then (3) separating the BHMT from the aliphatic hydrocarbon.
The step of contacting the aliphatic hydrocarbon with the still heels can be carried out ~t ~ temperature range below room temperature to the boil~ng polnt of the aliphatic hydrocarbon. Preferably the temperature i~
above about 20C, with mixing to ~peed the extraction.
The ~tep of separating the aliphatic hydrocarbon containing the dissolved BHMT is be~t accompli~hed by decantation.
The st~p of separating the BHMT from the aliphatic hydrocarbon can be carried out by distilling tho aliphatic hydrocarbon, or by cooling the aliphatio hydrocarbon containing the dissolved sHMT until the sHMT
3 ~3~ 34 crystallizes from the solution, or the BHMT may be separated by extracting it from the aliphatic hydrocarbon with water, and subsequently evaporating the water.
Detail ~
Many suitable aliphatic hydrocarbons may be used to extract the BHMT from the hexamethylenediamine still heels, some are shown in the table below:
Distillation ~an~e at 760 mm Hq Heptane 94-98 Hexane 66-71 Cyclohexane 80-81 Lacquer Diluent L 97-107 15 Mineral Spirits lS8-195 Odorless Mineral Spirits 179-198 Pentane 34-39 Petroleum Ether 35-60 Example Three hundred ~eventy grams of still heels of a commercial hexamethylenediamine plant containing 64~ BHMT
were continuously extracted with one liter of hexane for 6 hours, using an ether extraction apparatus, at room temperature. After 6 hours 240 grams of the still heels had gone into the hexane leaving 130 grams of BHMT-depleted residue.
The hexane-extract was distilled off at atmospheric pressure at about 71C, and then the BHMT-rich residue was distilled through a short Oldershaw* column at about 1 mm pressure. The initial product distilled ~the foreshot) was about 42 grams. The foreshot was primarily 6-aminocapronitrile. The heart cuts were distilled at 50 to 152C -- 90 grams were collected which solidified on .
cooling. The product was analy~ed and found to be *denotes trademark .,~''~
~3~2~L3~L
q bis(hexamethylene)triamine. rhe product had a melting point of 34 to 35C.
sHM~ can be recrystallized from hexane, or 8HMT
can be converted into a pourable white powder by melting distilled aHMT and pouring it slowly, with stirring, into cold hexane. The precipitate can then be filtered off and dried under vacuum.
Claims (5)
1. A process for the recovery of bis(hexamethylene)triamine from hexamethylenediamine still heels, which comprises (1) contacting the still heels with an aliphatic hydrocarbon having a boiling point between about 34°C and about 210°C whereby the bis(hexa-methylene)triamine is extracted from the still heels and dissolved in the aliphatic hydrocarbon, (2) separating the aliphatic hydrocarbon containing the dissolved bis(hexa-methylene)triamine from the remaining components of the still heels, and then (3) separating the bis(hexa-methylene)triamine from the aliphatic hydrocarbon.
2. The process of claim 1 in which the bis(hexamethylene)triamine is separated from the aliphatic hydrocarbon by distillation of the aliphatic hydrocarbon.
3. The process of claim 1 in which the bis(hexamethylene)triamine is separated from the aliphatic hydrocarbon by crystallization.
4. The process of claim 1 in which the bis(hexamethylene)triamine is separated from the aliphatic hydrocarbon by extracting the bis(hexamethyiene)triamine with water.
