CN103420912B - The method of the thick product of a kind of crystallization ε-caprolactam and prepare the method for hexanolactam - Google Patents
The method of the thick product of a kind of crystallization ε-caprolactam and prepare the method for hexanolactam Download PDFInfo
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Abstract
The method of the thick product of a kind of crystallization ε-caprolactam, it is characterized in that the method comprises and will contain the halohydrocarbon solution of the thick product of ε-caprolactam and the step of crystal seed contact pairs, said contact pairs carries out in the Metastable zone of the halohydrocarbon solution containing the thick product of ε-caprolactam, wherein said halohydrocarbon is selected from straight-chain halogenated hydrocarbon, side chain halohydrocarbon, dihalo hydrocarbon or three halohydrocarbon, and said crystal seed is 2 ~ 80 object hexanolactam particles.The method can obtain complete crystal form and oarse-grained crystal, and more than 90% particle is between 0.5 ~ 3mm pars granulosa, is beneficial to industrial separation.
Description
Technical field
The present invention relates to the crystallization method of the thick product of a kind of ε-caprolactam and prepare the method for hexanolactam.
Background technology
ε-caprolactam is one of important raw material of synthon and synthetic resins, mainly for the manufacture of tynex (nylon 6), resin and film etc.At present, the method for industrial production hexanolactam adopts oleum to make catalysts and solvents, cyclohexanone-oxime generation liquid phase Beckmann rearrangement.There is the deficiencies such as etching apparatus, contaminate environment and economic benefit be undesirable in this technique, and the ammonium sulfate that by-product is relatively large.
Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement on solid acid catalyst realizes the novel process of ε-caprolactam without sulphur ammonium, have without the problem such as equipment corrosion, non-environmental-pollution, the separating-purifying of product also will simplify greatly, therefore receive the very big concern of insider without the vapor phase beckmann rearrangement reaction novel process of sulphur ammonium.
For development is applicable to the solid acid catalyst of vapor phase beckmann rearrangement reaction, domestic and international investigator carries out excessive quantifier elimination to two class dominant catalyst such as oxide compound (composite oxides), zeolite molecular sieves, all can prepare ε-caprolactam.
But the ε-caprolactam that these methods obtain contains plurality of impurities.As everyone knows, ε-caprolactam is used to the raw material preparing polymeric amide, require that the ε-caprolactam product also manufacturing synthon and synthetic resins for the preparation of polymeric amide further has very high specification of quality, the impurity of μ g/g level all can affect the polyreaction of follow-up ε-caprolactam, not easily forms long filament.Therefore, the method of various separating-purifying is adopted to obtain crude epsi-caprolactam, then adopt various refining method finally obtained highly purified ε-caprolactam, highly purified like this ε-caprolactam could for the manufacture of products such as synthon, synthetic resins and films.
The separating-purifying of liquid phase Beckmann rearrangement ε-caprolactam needs through following operation: reset neutralization, the extraction of sulphur ammonium and stripping, benzene extraction, water extraction, ion-exchange, hydrogenation, triple effect evaporation, distillation etc., the separating-purifying operation of reaction product is more, and the existence of partly cause inorganic salt ammonium sulfate causes.
The impurity with ε-caprolactam chemical properties similar fully can not be removed with the separating and purifying method of extraction, distillation, ion-exchange, or the by product that boiling point and ε-caprolactam are close.At this moment, the method for hydrogenation is taked to be a kind of effectively means.On the one hand, tetrahydroazepine-2-ketone and structure isomeride thereof can be made to be converted into ε-caprolactam by hydrogenation reaction; On the other hand, the potassium permanganate absorption value in product effectively can be improved by hydrogenation reaction.
In sum, common separating and purifying method combines as the single means such as distillation, rectifying, extraction, ion-exchange, absorption and hydrogenation or multiple means, might not obtain the ε-caprolactam of the required purity of industry.
Preparing highly purified chemical substance with crystallization method is the most ancient and one of effective separation method, and polymer level CPL is heat-sensitive substance, requires that again foreign matter content is low, utilizes crystallization process separating-purifying to cause the extensive concern of Ge great caprolactam production company.Bayer Bitterfeld GmbH, Switzerland INVENT, Dutch DSM, SUMITOMO CHEMICAL etc. developed the caprolactam refining technique relevant to crystallization all in succession, crystallization method comprises water, organic solvent crystallization and solventless crystalline, solventless crystalline product particle is little, fouling is serious, cause and be industrially difficult to continuous operation, hinder its development.
