CN104876782A - Method for treating circular organic solvent and preparation method of caprolactam - Google Patents
Method for treating circular organic solvent and preparation method of caprolactam Download PDFInfo
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- CN104876782A CN104876782A CN201410069288.8A CN201410069288A CN104876782A CN 104876782 A CN104876782 A CN 104876782A CN 201410069288 A CN201410069288 A CN 201410069288A CN 104876782 A CN104876782 A CN 104876782A
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Abstract
The invention discloses a method for treating a circular organic solvent. The method is characterized in that a Beckmann rearrangement reaction is carried out to an amidation liquid obtained by contacting a caprolactam preparation process by a toluene method and an organic solution of cyclohexanone-oxime obtained from the caprolactam preparation process by a benzene method; the obtained organic solvent is separated and contacted with an alkaline substance, and the addition amount of the alkaline substance makes the content of octahydro phenazine in products of the Beckmann rearrangement reaction in which the circular used organic solvent participates not more than 15mug/g. The method can effectively prevent the influence of the cyclohexanone-oxime polycondensation on the caprolactam yield and prevent condensation polymer from blocking a pipeline in the material conveying process.
Description
Technical field
The present invention relates to the method for organic solvent and the preparation method of hexanolactam that circulate in the preparation process of process hexanolactam, the present invention relates to process furtherly and reset through the method for the organic solvent of Beckmann rearrangement process solvent vaporization cycle and corresponding Beckmann the method preparing hexanolactam.
Background technology
Hexanolactam is a kind of important Organic Chemicals, mainly for the production of nylon-6 fiber and nylon 6 engineering plastic.Currently be applied to industrial hexanolactam preparation method and mainly contained: pimelinketone-azanol production technique or oximes technique (being called for short " benzene method "), hexanaphthene photonitrosation technique and SNIA toluene technique.Wherein, pimelinketone-azanol production technique take benzene as raw material, resets through producing cyclohexane by benzene hydrogenation, cyclohexane oxidation preparing cyclohexanone, pimelinketone oximate or oximes preparing cyclohexanone oxime, cyclohexanone-oxime, obtains hexanolactam through neutralizing, extracting and refine again through Beckmannn; SNIA toluene technique take toluene as raw material, carry out with nitrosyl-sulfuric acid under phenylformic acid, Hydrogenation hexahydrobenzene formic acid, effect at oleum are produced in oxidation nitrosation reaction, again through be hydrolyzed, in and and refine and obtain hexanolactam.SNIA toluene method is compared with benzene method, and advantage is that processing condition are gentle, and early stage, process costs was lower, and the production cost of hexahydrobenzene formic acid is only 2/3 of cyclohexanone-oxime; But shortcoming is long flow path, producing ammonium sulfate byproduct is up to about 4.0 tons of ammonium sulfate/ton hexanolactams.In addition, the ammonium sulfate that by-product is a large amount of, also limit the expansion of existing apparatus throughput or the construction of new device.CN1130181A discloses a kind of when not increasing ammonium sulfate by-product amount, improve the method for SNIA toluene technique caprolactam production ability, namely, under aliphatic series and/or cycloaliphatic carboxylic acid exist, ketoxime and oleum are carried out Beckmannn and reset and generate acid amides.The mixture of carboxylic acids that it provides contains hexahydrobenzene formic acid, hexanolactam, sulphur trioxide and sulfuric acid; Cyclohexanone-oxime directly joins in mixture and carries out rearrangement reaction.
For the deficiency of existing SNIA toluene Technology, CN103012262A discloses a kind of method of producing hexanolactam, its process is that the cyclohexanone-oxime that the amidation liquid that obtains of toluene method and benzene method obtain carries out rearrangement reaction in rearrangement reactor, reaction product makes hexanolactam through neutralization, crystallization, extraction, treating process, this process employs sulphur trioxide in acid amides liquid and sulfuric acid is that catalyzer carries out rearrangement reaction.
