CN105017153A - Method for refining caprolactam - Google Patents
Method for refining caprolactam Download PDFInfo
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- CN105017153A CN105017153A CN201410165552.8A CN201410165552A CN105017153A CN 105017153 A CN105017153 A CN 105017153A CN 201410165552 A CN201410165552 A CN 201410165552A CN 105017153 A CN105017153 A CN 105017153A
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- hexanolactam
- purification
- melting
- crude caprolactam
- caprolactam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
- C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D223/08—Oxygen atoms
- C07D223/10—Oxygen atoms attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/16—Separation or purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for refining caprolactam. The method comprises the following steps: providing a caprolactam-containing benzene solution to be refined; evaporating the caprolactam-containing benzene solution under normal pressure to remove benzene, thus obtaining molten crude caprolactam; adding a solvent to the molten crude caprolactam, hot filtering after the molten crude caprolactam is completely dissolved, thus obtaining a filtrate; and crystallizing the filtrate at 15-60 DEG C and separating centrifugally to obtain refined caprolactam. The method for refining caprolactam is simple in process flow and moreover the water consumption of the process is reduced greatly.
Description
Technical field
The present invention relates to field of fine chemical, particularly relate to a kind of process for purification of hexanolactam.
Background technology
Industrially manufacturing hexanolactam is under oleum catalytic condition, cyclohexanone-oxime is made to carry out Beckmann rearrangement and generate hexanolactam, after rearrangement reaction, the mixing solutions ammoniacal liquor containing oleum and hexanolactam is neutralized, produce ammonium sulfate, then separation and purification ammonium sulfate and crude amide.Usually, first extract by organic solvent-benzene, obtain the benzole soln containing 30% hexanolactam of having an appointment.Due to the important source material that hexanolactam is synthesizing polyamides, the above-mentioned benzole soln containing 30% hexanolactam of having an appointment needs refining further just can reaching the highly purified requirement of polyamide raw materials.The process for purification of traditional hexanolactam is: the back extraction → ion-exchange → hydrogenation → evaporation → distillation of benzene extraction → water, and technical process is complicated and process feedwater amount is large.
Summary of the invention
Based on this, be necessary for traditional caprolactam refining method, the complicated and problem that process water consumption is large of technical process, provides a kind of technical process simple and the process for purification of the hexanolactam that process water consumption is few.
A process for purification for hexanolactam, comprises the following steps:
Benzole soln containing hexanolactam to be refined is provided;
By the described benzole soln evaporative removal benzene at ambient pressure containing hexanolactam, obtain the crude caprolactam of melting;
In the crude caprolactam of described melting, add solvent, carry out heat filtering after fully dissolving, obtain filtrate; And
By described filtrate 15 DEG C ~ 60 DEG C crystallizations, after centrifugation, obtain the hexanolactam refined.
Wherein in an embodiment, by the step of the described benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of described evaporation is 75 DEG C ~ 100 DEG C.
Wherein in an embodiment, by the step of the described benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of described evaporation is 80 DEG C ~ 90 DEG C.
Wherein in an embodiment, the crude caprolactam of described melting and the mass ratio of described solvent are 1:3 ~ 2:1.
Wherein in an embodiment, the crude caprolactam of described melting and the mass ratio of described solvent are 1:1.
Wherein in an embodiment, described solvent is the halo naphthenic hydrocarbon of propyl ether, butyl ether, Di Iso Propyl Ether, butyl ether, the direct-connected alkane of C6 ~ C12, the branched paraffin of C6 ~ C12, the naphthenic hydrocarbon of C6 ~ C12, the straight chain halogenated alkane of C6 ~ C12, the side chain halogenated alkane of C6 ~ C12 or C6 ~ C12.
Wherein in an embodiment, in the crude caprolactam of described melting, add solvent, carry out in the step of heat filtering after fully dissolving, the temperature of described heat filtering is 40 DEG C ~ 85 DEG C.
Wherein in an embodiment, in the crude caprolactam of described melting, add solvent, carry out in the step of heat filtering after fully dissolving, the temperature of described heat filtering is 60 DEG C ~ 75 DEG C.
