CN103449995B - Method of removing aldehydes impurities in cyclohexanone-containing technology materials - Google Patents
Method of removing aldehydes impurities in cyclohexanone-containing technology materials Download PDFInfo
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- CN103449995B CN103449995B CN201210171121.3A CN201210171121A CN103449995B CN 103449995 B CN103449995 B CN 103449995B CN 201210171121 A CN201210171121 A CN 201210171121A CN 103449995 B CN103449995 B CN 103449995B
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- cyclohexanone
- pimelinketone
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Abstract
The invention discloses a method of removing aldehydes impurities in cyclohexanone-containing technology materials. The method comprises following steps: introducing a mixture containing cyclohexanone and aldehydes impurities into a strong acid cation exchange resin fixed bed reactor, controlling the reaction temperature of the bed layer in the range of 25 to 70 DEG C and the liquid hourly space velocity in the range of 1 to 15 hr<-1>, preparing heavy components from aldehydes impurities after the reactions, and then subjecting the mixed materials to a refine treatment so as to obtain cyclohexanone. The method is mainly applied to the technology process of preparing caprolactam from cyclohexanone.
Description
Technical field:
The present invention relates to and prepare in pimelinketone technological process by hexanaphthene, particularly preparation is applicable to caprolactam production pimelinketone, removes the method for aldehyde type impurities in pimelinketone process stream.
Background technology:
In industrialized method, use cyclohexane oxidation to obtain pimelinketone, also form other compounds many comprising a small amount of aldehyde type impurities.
Industrial effectively separation with aldehyde type impurities by pimelinketone with regard to how have employed multiple means.As being pimelinketone by cyclohexane oxidation, the aldehyde type impuritiess such as n-hexyl aldehyde will be produced, when utilizing the cyclohexanone starting materials of the n-hexyl aldehyde containing high level to prepare hexanolactam, the permanganate number of hexanolactam can be caused to reduce, the hexanolactam of top grade product cannot be obtained, so the hexanolactam producing top grade product needs the content controlling n-hexyl aldehyde in raw material pimelinketone in lower scope or not containing n-hexyl aldehyde.Because the boiling point of pimelinketone and n-hexyl aldehyde is comparatively close, simple rectificating method is adopted effectively to be removed by the n-hexyl aldehyde in pimelinketone completely, therefore after other ways must be adopted the aldehyde type impurities major part in the material stream before pimelinketone rectifying to be removed, then the pimelinketone product of qualified hexanolactam is obtained through rectifying.
The second prior art utilizes alkaline hydrated oxide or carbonate and aldehyde type impurities to react, and forms heavy component, thus realize being separated of aldehyde type impurities and pimelinketone.There is serious defect in this kind of method, with for use alkaline hydrated oxide or carbonate facilitate pimelinketone from condensation, there is a large amount of side reactions, the yield of pimelinketone product is caused to reduce obviously, directly affect product cost, the polymkeric substance of the pimelinketone simultaneously formed also can have a strong impact on the quality of derived product hexanolactam.As: adopt the sodium hydroxide of higher concentration to carry out saponification to the material containing pimelinketone, then can obtain after extraction, washing, rectifying substantially not containing the high quality pimelinketone of n-hexyl aldehyde, but because needs control basicity is higher, cause the pimelinketone having 2 ~ 5% to consume due to condensation reaction, the material consumption cost of product pimelinketone significantly rises.
Pimelinketone as follows from the chemical reaction mechanism of condensation:
Make the method removed containing the aldehyde type impurities in the process stream of pimelinketone, publication as represented the second art methods that above-mentioned generality describes has: UK Patent Application NO.2,028,329, the patent application disclose and make alkaline hydrated oxide or carbonate as sodium hydroxide or sodium carbonate and react containing the aldehyde type impurities in the process stream of pimelinketone, alkaline hydrated oxide or carbonate and react the hydroxy aldehyde formed by rectifying separation based on the impurity of aldehyde.But what add in process stream that alkaline hydrogen oxygenate or carbonate facilitates pimelinketone produces polymeric rings hexanone from condensation, directly causes the production cost rising by a relatively large margin of pimelinketone.
