CN104072385B - A kind of processing method of cyclohexanone oxime and a kind of preparation method of caprolactam - Google Patents
A kind of processing method of cyclohexanone oxime and a kind of preparation method of caprolactam Download PDFInfo
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Abstract
The invention provides a kind of processing method of cyclohexanone oxime, the method makes cyclohexanone oxime solution and is selected from one or more in the inorganic salts of II A, I B, II B or VIII family metallic element and contacts. The present invention also provides a kind of preparation method of caprolactam, and the method is used cyclohexanone oxime that the disposal methods of above-mentioned cyclohexanone oxime obtains to carry out Beckmann rearrangement to prepare caprolactam. The invention solves volatility alkali impurity close with caprolactam physicochemical properties, be difficult to effective problem separating, utilize the large feature of chemical property difference of volatility alkali impurity and cyclohexanone oxime, remove in advance these impurity, thereby reduce the volatility alkali impurity of bringing rearrangement reaction and follow-up refining system into, improved caprolactam product quality.
Description
Technical field
The present invention relates to a kind of processing method of cyclohexanone oxime and a kind of preparation method of caprolactam, relate to especiallyAnd a kind of processing method of the cyclohexanone oxime that improves quality of caprolactam and a kind of preparation method of caprolactam.
Background technology
Caprolactam is a kind of important Organic Chemicals, and main application is that polymerization generates nylon-6 section,Further be processed into nylon fiber, engineering plastics and plastic sheeting, be widely used in weaving, automobile, electronicsAnd machinery etc. field. Caprolactam is as the monomer of polymer, very high to its purity requirement, even the utmost pointThereby also may participating in polymerisation, a small amount of impurity affects the intensity of fiber, heat resistance and Color. VolatilizationProperty alkali content be weigh that caprolactam product quality is main, one of modal index, affect this indexBe that a class is unstable under strong alkaline condition, can be hydrolyzed the assorted of volatility alkali such as producing ammonia or little molecule organic amineMatter. In the time of caprolactam polymerization, ammonia or organic amine that these impurity hydrolysis produce can consume molecular weight stabilizerAdipic acid or acetic acid, thus polymerization rate affected, reduce viscosity and the relative molecular weight of polymer. ?In high speed spinning production process, the fluctuation of volatility alkali content can cause shower nozzle stop up, make fiber end breakage rate andWaste silk rate increases. Therefore, polymerization technique requires the extremely low (GB of volatility alkali content of caprolactamGB/T13254-2008 regulation top grade product volatility alkali content≤0.4mmol/kg, primes0.4-0.8mmol/kg, certified products 0.8-1.5mmol/kg), and stable do not fluctuate.
Traditional caprolactam refining process comprises: the extraction of sulphur ammonium and stripping, extraction (benzene extraction, water washing,Water back extraction), zwitterion resins exchange, catalytic hydrogenation, triple effect evaporation, distillation etc., finally obtain purity and be99.99% caprolactam product. Above-mentioned subtractive process is all for removing specific impurity, to removing volatilityThe effect of alkali impurity is all not obvious, and its reason is physicochemical properties and the caprolactam of volatility alkali impurityVery approaching, and content is extremely low, is just difficult to effectively remove from caprolactam by above-mentioned means once produce.As volatility alkali impurity n-caproamide, 255 DEG C of boiling points, approaching with 262 DEG C of the boiling points of caprolactam, and contentOnly tens ppm, are difficult to effective separation. In caprolactam product, contain micro-above-mentioned impurity, just can make volatilizationProperty alkali content exceeds standard.
Cyclohexanone oxime is the important intermediate of producing caprolactam, and its quality will directly have influence on caprolactam matterAmount. In cyclohexanone oxime raw material, often contain plurality of impurities, comprise that micro-alkaline impurities is as aniline, hexylamine, ownNitrile, C3-C7 acid amides etc., if remove these impurity without pretreatment, its will be brought into rearrangement reaction andCaprolactam refining process, is finally brought in finished product, makes caprolactam volatility alkali content increase, and reducesProduct quality grade.