Wherein in an embodiment, the described benzole soln containing hexanolactam is obtained by following steps:
By cyclohexanone-oxime through liquid phase Beckmann rearrangement, obtain rearrangement reaction liquid; And
Described rearrangement reaction liquid benzene is extracted, obtains the described benzole soln containing hexanolactam.
The process for purification of above-mentioned hexanolactam, compared to the process for purification of traditional hexanolactam, eliminates the technological processs such as water back extraction and ion-exchange, and technical process is simple, and process water consumption greatly reduces.
Accompanying drawing explanation
Fig. 1 is the process for purification schema of the hexanolactam of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the process for purification of the hexanolactam of an embodiment, comprises the following steps:
S110, provide the benzole soln containing hexanolactam to be refined.
The above-mentioned benzole soln containing hexanolactam is obtained by following steps: by cyclohexanone-oxime through liquid phase Beckmann rearrangement, obtain rearrangement reaction liquid; Above-mentioned rearrangement reaction liquid benzene is extracted, obtains the above-mentioned benzole soln containing hexanolactam.
Be appreciated that above-mentioned containing in the benzole soln of hexanolactam, except containing except benzene and hexanolactam, also containing a small amount of ammonium sulfate and other impurity.
S120, by the above-mentioned benzole soln evaporative removal benzene at ambient pressure containing hexanolactam, obtain the crude caprolactam of melting.
Concrete, by the step of the above-mentioned benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of evaporation is 75 DEG C ~ 100 DEG C.
Preferably, by the step of the above-mentioned benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of evaporation is 80 DEG C ~ 90 DEG C.
In the step s 120, the benzene of evaporative removal can be recycled again, for extracting the rearrangement reaction liquid that cyclohexanone-oxime obtains through liquid phase Beckmann rearrangement, decreasing the discharge of waste liquid, reducing energy consumption.
S130, in the crude caprolactam of above-mentioned melting, add solvent, carry out heat filtering after fully dissolving, obtain filtrate.
Be appreciated that in the crude caprolactam of melting containing hexanolactam, a small amount of ammonium sulfate and other impurity.
Concrete, solvent is added in the crude caprolactam of above-mentioned melting, heat filtering is carried out after abundant dissolving, hexanolactam and wherein a part of impurity are dissolved in solvent completely, ammonium sulfate and other a part of impurity are separated out in solid form, through heat filtering, the ammonium sulfate of separating out in solid form and impurity are removed.
In the crude caprolactam of above-mentioned melting, add solvent, carry out in the step of heat filtering after fully dissolving, the temperature of heat filtering is 40 DEG C ~ 85 DEG C.
Preferably, in the crude caprolactam of above-mentioned melting, add solvent, carry out in the step of heat filtering after fully dissolving, the temperature of heat filtering is 60 DEG C ~ 75 DEG C.
In the present embodiment, the crude caprolactam of above-mentioned melting and the mass ratio of solvent are 1:3 ~ 2:1.Preferably, the crude caprolactam of above-mentioned melting and the mass ratio of solvent are 1:1.
Preferably, solvent is the halo naphthenic hydrocarbon of propyl ether, butyl ether, Di Iso Propyl Ether, butyl ether, the direct-connected alkane of C6 ~ C12, the branched paraffin of C6 ~ C12, the naphthenic hydrocarbon of C6 ~ C12, the straight chain halogenated alkane of C6 ~ C12, the side chain halogenated alkane of C6 ~ C12 or C6 ~ C12.
It should be noted that, butyl ether can be n-propyl n-butyl ether, n-propyl isobutyl ether, n-propyl tertbutyl ether, sec.-propyl n-butyl ether, isopropyl butyl ether or sec.-propyl tertbutyl ether.
Preferably, solvent is hexanaphthene or chlorocyclohexane.
Be appreciated that in other embodiments, solvent is not limited to listed above several, as long as hexanolactam can be dissolved, reaches the object of it being separated with ammonium sulfate and other impurity.
S140, by above-mentioned filtrate 15 DEG C ~ 60 DEG C crystallizations, obtain the hexanolactam refined after centrifugation.