Summary of the invention:
It is little that object of the present invention aims to provide a kind of scale of investment, and flow process is simple, and operation controls easy, and side reaction is few, temperature of reaction and the residence time can at any time on-line tuning be conducive to remove the method containing aldehyde type impurities in cyclohexanone process stream.
Technical scheme of the present invention is:
By the mixture obtaining cyclohexanone, hexalin and aldehyde type impurities after cyclohexane oxidation, by described mixture by storng-acid cation exchange resin fixed bed, aldehyde type impurities generation condensation is made to form heavy component; Then through rectifying, pimelinketone and aldehyde type impurities is isolated; Described fixed bed bed temperature of reaction controls at 25 ~ 70 DEG C, and liquid hourly space velocity is 1 ~ 15hr
-1, there is-SO on storng-acid cation exchange resin surface
3h functional group.
The temperature of above-mentioned reaction preferably controls at 30 ~ 60 DEG C, and liquid hourly space velocity is 4 ~ 10hr
-1.
The temperature of above-mentioned reaction most preferably controls at 30 ~ 50 DEG C, and liquid hourly space velocity is 5 ~ 8hr
-1.
Adopt concentrated acid sulfonation when storng-acid cation exchange resin can be used, after washing, drying to water content is can drop into reactor after 0 ~ 1%.
Storng-acid cation exchange resin can be polystyrene type storng-acid cation exchange resin.
Owing to obtaining in the process of cyclohexanone after cyclohexane oxidation, the aldehyde type impurities of trace can be formed simultaneously, and the mixture of a certain amount of ring alcohol, the present invention is by being incorporated in storng-acid cation exchange resin by mixture, and control certain temperature of reaction and reaction time, make impurity form heavy component to remove, the condensation amount of pimelinketone can be controlled, in minimum scope, significantly can reduce production cost again simultaneously.
The present invention is mainly applicable to synthesis of caprolactam containing the pimelinketone in the material of pimelinketone.But the aldehyde type impurities in any pimelinketone can affect the synthesis of hexanolactam, reduce the commercial viability of hexanolactam, the aldehyde type impurities content in the reduction pimelinketone of therefore how less expensive is emphasis of the present invention.The operational path of synthesis of caprolactam is as follows:
Contain in pimelinketone material what generate, generally also likely containing a certain amount of hexalin, aldehyde type impurities is mainly n-hexyl aldehyde, but is not limited only to n-hexyl aldehyde, and structural formula is as follows:
Be incorporated in storng-acid cation exchange resin reactor in the present invention by the mixture of technique gained, n-hexyl aldehyde and pimelinketone interact, and form 2-hexylidene cyclohexanone, structural formula is as follows:
Its boiling point is a lot of compared with the height of pimelinketone and n-hexyl aldehyde, and the method for rectifying therefore can be utilized to obtain meeting the chemical fiber grade cyclohexanone of caprolactam production specification of quality.
Contrast existing maturation process, although secondary saponification is the technology generally applied, but it is high to there is consumption in this technology, the shortcomings such as flow process is complicated, a kind of technique is also had to be add in pimelinketone distillation system by strong basicity oxyhydroxide or high boiling amine substance in addition, by the pimelinketone product adopting the form of similar reactive distillation to obtain high-quality.The method is on the one hand due to alkali lye skewness, and local side reaction may be caused too much, and material consumption is high, on the other hand condenses easily and alkali form alkaline residue, easily block packing layer, affect the long-period stable operation of device.Advantage of the present invention is:
1, on-line tuning can be carried out according to the concentration of n-hexyl aldehyde and pimelinketone condenses in reaction bed outlet material to temperature of reaction and the residence time.