The separating-purifying process for purification of ε-caprolactam disclosed in CN101070298A and CN101070299A, the method is included in the step containing crystallization ε-caprolactam in the ethereal solution of crude epsi-caprolactam or halohydrocarbon solution.Described separating-purifying process for purification is distilled by the alcoholic solution of the ε-caprolactam obtained through vapor phase beckmann rearrangement reaction, and removing alcohol, lower-boiling impurity and high-boiling-point impurity, obtain crude epsi-caprolactam; Molten state crude epsi-caprolactam is dissolved in ether or halohydrocarbon, carry out crystallisation by cooling and carry out centrifugation obtaining ε-caprolactam crystal through solvent wash separation, and in the presence of a hydrogenation catalyst, ε-caprolactam is contacted with hydrogen and carries out hydrogenation reaction, thus obtain the extinction value of ε-caprolactam, volatility base number and potassium permanganate absorption value and meet the ε-caprolactam product that Industrial products require.
CN1332158A reports the separating and purifying method of the crude caprolactam obtained by vapor phase beckmann rearrangement reaction, and the method comprises: the important procedures such as distillation, recrystallization and hydrofining.
The ubiquitous problem of aforesaid method is the hexanolactam particle obtained little (being less than 600 μm), solid-liquid separation difficulty, particularly can there is the difficulties such as solid-liquid conveying, solid-liquid separation in engineering amplification process, affect the continuous seepage problem of hexanolactam.
Summary of the invention
An object of the present invention is on the basis of existing technology, provides a kind of simple and effective, method that can obtain even macrobead, be conducive to the thick product of crystallization ε-caprolactam of industrial applicability.
Two of object of the present invention provides a kind of preparation method meeting the hexanolactam that Industrial products require on new crystallization method basis.
The present inventor is surprised to find that on the basis of great many of experiments, when in the operation steps of the crystallization of crystallisation process, when throwing in the halohydrocarbon solution of the thick product of the hexanolactam of a small amount of hexanolactam particle in Metastable zone, the hexanolactam crystal of larger particle degree and complete crystal form can be obtained under certain temperature, be beneficial to industrial separation.Based on this, complete the present invention.
Therefore, the crystallization method of the thick product of ε-caprolactam provided by the invention, it is characterized in that the method comprises crystal seed and the step of halohydrocarbon solution contact pairs being in the thick product of ε-caprolactam in Metastable zone, wherein said halohydrocarbon is selected from one or more in straight-chain halogenated hydrocarbon, side chain halohydrocarbon, dihalo hydrocarbon or three halohydrocarbon, and said crystal seed is 2 ~ 80 object hexanolactam particles.
Present invention also offers a kind of preparation method of hexanolactam, comprise the mixed solution of ε-caprolactam and the reaction solvent obtained by Beckmann rearrangement through distilling the step obtaining the thick product of ε-caprolactam, the step of crystallization, solvent wash after crystallization, be separated the step obtaining ε-caprolactam crystal, exist at hydrogenation catalyst, make the step that ε-caprolactam contacts with hydrogen, and finally obtain the step of ε-caprolactam finished product, it is characterized in that in the step of said crystallization, comprise crystal seed and the process of halohydrocarbon solution contact pairs being in the thick product of ε-caprolactam in Metastable zone, wherein said halohydrocarbon is selected from straight-chain halogenated hydrocarbon, side chain halohydrocarbon, one or more in dihalo hydrocarbon or three halohydrocarbon, said crystal seed is 2 ~ 80 object hexanolactam particles.
The crystallization method of the thick product of ε-caprolactam provided by the invention, can obtain complete crystal form and oarse-grained crystal, and in its crystal obtained, more than 90% particle is between 0.5 ~ 3mm pars granulosa, is particularly conducive to industrial separation.The preparation method of hexanolactam provided by the invention, can obtain the hexanolactam finished product of purity more than 99.995%, meet Industrial products requirement.
Accompanying drawing explanation
Fig. 1 is the saturation solubility curve of hexanolactam in halogenated hydrocarbon solvent and supersaturation solubility curve schematic diagram.
Fig. 2 is particle size distribution figure, and wherein, curve 1 is the size distribution curve of the ε-caprolactam crystal grain that comparative example 1 obtains, and curve 2 is the size distribution curve of the ε-caprolactam crystal grain that embodiment 1 obtains.