Concrete, by above-mentioned filtrate 15 DEG C ~ 60 DEG C crystallizations, obtain in the step of the hexanolactam refined after centrifugation, the mode of crystallization is selected from the one in single still crystallisation by cooling, single still evaporative crystallization, continuously autoclave evaporative crystallization, OSLO crystallizer thermostatical crystallization and OSLO crystallizer evaporative crystallization.
By above-mentioned filtrate 15 DEG C ~ 60 DEG C crystallizations, obtain in the step of the hexanolactam refined after centrifugation, the whizzer that centrifugation adopts is scraper type whizzer, piston-type whizzer, helical conveyor centrifuge or centrifugal force type conveyer centrifugal.
Preferably, whizzer is scraper type whizzer.The rotating speed of whizzer is 1000r/min ~ 3000r/min.
Be appreciated that in step S140, the hexanolactam in filtrate is 15 DEG C ~ 60 DEG C crystallizations, and the impurity being dissolved in solvent still dissolves in a solvent, by centrifugation, the hexanolactam of crystallization and solution is separated, obtains the hexanolactam refined.
The process for purification of above-mentioned hexanolactam, by heat filtering and centrifugation, reduce the ammonium sulfate in solvent and other foreign matter content, and compared to the process for purification of traditional hexanolactam, eliminate the technological processs such as water back extraction and ion-exchange, avoid using and processing of a large amount of process water, reduce the generation of waste water, reduce energy consumption, improve the final product quality of hexanolactam, reduce environmental pollution.
It is below specific embodiment.
Embodiment 1
There is provided the benzole soln containing hexanolactam to be refined, the above-mentioned benzole soln containing hexanolactam is heated to 75 DEG C, and evaporative removal benzene under normal pressure, obtains the crude caprolactam of melting.In the crude caprolactam of above-mentioned melting, add Di Iso Propyl Ether, the crude caprolactam of melting and the mass ratio of Di Iso Propyl Ether are 1:3, carry out heat filtering, obtain filtrate after fully dissolving at 40 DEG C.By above-mentioned filtrate 15 DEG C of crystallizations, after centrifugation, obtain the hexanolactam refined.
Embodiment 2
There is provided the benzole soln containing hexanolactam to be refined, the above-mentioned benzole soln containing hexanolactam is heated to 100 DEG C, and evaporative removal benzene under normal pressure, obtains the crude caprolactam of melting.In the crude caprolactam of above-mentioned melting, add hexanaphthene, the crude caprolactam of melting and the mass ratio of hexanaphthene are 2:1, carry out heat filtering, obtain filtrate after fully dissolving at 85 DEG C.By above-mentioned filtrate 60 DEG C of crystallizations, after centrifugation, obtain the hexanolactam refined.
Embodiment 3
There is provided the benzole soln containing hexanolactam to be refined, the above-mentioned benzole soln containing hexanolactam is heated to 80 DEG C, and evaporative removal benzene under normal pressure, obtains the crude caprolactam of melting.In the crude caprolactam of above-mentioned melting, add normal hexane, the crude caprolactam of melting and the mass ratio of normal hexane are 1:1, carry out heat filtering, obtain filtrate after fully dissolving at 60 DEG C.By above-mentioned filtrate 40 DEG C of crystallizations, after centrifugation, obtain the hexanolactam refined.
Embodiment 4
There is provided the benzole soln containing hexanolactam to be refined, the above-mentioned benzole soln containing hexanolactam is heated to 90 DEG C, and evaporative removal benzene under normal pressure, obtains the crude caprolactam of melting.In the crude caprolactam of above-mentioned melting, add chlorocyclohexane, the crude caprolactam of melting and the mass ratio of chlorocyclohexane are 2:1, carry out heat filtering, obtain filtrate after fully dissolving at 75 DEG C.By above-mentioned filtrate 50 DEG C of crystallizations, after centrifugation, obtain the hexanolactam refined.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a process for purification for hexanolactam, is characterized in that, comprises the following steps:
Benzole soln containing hexanolactam to be refined is provided;
By the described benzole soln evaporative removal benzene at ambient pressure containing hexanolactam, obtain the crude caprolactam of melting;
In the crude caprolactam of described melting, add solvent, carry out heat filtering after fully dissolving, obtain filtrate; And
By described filtrate 15 DEG C ~ 60 DEG C crystallizations, after centrifugation, obtain the hexanolactam refined.