CN1226553A and CN1138576A disclose by the methyl-cyclopentanone class impurity in control loop hexanoneBe not more than the method that 400ppm improves quality of caprolactam. The disclosed method of CN101119957A is at ringIn hexanone raw material, add amine substance to react with ketone and aldehyde type impurities, generate high boiling heavy product, thereby withCyclohexanone separates, and improves caprolactam product quality. US6784316 uses the alkaline medium purity rings such as NaOHHexanone oxime, has reduced high-boiling-point impurity, thereby has reduced reactor coking, and the method is mainly for for gasThe cyclohexanone oxime of phase Beckmann rearrangement device is refining. US4873369 uses acid/alkali resin purification cyclohexanone oxime,The Inorganic Ammonium ions such as the ammonium sulfate in main removal cyclohexanone oxime. CN102030708A discloses at Beckman weightAfter row's reaction, increase the curing step of neutralized rearrangement mixture, can effectively improve rearrangement reaction quality, reduce and resetThe titration value of mixture and extinction value, reduce finished product caprolactam volatility alkali content, improves the quality of products.
Summary of the invention
The present inventor finds by a large amount of development tests, the cyclohexanone oxime raw material that contains plurality of impurities withThe inorganic salts contact of some metallic elements is processed, and can make impurity absorption in the inorganic salts solid of metallic elementOn particle, the impurity content in cyclohexanone oxime is obviously reduced, improve cyclohexanone oxime purity, then will processAfter cyclohexanone oxime carry out Beckmann rearrangement, can make the caprolactam of low volatility alkali content, improveProduct quality.
One of object of the present invention be in cyclohexanone oxime preparation process and caprolactam refining operation in impurityThe defect that is difficult to remove completely, provides a kind of processing method of the cyclohexanone oxime that is different from prior art, removesIn cyclohexanone oxime, affect the impurity of caprolactam volatility alkali content; Two of object of the present invention is to provide oneThe preparation method of the caprolactam that can improve the quality of products.
The processing method of cyclohexanone oxime provided by the invention, is characterized in that making cyclohexanone oxime solution and is selected from IIOne or more contacts in the inorganic salts of A, I B, II B or VIII family metallic element.
The present invention also provides a kind of preparation method of caprolactam, it is characterized in that using above-mentioned cyclohexanone oximeThe cyclohexanone oxime that obtains of disposal methods carry out Beckmann rearrangement and prepare caprolactam.
The processing method of cyclohexanone oxime provided by the invention, has solved volatility alkali impurity and caprolactam physicsChemical property is close, be difficult to the problem that effectively separates, utilizes the chemistry of volatility alkali impurity and cyclohexanone oximeThe feature that matter difference is large, removes these impurity in advance, brings rearrangement reaction and follow-up refining system into thereby reducedThe volatility alkali impurity of system, has improved caprolactam product quality.
Detailed description of the invention
The processing method of cyclohexanone oxime provided by the invention, is characterized in that making cyclohexanone oxime solution and is selected from IIOne or more contacts in the inorganic salts of A, I B, II B or VIII family metallic element.
In the processing method of cyclohexanone oxime provided by the invention, the inorganic salts of described metallic element can be selected from IIAnhydrous halide salt, anhydrous sulfate or the anhydrous nitrate of A, I B, II B or VIII family metallic element, more excellentChoosing the concrete but inorganic salts of the metallic element that is not limited to can be selected from anhydrous CaCl2, anhydrous Mg (NO3)2、Anhydrous CuCl2, anhydrous ZnSO4With anhydrous FeCl3Deng. In a most preferred embodiment of the present invention,The inorganic salts of the metallic element adopting are anhydrous Mg (NO3)2, the purity of the cyclohexanone oxime that its processing obtains,Volatility alkali content in major impurity content wherein and the caprolactam obtaining through Beckmann rearrangement is equalReach more excellent effect.