Summary of the invention
Because cyclohexanone-oxime dissolved solution degree is low, the reaction heat of Beckmannn rearrangement reaction is large again, can not adopt fresh organic solvent completely, therefore, the circulation of the organic solvent of evaporation need be re-used.There is impurity in the organic solvent that circulation re-uses, impel cyclohexanone-oxime polycondensate to be formed, not only affect quality product, and can blocking pipeline.Contriver finds on the basis of great many of experiments, with toluene and benzene for initial feed, namely manufacture in caprolactam process with toluene method organic solution that the amidation liquid that obtains and benzene legal system make the cyclohexanone-oxime obtained in caprolactam process to contact the integrated technology carrying out Beckmann rearrangement reaction and prepare in the process of hexanolactam, a small amount of alkaline matter is added in the organic solvent of circulation, cyclohexanone-oxime polycondensation effectively can be prevented the impact of cyclohexanone-oxime yield and reduce polycondensate to line clogging in material conveying process, and final raising caprolactam product quality.Based on this, form the present invention.
An object of the present invention is for the deficiencies in the prior art, a kind of method of organic solvent of cycle for the treatment of is provided, two of object is to provide a kind of preparation method of hexanolactam, the method can to solve better when toluene and benzene are initial feed cyclohexanone-oxime generation polycondensation and and polycondensate at material conveying process to line clogging problem, and finally improve caprolactam product quality.
The method of the organic solvent of cycle for the treatment of provided by the invention, it is characterized in that, carry out Beckmann rearrangement reaction and be separated the organic solvent obtained contacting with alkaline matter with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process by coming from the amidation liquid obtained in toluene method manufacture caprolactam process, the octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that alkaline matter add-on makes the organic solvent recycled participate in is no more than 15 μ g/g.
The preparation method of a kind of hexanolactam that the present invention also provides, toluene method is manufactured the amidation liquid obtained in caprolactam process to carry out Beckmann rearrangement reaction and be separated obtaining reaction product and organic solvent with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process, wherein, said reaction product is again through comprising neutralization, crystallization, extraction and treating process obtain hexanolactam, and said organic solvent is through recycling, it is characterized in that, in the organic solution of said cyclohexanone-oxime, organic solvent comes from organic solvent and the said organic solvent the recycled elder generation before contacting preparation with cyclohexanone-oxime and obtaining the organic solution of cyclohexanone-oxime recycled at least partly and contacts with a kind of alkaline matter, octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that the organic solvent through recycling is participated in is no more than 15 μ g/g.
The method of the organic solvent of cycle for the treatment of provided by the invention and the preparation method of hexanolactam, can effectively prevent cyclohexanone-oxime polycondensation, reduces polycondensate in the degree of material conveying process to line clogging.
Accompanying drawing explanation
Accompanying drawing is one embodiment of the invention.
Illustrate one embodiment of the invention.
In the accompanying drawings, preparation cyclohexanone-oxime organic solution (6) in stirring tank (1) of cyclohexanone-oxime (4) and the circulation organic solvent after contacting with alkaline matter (7), in reactor (2), Beckmann rearrangement reaction is there is and obtains rearrangement reaction liquid (10) in cyclohexanone-oxime organic solution (6) with amidate action liquid (5), and the organic solvent (8) of heat release evaporation contacts with alkaline matter (9) and obtains circulation organic solvent (7) in reactor (3), said rearrangement reaction liquid (10) is again through hydrolysis, neutralization, crystallization, extraction and treating process obtain caprolactam product.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
Comparative example 1
This comparative example illustrates the result that organic solvent is not treated, recycle.
The hexane preparation cyclohexanone-oxime hexane solution of circulation: preparation temperature about 60 DEG C, preparation carries out in the still of band stirring.Cyclohexanone-oxime feeding temperature 92 DEG C, hexane feed temperature 56 DEG C, hexane flow 34000kg/h, cyclohexanone-oxime flow 6000kg/h, preparation obtains the cyclohexanone-oxime hexane solution that cyclohexanone-oxime massfraction is about 15wt%, the hexane solution of the cyclohexanone-oxime prepared is stored in tundish, in preparation, create the polycondensation of cyclohexanone-oxime, and define black colloid, contain a large amount of to the influential impurity of caprolactam product quality in burnt pledge, and burnt pledge finally result in the blocking of line of pipes.
Carry out Beckmann rearrangement with it further, in gained rearrangement product, octahydro azophenlyene content is 50 μ g/g.
Embodiment
The method of the organic solvent of cycle for the treatment of provided by the invention, it is characterized in that, carry out Beckmann rearrangement reaction and be separated the organic solvent obtained contacting with alkaline matter with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process by coming from the amidation liquid obtained in toluene method manufacture caprolactam process, the octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that alkaline matter add-on makes the organic solvent recycled participate in is no more than 15 μ g/g.
