Organic compounds -- part of the class 532-570 series – Organic compounds – Unsubstituted hydrocarbyl chain between the ring and the -c-...
Reexamination Certificate
1999-04-21
2001-03-27
Kifle, Bruck (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Unsubstituted hydrocarbyl chain between the ring and the -c-...
Reexamination Certificate
active
06207827
ABSTRACT:
The invention relates to a process to separate &egr;-caprolactam from 6-aminocaproamide and 6-aminocaproamide oligomers.
Such a process is known from U.S. Pat. No. 5495016. This patent publication describes a separation of &egr;-caprolactam from its nylon-6 oligomers by distillation.
A disadvantage of distillation is that &egr;-caprolactam will partly convert to more oligomers (2 wt. % absolute according to Example 1 of U.S. Pat. No. 5495016). Another disadvantage is fouling of pipes and other process equipment because of solidification of the oligomers present in the distillation residue.
The object of the present invention is to provide a method to separate &egr;-caprolactam from 6-aminocaproamide and its oligomers in which no &egr;-caprolactam is lost.
The object is achieved in that &egr;-caprolactam, 6-aminocaproamide and 6-aminocaproamide oligomers are present in a first aqueous starting mixture, which mixture is contacted with an alcohol extraction solvent, resulting in a first aqueous raffinate phase which is poor in &egr;-caprolactam and an alcohol phase which is rich in &egr;-caprolactam and which alcohol phase contains 6-aminocaproamide and/or 6-aminocaproamide oligomers, wherein the latter alcohol phase is subsequently contacted with water (backwash water) resulting in an alcohol extract phase poor in 6-aminocaproamide and/or 6-aminocaproamide oligomers and a second aqueous raffinate phase rich in 6-aminocaproamide and/or 6-aminocaproamide oligomers.
It has been found that by performing the process according the invention &egr;-caprolactam can be succesfully separated from 6-aminocaproamide and 6-aminocaproamide
EP-A-729944 describes that &egr;caprolactam may be recovered from aqueous mixtures containing also oligomers of 6-aminocaproamide by extraction using methylene chloride, cyclohexane, toluene, benzene, chloroform or trichloroethane. This patent publication does not teach alcohol solvents as extraction agents. It has been found that the most promising extraction solvents of EP-A-729944 are the exemplified chloronated solvents. These solvents are however preferably not used because of environmental reasons.
NL-A-6803152 describes experiments of an extraction of &egr;-caprolactam from an aqueous mixture using a C
4
-C
8
(cyclo)aliphatic alcohol solvent. This patent publication does not describe the presence of 6-aminocaproamide or its oligomer in the aqueous mixture. Furthermore no second extraction using water is described.
The first aqueous starting mixture may also contain 6-aminocaproic acid and 6-aminocaproic acid oligomers. Such mixtures are, for example, obtained in the process of EP-A-729944. It has been found that these compounds are also effectively separated from &egr;-caprolactam when performing the process according to the invention.
The oligomers are generally dimers and trimers of 6-aminocaproic acid or of 6-aminocaproamide. Higher oligomers can be present in a much lower content.
The concentration oligomers in the first aqueous mixture is preferably higher than 0.5 wt. %. More preferably not more than 10 wt. %.
The concentration of &egr;-caprolactam, 6minocaproic acid, 6-aminocaproamide and oligomers in the first aqueous mixture is preferably between 5-50 wt. % and more preferably between 10-35 wt. %. The concentration of &egr;-caprolactam is preferably between 5-30 wt. %. The concentration of 6-aminocaproamide is preferably between 0.1 and 10 wt. %. The concentration of 6-aminocaproic acid is preferably between 0.1 and 10 wt. %.
The alcohol extraction solvent is preferably a solvent which is substantially immiscible with the first aqueous mixture. By substantially immiscible is here meant that the mixture of alcohol solvent and the aqueous mixture results in two segregated phases at the extraction temperature. Preferable the mutual solubility under the conditions of the extraction is not higher than 30 wt. % and more preferably less than 20 wt. %.
The alcohol extraction solvent is preferably an aliphatic or cycloaliphatic compound having one or more hydroxyl groups. Such alcohols have preferably 4-12 carbon atoms and more preferably 5-8 carbon atoms. Preferably one or two and more preferably only one hydroxyl group is present. Preferably hindered alcohols are used. A hindered alcohol is a compound in which the hydroxyl group is bonded to a —CR
1
R
2
R
3
in which R
1
and R
2
are alkyl groups and R
3
is an alkyl group or hydrogen. This is advantageous in a process in which the resulting aqueous phases are used as feed to prepare &egr;-caprolactam. Hindered alcohols are less susceptible to react to N-alkylation products of &egr;-caprolactam.
Examples of compounds having two hydroxyl groups are hexanediol, nonanediol, neopentylglycol, methyl-methylpropanediol, ethyl-methylpropanediol or butyl-methylpropanediol. Examples of compounds having one hydroxyl group are cyclohexanol, n-butanol, n-pentanol, 2-pentanol, n-hexanol, 4-methyl-2-pentanol, 2-ethyl-1-hexanol, 2-propyl-1-heptanol, n-octanol, iso-nonylalcohol, n-decylalcohol and mixtures of linear and branched C
8
-alcohols, mixtures of linear and branched C
9
-alcohols and mixtures of linear and branched C
10
-alcohols. Mixtures of the above mentioned alcohols can also be used. Preferred alcohols have a high affinity for &egr;-caprolactam, a lower boiling point than &egr;-caprolactam, a large density difference with water, commercially available, low mutual solubility with water and/or are biodegradable.
The back wash water may be pure water or water contaminated with other compounds, for example the alcohol compound. Preferably the water used is at least 95 wt. % pure water.
The first and second aqueous raffinate phases may be combined to form one aqueous mixture which can be used further. Preferably the first aqueous raffinate phase is combined with the aqueous starting mixture. Such a preferred embodiment of the process is preferably performed continuously in one process apparatus. This embodiment is characterized in that the extraction is performed in a vertically positioned vessel, wherein the aqueous starting mixture is fed at an intermediate position along the vessel, the alcohol extraction solvent is fed to the bottom of the vessel and the backwash water is fed to the top of the vessel, and in which the resulting aqueous raffinate and alcohol extract phases are obtained at the bottom and the top of the vessel respectively.
The amount of alcohol extraction solvent- and backwash water will depend on the partitioning coefficient of the components to be separated, which can be easily determined by one skilled in the art.
The extraction step is carried out at a temperature which is high enough in order to avoid precipitation of oligomers. The temperature of extraction can be generally between room temperature and 200° C. and is preferably between 20 and 170° C. Temperatures between 50 and 130° C. are even more preferred.
The pressure during the extraction step is not critical and can be, for example, between about 0.1 MPa and about 2.0 MPa, and preferably, between about 0.1 MPa and about 0.5 MPa. The pressure must be sufficient to maintain liquid phases during extraction.
The extraction can be carried out in well known extraction apparatuses, for example a counter current column, a series of mixer settlers, rotating disc contactors or pulsed packed columns.
The extraction step preferably yields a &egr;-caprolactam-containing alcohol phase which may contain between 10-40 wt. % &egr;-caprolactam.
After the extraction &egr;-caprolactam may be recovered from the alcohol phase by known separation methods, for example distillation and extraction. Preferably distillation is used in which the lower boiling alcohol and any water present in the alcohol phase is distilled from the &egr;-caprolactam. The alcohol solvent and water thus obtained is preferably reused in the extraction according to the invention.
The invention relates especially to the separation of &egr;-caprolactam from aqueous mixtures obtained in (I) a process to prepare &egr;-caprolactam in which 6-aminocapronitrile is converted into
DSM N.V.
Kifle Bruck
Pillsbury & Winthrop LLP
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