Industrial extensively by phosphatic hydroxylamine method (HPO method) or liquid phase ammonia oximate legal system for cyclohexanone oxime, due toAll, taking cyclohexanone as raw material, the cyclohexanone oxime of two kinds of method productions contains multiple identical impurity. The invention providesProcessing method in, said cyclohexanone oxime derives from the cyclohexanone oxime that above-mentioned any method is produced. LogicalOften, before the inventive method is processed, the purity of cyclohexanone oxime is 99.1～99.9%, and total impurities is 0.1～0.9%,And in main impurity, hexylamine content is no more than 100 μ g/g, aniline content is no more than 200 μ g/g, positive hexanoylAmine content is no more than 300 μ g/g.
In processing method provided by the invention, the weight concentration of described cyclohexanone oxime solution is 1-50%, preferred5-25%. Processing method of the present invention is applicable to the cyclohexanone oxime solution under various solvents existence. Described hexamethyleneIn ketoxime solution, solvent is hydrocarbon solvent, comprises C5-C8 hydrocarbon, preferably n-hexane, cyclohexane, benzene and toluene,More preferably toluene and n-hexane.
Processing method provided by the invention, can be uniformly mixed mode by slurry state bed and realize, and also can pass throughFixed bed mode realizes, and cyclohexanone oxime solution is contacted with the solid particle of the inorganic salts of metallic element. WhenRealize time of the present invention by slurry state bed, the inorganic salts of described metallic element be cyclohexanone oxime weight 0.1-10%,Preferably 1-5%, treatment temperature is 10-150 DEG C, preferred 30-60 DEG C, the processing time is 5-60min, preferred15-30min. When realizing by fixed bed time of the present invention, reactor batch temperature be 10-150 DEG C, preferably30-100 DEG C, cyclohexanone oxime air speed 20-100h-1, preferably air speed 40-80h-1(be equivalent to starch in state bed inorganicSalt consumption is 5% of cyclohexanone oxime weight, and being equivalent to starch the processing time in state bed is 15-30min).
The present invention also further provides a kind of preparation method of caprolactam, it is characterized in that using above-mentioned ringThe cyclohexanone oxime that the disposal methods of hexanone oxime obtains, rubs at 80 DEG C-110 DEG C, sour oxime by oleumYou prepare caprolactam than carrying out Beckmann rearrangement under the condition for 1.05-1.5.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In embodiment and comparative example, impurity content capillary gas chromatography quantitative analysis in cyclohexanone oxime,Caprolactam volatility alkali content adopts methods analyst in GB/T13255.4-2009.
Embodiment 1
The present embodiment illustrates that the processing method of cyclohexanone oxime of the present invention is in the implementation of starching in state bed.
By the impure standby cyclohexanone oxime of cyclohexanone oxime A(cyclohexanone liquefied ammonia oximate legal system, consist of ringHexanone oxime 99.91%, total impurities is 0.09%, wherein hexylamine 30 μ g/g, aniline 40 μ g/g, n-caproamide60 μ g/g), with toluene dissolving, be made into the cyclohexanone oxime solution of weight concentration 50%. Add with respect to cyclohexanoneThe dried anhydrous CaCl of oxime weight 1%2Particle, stirring reaction 60min at 60 DEG C. Chromatogram quantification dividesAnalyse the cyclohexanone oxime toluene solution after filtration, cyclohexanone oxime 99.94%, total impurities is 0.06%, wherein ownAmine 5 μ g/g, aniline 12 μ g/g, n-caproamide 15 μ g/g.
Embodiment 2
The present embodiment illustrates that the processing method of cyclohexanone oxime of the present invention is in the implementation of starching in state bed.
By the impure standby cyclohexanone oxime of cyclohexanone oxime A(cyclohexanone liquefied ammonia oximate legal system, consist of ringHexanone oxime 99.91%, total impurities is 0.09%, wherein hexylamine 30 μ g/g, aniline 40 μ g/g, n-caproamide60 μ g/g) dissolve with benzene, be made into the cyclohexanone oxime solution of weight concentration 25%. Add with respect to cyclohexanone oximeThe dried anhydrous CaCl of weight 8%2Particle, stirring reaction 45min at 25 DEG C. Chromatographic quantitative analysisCyclohexanone oxime benzole soln after filtration, cyclohexanone oxime 99.96%, total impurities is 0.04%, wherein hexylamine5 μ g/g, aniline 10 μ g/g, n-caproamide 12 μ g/g.