In order to make cyclohexanone-oxime be dispersed in amidate action liquid very well, adopt the feed process of the organic solution of cyclohexanone-oxime.In rearrangement reaction, the effect of organic solvent has two aspects, and one is the mixing that cyclohexanone-oxime charging can realize its molecular scale, and two is remove reaction heat by organic solvent evaporation, and temperature of reaction can be kept to stablize.Method provided by the invention, said organic solvent be selected from benzene, toluene, hexanaphthene and hexane one or more, wherein preferred organic solvent is hexane.Because under cyclohexanone-oxime normal temperature, solubleness is limited in organic solvent, the reaction heat of Beckmannn rearrangement reaction is large again, solvent load is very large, therefore fresh organic solvent can not be adopted completely, the solvent cycle of evaporation need be re-used, what come from that the organic solvent recycled accounts for total organic solvent amount usually is no less than 95%, deducts normal loss, preferably, normally very recycle.
Said alkaline matter is mineral alkali or its aqueous solution, one or more in mineral alkali selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate and ammoniacal liquor, wherein be preferably sodium hydroxide or ammoniacal liquor, said alkaline matter, its concentration of aqueous solution is close to saturation concentration or saturation concentration, wherein preferred saturation concentration.Method provided by the invention, the content's index of the critical impurities octahydro azophenlyene in the rearrangement reaction product obtained by the integrated process participated in the organic solvent that re-uses of circulating is no more than 15 μ g/g, control preferably more than 10 μ g/g, sets the add-on of said alkaline matter.The Adding Way of said alkaline matter joins in circulation organic solvent by Hi-mixer by alkali lye, and circulation organic solvent is external phase, and alkali lye is disperse phase, reaches the short mix of two-phase.Said organic solvent is in the step contacted with alkaline matter, and Contact Temperature is 5-80 DEG C, preferred 25-60 DEG C.
The preparation method of the hexanolactam that the present invention provides on the method basis of the organic solvent of cycle for the treatment of, toluene method is manufactured the amidation liquid obtained in caprolactam process to carry out Beckmann rearrangement reaction and be separated obtaining reaction product and organic solvent with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process, wherein, said reaction product is again through comprising neutralization, crystallization, extraction and treating process obtain hexanolactam, and said organic solvent is through recycling, it is characterized in that, in the organic solution of said cyclohexanone-oxime, organic solvent comes from organic solvent and the said organic solvent the recycled elder generation before contacting preparation with cyclohexanone-oxime and obtaining the organic solution of cyclohexanone-oxime recycled at least partly and contacts with a kind of alkaline matter, octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that the organic solvent through recycling is participated in is no more than 15 μ g/g.
The organic solvent of circulation contacts with alkaline matter by the present invention, octahydro azophenlyene content in the product of the Beckmann rearrangement reaction participated in by the organic solvent controlled through recycling is no more than 15 these parameters of μ g/g, the organic solution of preparation cyclohexanone-oxime is participated in the organic solvent of circulation up to standard, cyclohexanone-oxime generation polycondensation can be avoided, reach above-mentioned reduction polycondensate in the object of material conveying process to line clogging degree.
In method provided by the invention, the said organic solvent recycled is 0-80 DEG C contacting the temperature that preparation obtains the organic solution of cyclohexanone-oxime with cyclohexanone-oxime, cyclohexanone-oxime feeding temperature is greater than its fusing point, cyclohexanone-oxime and organic solvent add-on depending on prepare the concentration of cyclohexanone-oxime organic solution determine, be prepared in the container with Agitation and mixing function and carry out.In the organic solution of said cyclohexanone-oxime, come from that the organic solvent recycled accounts for total organic solvent 95 ~ 100%.
Embodiment 1
The present embodiment illustrates the method for organic solvent and the preparation method of hexanolactam of cycle for the treatment of.
Be that the circulation hexane of 0.385wt% mixes with the 25wt% ammoniacal liquor of temperature 20 DEG C, flow 375kg/h and contacts in stirring tank by temperature 61 DEG C, flow 34000kg/h, octahydro azophenlyene foreign matter content, obtain the hexane processed.