2. the process for purification of hexanolactam according to claim 1, is characterized in that, by the step of the described benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of described evaporation is 75 DEG C ~ 100 DEG C.
3. the process for purification of hexanolactam according to claim 1, is characterized in that, by the step of the described benzole soln containing hexanolactam evaporative removal benzene at ambient pressure, the temperature of described evaporation is 80 DEG C ~ 90 DEG C.
4. the process for purification of hexanolactam according to claim 1, is characterized in that, the crude caprolactam of described melting and the mass ratio of described solvent are 1:3 ~ 2:1.
5. the process for purification of hexanolactam according to claim 1, is characterized in that, the crude caprolactam of described melting and the mass ratio of described solvent are 1:1.
6. the process for purification of hexanolactam according to claim 1, it is characterized in that, described solvent is the halo naphthenic hydrocarbon of propyl ether, butyl ether, Di Iso Propyl Ether, butyl ether, the direct-connected alkane of C6 ~ C12, the branched paraffin of C6 ~ C12, the naphthenic hydrocarbon of C6 ~ C12, the straight chain halogenated alkane of C6 ~ C12, the side chain halogenated alkane of C6 ~ C12 or C6 ~ C12.
7. the process for purification of hexanolactam according to claim 1, is characterized in that, in the crude caprolactam of described melting, add solvent, and carry out in the step of heat filtering after fully dissolving, the temperature of described heat filtering is 40 DEG C ~ 85 DEG C.
8. the process for purification of hexanolactam according to claim 1, is characterized in that, in the crude caprolactam of described melting, add solvent, and carry out in the step of heat filtering after fully dissolving, the temperature of described heat filtering is 60 DEG C ~ 75 DEG C.
9. the process for purification of hexanolactam according to claim 1, is characterized in that, the described benzole soln containing hexanolactam is obtained by following steps:
By cyclohexanone-oxime through liquid phase Beckmann rearrangement, obtain rearrangement reaction liquid; And
Described rearrangement reaction liquid benzene is extracted, obtains the described benzole soln containing hexanolactam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410165552.8A CN105017153A (en) | 2014-04-24 | 2014-04-24 | Method for refining caprolactam |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410165552.8A CN105017153A (en) | 2014-04-24 | 2014-04-24 | Method for refining caprolactam |
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| CN105017153A true CN105017153A (en) | 2015-11-04 |
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| CN201410165552.8A Pending CN105017153A (en) | 2014-04-24 | 2014-04-24 | Method for refining caprolactam |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110066249A (en) * | 2019-05-23 | 2019-07-30 | 河北美邦工程科技股份有限公司 | A kind of novel caprolactam refining purification process |
| CN111592492A (en) * | 2019-02-21 | 2020-08-28 | 中国石油化工股份有限公司 | Method for improving quality of caprolactam product subjected to liquid phase Beckmann rearrangement |
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| CN101070299A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Method for purifying and refining epsi caprolactam |
| CN102452982A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for purifying epsilon-caprolactam and method for preparing epsilon-caprolactam |
| CN102658191A (en) * | 2012-05-16 | 2012-09-12 | 河北工业大学 | Catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement |
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2014
- 2014-04-24 CN CN201410165552.8A patent/CN105017153A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070299A (en) * | 2006-05-12 | 2007-11-14 | 中国石油化工股份有限公司 | Method for purifying and refining epsi caprolactam |
| CN102452982A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for purifying epsilon-caprolactam and method for preparing epsilon-caprolactam |
| CN102658191A (en) * | 2012-05-16 | 2012-09-12 | 河北工业大学 | Catalyst for preparing caprolactam from cyclohexanone-oxime by liquid-phase Beckmann rearrangement |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592492A (en) * | 2019-02-21 | 2020-08-28 | 中国石油化工股份有限公司 | Method for improving quality of caprolactam product subjected to liquid phase Beckmann rearrangement |
| CN110066249A (en) * | 2019-05-23 | 2019-07-30 | 河北美邦工程科技股份有限公司 | A kind of novel caprolactam refining purification process |
| CN110066249B (en) * | 2019-05-23 | 2020-10-27 | 河北美邦工程科技股份有限公司 | Novel caprolactam refining and purifying method |
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