2, catalyst system reaction evenly, and side reaction can effectively reduce.
3, scale of investment is little, and flow process is simple, and operation controls easy.
Embodiment
Below will the invention will be further described by a series of particularly embodiment:
In an embodiment, material containing pimelinketone only does the content detection of n-hexyl aldehyde and cyclohexenyl hexamethylene ketone, analyzes the change of contrast by the content of n-hexyl aldehyde in material after storng-acid cation exchange resin fixed-bed reactor and cyclohexenyl hexamethylene ketone (calling ketal in the following text).
Load 500g storng-acid cation exchange resin as catalyzer at ∮ 57mm × 1000mm jacketed pipe type reactor, form fixed-bed reactor, temperature of reaction carries out temperature control by injecting recirculated water in chuck.The pimelinketone mixed solution of aldehyde-containing type impurity enters reactor by metering infusion after being preheated to temperature of reaction, makes it pass through fixed-bed reactor with different temperature and the different residence time.
The temperature of reaction of embodiment 1-6 and the liquid hourly space velocity of control, and to process before and after n-hexyl aldehyde and cyclohexenyl hexamethylene ketone analyze obtain the results are shown in following table:
As can be seen from embodiment data, along with the rising of temperature of reaction, the generation of ketal will sharply rise, and practical situation according to the content of hexanal in charging, can adjust accordingly liquid hourly space velocity and temperature.
Claims (2)
1. remove the method for aldehyde type impurities in cyclohexanone process stream for one kind, by the mixture obtaining cyclohexanone, hexalin and aldehyde type impurities after cyclohexane oxidation, by described mixture by storng-acid cation exchange resin fixed bed, make aldehyde type impurities generation condensation form heavy component, wherein heavy component is containing 2-hexylidene cyclohexanone; Then through rectifying, pimelinketone and aldehyde type impurities is isolated;-SO is contained on the surface of described storng-acid cation exchange resin
3the functional group of H; Described fixed bed bed temperature of reaction is 25 ~ 70 DEG C, and liquid hourly space velocity is 1 ~ 15h
-1; Described aldehyde type impurities is mainly aldehyde just.
2. method according to claim 1, described fixed bed bed temperature of reaction is 30 ~ 60 DEG C; The liquid hourly space velocity of described storng-acid cation exchange resin fixed bed is 4 ~ 10h
-1.
3. method according to claim 2, described fixed bed bed temperature of reaction is 30 ~ 50 DEG C, and liquid hourly space velocity is 5 ~ 8h
-1.
4. the method according to any one of claim 1-3, storng-acid cation exchange resin is polystyrene type storng-acid cation exchange resin.
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| CN104003859B (en) * | 2014-06-10 | 2015-10-28 | 沧州旭阳化工有限公司 | A kind of method by distillation absorption purification pimelinketone |
| CN105016993B (en) * | 2015-05-26 | 2017-03-08 | 岳阳昌德化工实业有限公司 | A kind of process for purification of n-hexyl aldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283560A (en) * | 1979-11-30 | 1981-08-11 | Union Carbide Corporation | Bulk cyclohexanol/cyclohexanone separation by selective adsorption on zeolitic molecular sieves |
| CN102276435A (en) * | 2010-06-12 | 2011-12-14 | 中国石油化工集团公司 | Method for producing chemical fiber grade cyclohexanone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4283560A (en) * | 1979-11-30 | 1981-08-11 | Union Carbide Corporation | Bulk cyclohexanol/cyclohexanone separation by selective adsorption on zeolitic molecular sieves |
| CN102276435A (en) * | 2010-06-12 | 2011-12-14 | 中国石油化工集团公司 | Method for producing chemical fiber grade cyclohexanone |
Non-Patent Citations (1)
| Title |
|---|
| 树脂吸附环己酮中己醛的研究;李皓凌;《化学工程师》;200803;第总150卷(第3期);第11-13页 * |
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