The hexane of above-mentioned process is used for the preparation of the hexane solution of cyclohexanone-oxime, be formulated in the still of band stirring and carry out, cyclohexanone-oxime feeding temperature 92 DEG C, flow 6000kg/h, hexane feed temperature 56 DEG C, flow 34000kg/h, cyclohexanone-oxime flow 6000kg/h, preparation obtains the cyclohexanone-oxime hexane solution of about 15wt%.The solution storage prepared is in tundish, and in preparation, do not have the burnt pledge of black to generate, cyclohexanone-oxime hexane solution has no pipeline blockage problem in transport pipe, illustrates that polycondensation does not occur cyclohexanone-oxime.
Beckmann rearrangement is carried out further, octahydro azophenlyene content 12 μ g/g in gained rearrangement product with it.
Embodiment 2
The present embodiment illustrates the method for organic solvent and the preparation method of hexanolactam of cycle for the treatment of.
Be that the circulation hexane of 0.385wt% mixes with the 40wt% sodium hydroxide of temperature 20 DEG C, flow 270kg/h and contacts in stirring tank by temperature 61 DEG C, flow 34000kg/h, octahydro azophenlyene foreign matter content, obtain the hexane processed.
The hexane of above-mentioned process is used for the preparation of the hexane solution of cyclohexanone-oxime, be formulated in the still of band stirring and carry out, cyclohexanone-oxime feeding temperature 91 DEG C, flow 6000kg/h, hexane feed temperature 58 DEG C, flow 34000kg/h, preparation obtains the hexane solution of the cyclohexanone-oxime of about 15wt%.The solution storage prepared is in tundish, and in preparation, do not have the burnt pledge of black to generate, the hexane solution of cyclohexanone-oxime has no pipeline blockage problem in transport pipe, illustrates that polycondensation does not occur cyclohexanone-oxime.
Beckmann rearrangement is carried out further, octahydro azophenlyene content 10 μ g/g in gained rearrangement product with it.
Claims (10)
1. the method for the organic solvent of a cycle for the treatment of, it is characterized in that, carry out Beckmann rearrangement reaction and be separated the organic solvent obtained contacting with alkaline matter with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process by coming from the amidation liquid obtained in toluene method manufacture caprolactam process, the octahydro azophenlyene content in the Beckmann rearrangement reaction product that alkaline matter add-on makes the organic solvent recycled participate in is no more than 15 μ g/g.
2. according to the process of claim 1 wherein, said alkaline matter be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, calcium carbonate and ammoniacal liquor one or more.
3. according to the method for claim 1 or 2, wherein, said alkaline matter, its concentration of aqueous solution is its saturation concentration.
4. according to the process of claim 1 wherein, said organic solvent contacts with alkaline matter, and its Contact Temperature is 5-80 DEG C.
5., according to the process of claim 1 wherein, the octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that said alkaline matter add-on makes the organic solvent recycled participate in is no more than 10 μ g/g.
6. according to the method for claim 1,4 or 5, wherein, said organic solvent is selected from one or more in benzene, toluene, hexanaphthene and hexane.
7., according to the process of claim 1 wherein, the organic solution of said cyclohexanone-oxime is the hexane solution of cyclohexanone-oxime, and its concentration is 5-20wt%.
8. the preparation method of a hexanolactam, toluene method is manufactured the amidation liquid obtained in caprolactam process to carry out Beckmann rearrangement reaction and be separated obtaining reaction product and organic solvent with the organic solution contact that benzene legal system makes the cyclohexanone-oxime obtained in caprolactam process, wherein, said reaction product is again through comprising neutralization, crystallization, extraction and treating process obtain hexanolactam, and said organic solvent is through recycling, it is characterized in that, in the organic solution of said cyclohexanone-oxime, organic solvent comes from organic solvent and the said organic solvent the recycled elder generation before contacting preparation with cyclohexanone-oxime and obtaining the organic solution of cyclohexanone-oxime recycled at least partly and contacts with a kind of alkaline matter, octahydro azophenlyene content in the product of the Beckmann rearrangement reaction that the organic solvent through recycling is participated in is no more than 15 μ g/g.
9. according to the method for claim 8, wherein, the said organic solvent recycled is 0-80 DEG C contacting the temperature that preparation obtains the organic solution of cyclohexanone-oxime with cyclohexanone-oxime.
10. according to the method for claim 8, wherein, in the organic solution of said cyclohexanone-oxime, come from that the organic solvent recycled accounts for total organic solvent 95 ~ 100%.
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| US20090312542A1 (en) * | 2008-06-13 | 2009-12-17 | China Petrochemical Development Corporation | System and method for recovering caprolactam from rearrangement mixtures |
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