Embodiment 3
The present embodiment illustrates that the processing method of cyclohexanone oxime of the present invention is in the implementation of starching in state bed.
By the impure standby cyclohexanone oxime of cyclohexanone oxime A(cyclohexanone liquefied ammonia oximate legal system, consist of ringHexanone oxime 99.91%, total impurities is 0.09%, wherein hexylamine 30 μ g/g, aniline 40 μ g/g, n-caproamide60 μ g/g) dissolve with cyclohexane, be made into the cyclohexanone oxime solution of weight concentration 10%. Add with respect to hexamethyleneThe dried anhydrous CaCl of ketoxime weight 8%2Particle, stirring reaction 15min at 60 DEG C. Chromatogram quantificationCyclohexanone oxime benzole soln after analysis and filter, cyclohexanone oxime 99.94%, total impurities is 0.06%, wherein ownAmine 7 μ g/g, aniline 13 μ g/g, n-caproamide 15 μ g/g.
Embodiment 4
The present embodiment illustrates the method for raising caprolactam product quality of the present invention.
In the reactor stirring with turbine power, add cyclohexanone oxime that embodiment 1 process processing obtains,10% oleum, maintains the mol ratio 1:1.5 of cyclohexanone oxime to sulfuric acid, 105 DEG C of reaction temperatures, stopTime 30min, obtains Beckmann rearrangement solution. At 50 DEG C,, then use to pH4.5 with ammonia neutralizationBenzene extraction crude caprolactam, the benzene caprolactam solution water back extraction again obtaining, is removed most of water-solubleThe crude caprolactam water solution of property and oil-soluble organic impurities, then remove NH by anion/cation resin bed4 +，Finally add appropriate NaOH to carry out reduced vacuum distillation, collect 5% head fraction, 90% midbarrelWith 5% remainder. The caprolactam of midbarrel is the caprolactam product of purifying, analyzes it and wavesThe property sent out alkali content is 0.30mmol/kg.
Embodiment 5
The implementation of the processing method that the present embodiment illustrates cyclohexanone oxime of the present invention in fixed bed and carryingThe method of high caprolactam product quality.
Cyclohexanone oxime B(is consisted of to cyclohexanone oxime 99.90%, and total impurities is 0.10%, wherein hexylamine32 μ g/g, aniline 41 μ g/g, n-caproamide 63 μ g/g) with n-hexane dissolution, be made into weight concentration 5%Cyclohexanone oxime solution. By dried about 10g anhydrous CaCl2Particle packing is in the glass adsorption column of jacketedIn, cyclohexanone oxime is at 40 DEG C, with air speed 40h-1Flow pass through adsorption column. InhaleAttached cyclohexanone oxime solution carries out chromatography, cyclohexanone oxime 99.93%, and total impurities 0.07%, whereinHexylamine 8 μ g/g, aniline 15 μ g/g, n-caproamide 16 μ g/g. Taking the method cyclohexanone oxime after treatment as formerMaterial, the caprolactam volatility alkali content of preparing according to same procedure in embodiment 4 is 0.44mmol/kg.
Comparative example 1
The explanation of this comparative example is without the process of the preparing caprolactam with cyclohexanone-oxime of processing method of the present invention.
Process is with embodiment 4, and difference is that cyclohexanone oxime used is the impure cyclohexanone of embodiment 1Oxime A.
Analyzing caprolactam volatility alkali content is 1.05mmol/kg.
Embodiment 6-9
Embodiment 6-9 illustrates in the processing method of cyclohexanone oxime of the present invention and adopts different metal element inorganic saltsProcess and improve accordingly the method for caprolactam product quality.
By impure cyclohexanone oxime B, with toluene dissolving, be made into the cyclohexanone oxime solution of weight concentration 10%,Add the anhydrous CuCl with respect to cyclohexanone oxime weight 5%2, anhydrous ZnSO4, anhydrous FeCl3, anhydrousMg(NO3)2Particle, stirring reaction 30min at 40 DEG C, filters, and under nitrogen protection, decompression distillation removesToluene solvant, carries out Beckmann rearrangement and product purification according to embodiment 4 processes.
The purity of the rear cyclohexanone oxime of processing and its major impurity content and the caprolactam of preparing as raw material are wavedThe property sent out alkali content is in table 1.
Table 1
Claims (13)
1. a processing method for cyclohexanone oxime, is characterized in that making cyclohexanone oxime solution and is selected from II A, I B, IIOne or more Contact-sorptions in the inorganic salts of B or VIII family metallic element affect caprolactam to removeThe impurity of volatility alkali content, the inorganic salts of described metallic element are cyclohexanone oxime weight0.1-10％。
2. method according to claim 1, wherein, the inorganic salts of described metallic element are anhydrous halide salt, nothingWater sulfate, anhydrous nitrate.
3. method according to claim 1, wherein, the inorganic salts of described metallic element are anhydrous CaCl2, nothingWater Mg (NO3)2, anhydrous CuCl2, anhydrous ZnSO4, anhydrous FeCl3。
4. method according to claim 1, wherein, described cyclohexanone oxime solution derives from cyclohexanone and prepares hexamethyleneThe process of ketoxime.
5. method according to claim 1, wherein, the weight concentration of described cyclohexanone oxime solution is 1-50%.
6. method according to claim 1, wherein, the weight concentration of described cyclohexanone oxime solution is 10-25%.
7. method according to claim 1, described cyclohexanone oxime solution, its solvent is hydrocarbon solvent.
8. method according to claim 1, described cyclohexanone oxime solution, its solvent is C5-C8 family hydrocarbon solvent.
9. method according to claim 1, described cyclohexanone oxime solution, its solvent be n-hexane, cyclohexane,Benzene, toluene.
10. method according to claim 1, wherein, described contact is by fixed bed mode or slurry state bed sideFormula realizes.
11. methods according to claim 1, wherein, described Contact Temperature is 10-150 DEG C.
12. methods according to claim 1, wherein, be 5-60min described time of contact.
13. 1 kinds are improved the method for caprolactam product quality, it is characterized in that right to use requires one of 1-12 instituteThe cyclohexanone oxime that the method for stating was processed carries out Beckmann rearrangement and prepares caprolactam.
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| US3527568A (en) * | 1966-12-16 | 1970-09-08 | Bayer Ag | Process for the preparation of lactams |
| US3904608A (en) * | 1972-09-08 | 1975-09-09 | Toray Industries | Process for the production of lactam |
| CN1660786A (en) * | 2003-11-28 | 2005-08-31 | 住友化学株式会社 | Stabilization method of cycloalkanone oxime |
| CN1741987A (en) * | 2003-01-30 | 2006-03-01 | 帝斯曼知识产权资产管理有限公司 | Processing contains the method for the organic solution of cyclohexanone-oxime, pimelinketone and organic solvent |
| CN103204809A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Production method of caprolactam |
| CN103827045A (en) * | 2011-10-28 | 2014-05-28 | 住友化学株式会社 | Method for treating waste water |
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2013
- 2013-03-29 CN CN201310108160.3A patent/CN104072385B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527568A (en) * | 1966-12-16 | 1970-09-08 | Bayer Ag | Process for the preparation of lactams |
| US3904608A (en) * | 1972-09-08 | 1975-09-09 | Toray Industries | Process for the production of lactam |
| CN1741987A (en) * | 2003-01-30 | 2006-03-01 | 帝斯曼知识产权资产管理有限公司 | Processing contains the method for the organic solution of cyclohexanone-oxime, pimelinketone and organic solvent |
| CN1660786A (en) * | 2003-11-28 | 2005-08-31 | 住友化学株式会社 | Stabilization method of cycloalkanone oxime |
| CN103827045A (en) * | 2011-10-28 | 2014-05-28 | 住友化学株式会社 | Method for treating waste water |
| CN103204809A (en) * | 2012-01-13 | 2013-07-17 | 中国石油化工股份有限公司 | Production method of caprolactam |
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