5. The process of claim 4 in which the aliphatic hydrocarbon is hexane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US038,659 | 1987-04-15 | ||
| US07/038,659 US4803304A (en) | 1987-04-15 | 1987-04-15 | Recovery of bis(hexamethylene)triamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1302434C true CA1302434C (en) | 1992-06-02 |
Family
ID=21901177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000563856A Expired - Lifetime CA1302434C (en) | 1987-04-15 | 1988-04-12 | Process for recovery of bis(hexamethylene)triamine |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4803304A (en) |
| CA (1) | CA1302434C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19704612A1 (en) * | 1997-02-07 | 1998-08-13 | Basf Ag | Process for obtaining hexamethylenediamine from mixtures containing hexamethylenediamine |
| BR112022001863B1 (en) * | 2020-10-09 | 2023-03-07 | Ascend Performance Materials Operations Llc | ANTI-STRIPPING AND BITUMEN COMPOSITIONS, AS WELL AS PROCESS FOR IMPROVING THE DURABILITY OF A BITUMEN COMPOSITION |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2987452A (en) * | 1959-06-26 | 1961-06-06 | Chemstrand Corp | Method for the purification of hexamethylenediamine |
| US3523973A (en) * | 1967-11-27 | 1970-08-11 | Monsanto Co | Diamine preparation |
| US3510522A (en) * | 1968-09-09 | 1970-05-05 | Celanese Corp | Purification of hexamethylenediamine by recrystallization from cyclohexane |
| US4115304A (en) * | 1977-09-14 | 1978-09-19 | Mobay Chemical Corporation | Hydroxyl containing materials from distillation residue obtained by distilling hexamethylene diamine from a mixture thereof with by-products obtained in the hydrogenation of adiponitrile to produce hexamethylene diamine |
-
1987
- 1987-04-15 US US07/038,659 patent/US4803304A/en not_active Expired - Lifetime
-
1988
- 1988-04-12 CA CA000563856A patent/CA1302434C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4803304A (en) | 1989-02-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BE1009330A3 (en) | Depolymerizing polyamides. | |
| DE3853394T2 (en) | Process for the recovery of trimethoxysilane from a mixture of trimethoxysilane and methanol. | |
| JPH0725841A (en) | Purification of 2-methylglutaronitrile or adiponitrile | |
| KR100527321B1 (en) | Method for Obtaining Hexamethylene Diamine from Mixtures Containing Hexamethylene Diamine | |
| CA1302434C (en) | Process for recovery of bis(hexamethylene)triamine | |
| CA2044214C (en) | Azeotropic distillation process for recovery of diamondoid compounds from hydrocarbon streams | |
| CA1173040A (en) | Production of methylnaphthalenes and tar bases including indole | |
| CN108546224A (en) | The manufacturing method of nitrile and its corresponding amine | |
| US4276126A (en) | Separation of ethylene glycol from N-methylpyrrolidone | |
| JP2000504743A (en) | Method for preparing ε-caprolactam from 6-aminocaproic acid | |
| US3950229A (en) | Purification of adiponitrile | |
| CN1152856C (en) | The method for separating 6-aminocapronitrile from the mixture containing 6-aminocapronitrile and imine | |
| US3895071A (en) | Separation of nitroketone from a crude nitrooxidation reaction product | |
| JPH10500941A (en) | Purification of amidocarboxylic acid | |
| US5015787A (en) | Process for production cyclohexanol | |
| US10100002B2 (en) | Method for separating N,N,N'-trimethylbisaminoethylether and/or N,N-dimethylbisaminoethylether from a mixture | |
| DD298403A5 (en) | METHOD FOR THE PRODUCTION OF KETOXIMOSILANES | |
| EP0041751B1 (en) | Process for the purification of 2-pyrrolidone | |
| KR930003935B1 (en) | 2, 2-dimethylpropane-1, 3-diol production process | |
| CN1656060B (en) | Method for reducing the content of unsaturated amines in mixtures containing aminonitriles, diamines, dinitriles or mixtures thereof | |
| US3652545A (en) | Process for preparing n-(6-aminohexyl) hexamethyleneimine | |
| KR100446372B1 (en) | PROCESS TO SEPARATE ε-CAPROLACTAM FROM 6-AMINOCAPROAMIDE AND 6-AMINOCAPROAMIDE OLIGOMERS | |
| JP2785629B2 (en) | Method for producing pyrrolidones | |
| US5019653A (en) | Purification of polyamines derived from polyhydroxyl compounds | |
| US3817841A (en) | Separating adiponitrile from mixtures |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |