CH301433A - Process for separating caprolactam from its solutions in sulfuric acid or oleum. - Google Patents
Process for separating caprolactam from its solutions in sulfuric acid or oleum.Info
- Publication number
- CH301433A CH301433A CH301433DA CH301433A CH 301433 A CH301433 A CH 301433A CH 301433D A CH301433D A CH 301433DA CH 301433 A CH301433 A CH 301433A
- Authority
- CH
- Switzerland
- Prior art keywords
- solutions
- sulfuric acid
- oil
- neutralization
- oleum
- Prior art date
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 6
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 210000002837 heart atrium Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Other In-Based Heterocyclic Compounds (AREA)
Description
Verfahren zum Trennen von Caprolactam aus seinen Lösungen in Schwefelsäure oder Oleum. Die Erfindung bezieht sich auf ein Ver fahren zum Trennen von Caprolaetam aus seinen Lösungen in Sehwefelsäure oder Oleum, wie sie bei der Herstellung von Ca.pro- laetani aus Cy clohexanonoxim gemäss der be kannten Beckrnannsehen Methode erhalten -erden.
Es ist. üblich, die Trennung des Capro- laetams durch Neutralisation dieser Lösungen und anschliessende Destillation des bei dieser Neutralisation als Öl ausgesehiedenen Capro- laetams zu bewerkstelligen. Diese Neutra lisation wird häufig mittels Alkalihydroxvd oder alkaliseh reagierender Alkalisalze, wie NatriLrmcarbonat, durchgeführt.
Um zu verhüten, dass bei der Neutrali sation Alkalisulfate als Nebenprodukte anfal len, für welche Salze nur in beschränktem Masse Anwendungsmögliehkeiten vorliegen, kann die Neutralisation,--mittels Ammoniak oder Ammoniumsalze durehgeführt werden, wobei als Nebenprodukt Ammonsulfat erhal ten wird, (las als Kunstdünger wertvoll ist.
Die Neutralisation mittels Ammoniak oder Aninioniumsalze ei-weist sieh als mit Schwie rigkeiten verbunden, weil in dem rohen Capro- laetam, das beim Neutralisieren in Form eines Öls erhalten wird, sieh Ammansulfat auflöst.
Das erwähnte Öl enthält meistens 4 bis 6 Pro zente Ammansulfat, das sich während der Destillation unter Bildung von Sehwefelsäure zersetzt, und folglich bewirkt, da.ss ein gro- sser Destillationsrückstand zurückbleibt und die Ausbeute an Caprolaetam niedrig ist;
ausserdem enthält das in dieser Weise abge trennte Caprolactam noch Schwefelverbin- dimgen, die die Geschwindigkeit., mit. der die Polymerisation des Caprolactams vor sich geht, sowie die Güte der aus diesem Capro- lactam hergestellten Polvmerisate nachteilig beeinflussen.
Es wurde nunmehr gefunden, dass beim Trennen des Caprolactams aus seinen Lösun gen in Schwefelsäure oder 0leLim durch Neu tralisation dieser Lösungen mit Ammoniak oder Ammoniumsalzen und Destillation des bei dieser Neutralisation als Öl ausgeschie denen Caprolactams die erwähnten.
Nachteile dadurch vermieden werden können, dass erfindungsgemäss das bei der Neutralisation ausgeschiedene Öl mit einer alkalise.h reagie renden Alkalimetall- oder Erdalkalimetallver- bindung gemischt und, nachdem die festen Stoffe beseitigt worden sind, destilliert wird.
Der Zusatz. dieser alkalisch reagierenden Verbindung bewirkt, dass das im Öl enthal tene Ammansulfat in Alkali- bzw. Erdalkali- sulfat umgewandelt wird, während gleieli- zeitig Ammoniak oder Ammoniumverbindun- gen entstehen, die bei der Destillation des Öls nicht schädlich sind.
Die Vermengung des Öls mit den alkaliseh reagierenden Alkalimetall- oder Erdalkali- rnetallverbindungen kann in einfaeher Weise, z. B. dmreh intensives Rühren:, bewerkstelligt werden. Die erwälintvn Verbindungen können sowohl pulverförmig wie auch in Form einer wässrigen Lösung oder Suspension angewandt werden.
Als alkalisch reagierende Alkalimetall- oder Erdalkalimetallverbindungen kommen z. B. N atriumhydroxyd, Natriumcarbonat, Natriumborat, Bariumhydroxyd, Calcium- liydroxy d, Kaliumhydroxyd, Kaliumcarbonat oder Kaliumsilikat in Betracht. Auch können Salze, die von organischen Säuren herrühren, z. B. Natriiunformiat oder Kaliumacetat, an gewandt werden.
Das Entfernen der festen Stoffe aus dein Reaktionsgemisch ist nicht mit. besonderen Schwierigkeiten verbunden und kann z. S. durch Filtrierung erfolgen.
Das Destillieren des Öls erfolgt vorzugs weise unter herabgesetztem Druck; hierbei wird zuerst etwas Wasser aufgefangen, an schliessend geht das Caprolactam- über, wäh rend nur eine geringe Menge Rückstand zu rückbleibt.
<I>Beispiel.:</I> Eine aus Cyclohexanonoxim erhaltene, ge mäss der Beckmannsehen Methode hergestellte schwefelsaure Caprolaetam-Lösung wird mit einer 13 %igen. AmmoninmhZrdrox-ydlösung (berechnet als NH3) neutralisiert.
Von dem in dieser Weise erhaltenen Öl, das 4 C ewichtsprozente Ammonsulfat und 30 Gewichtsprozente Wasser c,iltliält, wurden 100 kg durch Rühren finit '_',:5 kr Nat.riui:
i- hydroxyd, das in 3 kg Wasser aufgelöst wor den war, gemischt. Die gebildeten Natriuni- sulfatkristalle wurden durch Filtrzerung entfernt. Nach Entfernung des Kristallwas- sers belief sieh die Menge Natriumsulfat auf 4,4 kg.
Das filtrierte Öl wurde sodann destilliert; es wurden hierbei 60 kg Caprolaetani erbal ten, während 4,? kg Rückstand in dem De stilliergefäss zurückblieben.
Wird zu Vergleiehszweeken die Behand lung mit N atriumhvdroxyd ausgelassen un @l das als Öl. ausgeschiedene Caprolaeiam direkt destilliert, so beträgt. die Ausbeute an Capro- lactam nur 60 bis 75% der obigen Menge.
Process for separating caprolactam from its solutions in sulfuric acid or oleum. The invention relates to a process for separating caprolaetam from its solutions in sulfuric acid or oleum, as they are obtained in the production of Ca.prolaetani from cyclohexanone oxime according to the known Beckmann method.
It is. It is customary to accomplish the separation of the caproletam by neutralization of these solutions and subsequent distillation of the caproletam separated out as oil during this neutralization. This neutralization is often carried out using alkali metal hydroxide or alkali metal salts with an alkaline reaction, such as sodium carbonate.
In order to prevent the neutralization of alkali sulfates as by-products, for which salts are only available to a limited extent, the neutralization can be carried out using ammonia or ammonium salts, whereby ammonium sulfate is obtained as a by-product (read as artificial fertilizer is valuable.
Neutralization by means of ammonia or anionic salts is found to be difficult because amman sulfate dissolves in the crude caproletam, which is obtained in the form of an oil during neutralization.
The oil mentioned usually contains 4 to 6 percent ammonium sulfate, which decomposes during the distillation to form sulfuric acid, and consequently causes a large distillation residue to remain and the yield of caprolaetam is low;
In addition, the caprolactam separated off in this way also contains sulfur compounds which increase the speed. which the polymerization of the caprolactam takes place, as well as the quality of the polymers produced from this caprolactam adversely affect.
It has now been found that when the caprolactam is separated from its solutions in sulfuric acid or oil by neutralization of these solutions with ammonia or ammonium salts and distillation of the caprolactam which was eliminated as oil during this neutralization, the aforementioned.
Disadvantages can be avoided in that, according to the invention, the oil separated out during the neutralization is mixed with an alkali metal or alkaline earth metal compound which reacts with alkaline, and is distilled after the solid substances have been removed.
The addition. This alkaline reacting compound causes the amman sulfate contained in the oil to be converted into alkali or alkaline earth sulfate, while ammonia or ammonium compounds are formed at the same time, which are not harmful during the distillation of the oil.
The mixing of the oil with the alkaline-reacting alkali metal or alkaline earth metal compounds can be carried out in a simple manner, e.g. B. intense stirring: can be accomplished. The compounds mentioned can be used both in powder form and in the form of an aqueous solution or suspension.
As alkaline alkali metal or alkaline earth metal compounds come z. B. N atrium hydroxide, sodium carbonate, sodium borate, barium hydroxide, calcium liydroxy d, potassium hydroxide, potassium carbonate or potassium silicate into consideration. Also salts derived from organic acids, e.g. B. sodium formate or potassium acetate to be used.
Removing the solids from your reaction mixture is not involved. associated with particular difficulties and may e.g. S. done by filtration.
The oil is preferably distilled under reduced pressure; some water is first collected, then the caprolactam passes over, while only a small amount of residue remains.
<I> Example: </I> A sulfuric acid caprolaetam solution obtained from cyclohexanone oxime and produced according to the Beckmann method is treated with a 13% strength. AmmoninmhZrdrox-yd solution (calculated as NH3) neutralized.
100 kg of the oil obtained in this way, which contains 4 percent by weight of ammonium sulfate and 30 percent by weight of water, were finely stirred to 100 kg: 5 kr Nat.riui:
i-hydroxyd, which was dissolved in 3 kg of water, mixed. The sodium sulfate crystals formed were removed by filtering. After the crystal water had been removed, the amount of sodium sulfate was 4.4 kg.
The filtered oil was then distilled; 60 kg of Caprolaetani were inherited, while 4,? kg residue remained in the De stilliergefäß.
If the treatment with sodium hydroxide is omitted for comparison purposes and then as an oil. precipitated Caprolaeiam distilled directly, so is. the yield of caprolactam is only 60 to 75% of the above amount.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL301433X | 1951-01-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH301433A true CH301433A (en) | 1954-09-15 |
Family
ID=19783299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH301433D CH301433A (en) | 1951-01-18 | 1952-01-17 | Process for separating caprolactam from its solutions in sulfuric acid or oleum. |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH301433A (en) |
-
1952
- 1952-01-17 CH CH301433D patent/CH301433A/en unknown
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