Embodiment
Region between saturation solubility curve and supersaturation solubility curve is Metastable zone, and Fig. 1 shows saturation solubility curve in the halogenated hydrocarbon solvent of the hexanolactam of experimental determination and supersaturation solubility curve.The present inventor finds, if do not add crystal seed or not by other conditioned stimulus in Metastable zone, can not crystallize out automatically, and if add crystal seed, solute can be separated out and be grown up on crystal seed.For industrial operation, Metastable zone has important meaning.Contriver finds further, is controlled by crystallisation process at Metastable zone and in lower supersaturation solubleness, then a small amount of nucleus can only be had in a long time to produce, mainly add growing up of crystal seed, so can obtain granularity uniform crystalline product greatly; And if crystallisation process is in sphere of instability, namely higher supersaturation solubleness, then can break out nucleation, the crystalline product particle obtained is very little, is unfavorable for very much the solid-liquid separation of hexanolactam, amplifies cause very large difficulty to engineering.Therefore, if in crystallisation process, in Metastable zone, add a small amount of crystal seed, control Precipitation Temperature well, make hexanolactam be within the scope of low degree of supersaturation, the growth that can be conducive to crystal with grow up, thus obtain macrobead, uniform crystalline product.
The crystallization method of the thick product of ε-caprolactam provided by the invention, it is characterized in that the method comprises crystal seed and the step of halohydrocarbon solution contact pairs being in the thick product of ε-caprolactam in Metastable zone, wherein said halohydrocarbon is selected from one or more in straight-chain halogenated hydrocarbon, side chain halohydrocarbon, dihalo hydrocarbon or three halohydrocarbon, and said crystal seed is 2 ~ 80 object hexanolactam particles.
In more detail, the crystallization method of ε-caprolactam provided by the invention, is characterized in that the method comprises and is dissolved in said halohydrocarbon by thick for ε-caprolactam product, obtain the halohydrocarbon solution of the thick product of ε-caprolactam; To contact with the halohydrocarbon solution of the thick product of ε-caprolactam of 45 ~ 62 DEG C of temperature ranges in Metastable zone with said crystal seed again and carry out thermostatical crystallization, obtain hexanolactam crystal grain, then through solid-liquid separation, reclaim hexanolactam crystal.
In method provided by the invention, preferably carry out thermostatical crystallization with the halohydrocarbon solution contact pairs of the thick product of ε-caprolactam of 50 ~ 60 DEG C of temperature ranges in said crystal seed and Metastable zone, namely substantially keep this temperature range that the hexanolactam of large grain size is formed gradually; Then cool the temperature to crystallization final temperature (generally at 35 ~ 45 DEG C), carry out solid-liquid separation, obtain the hexanolactam crystal of a large amount of macrobead (0.5 ~ 3mm).
In the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1: 1 ~ 10; Preferred further, in the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1: 1.2 ~ 8; Further preferred, in the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1: 2 ~ 5.
The thick product of said ε-caprolactam preferably but be not limited to be that zeolite [molecular sieve by cyclohexanone-oxime and MFI topology carries out vapor phase beckmann rearrangement reaction, then obtains after distilling out reaction solvent.In the thick product of above-mentioned said ε-caprolactam, usually be the hexanolactam of 99.0 ~ 99.6% containing purity, and tetrahydroazepine-2-ketone, hexanal, pimelinketone, other weight impurity such as cyclonene, 2-heptanone, cyclohexanone-oxime, n-valeramide, n-caproamide, adipimide, dimethyl-aniline, N-methyl-hexanolactam, octahydro acridine, octahydro azophenlyene, tetrahydro naphthylamine, tetrahydro carbazole.。
In method provided by the invention, said crystal seed is hexanolactam particle, and its order number is 2 ~ 80 orders.Said order number in the present invention, its concept refers in the length of 1 inch (25.4mm), and a total how many holes arrangement is exactly how many orders.Such as, 10 orders represent in the length of 1 inch, are arranged with altogether 10 holes; And 40 orders represent in the length of 1 inch, be arranged with altogether 40 holes, 80 orders represent in the length of 1 inch, are arranged with altogether 80 holes.The implication of said 2 ~ 80 object hexanolactam particles refers to and can leak through from 2 object mesh and the hexanolactam particle that can not leak through from 80 object mesh.
In method provided by the invention, said crystal seed is 2 ~ 80 object hexanolactam particles, and its add-on is 1 ~ 15 heavy % of the thick product of ε-caprolactam.The order numerical example of said crystal seed is as being 10 ~ 20 orders, and also can be 20 ~ 40 orders, can also be 30 ~ 60 orders, or can be 40 ~ 80 orders.According to the difference of the order number scope of the crystal seed added, the add-on of crystal seed is also differentiated.Such as, at 40 ~ 60 object crystal seeds, its add-on is 1 ~ 5 heavy %, preferably 2 ~ 4 heavy % of the thick product of ε-caprolactam; 20 ~ 40 its add-ons of object crystal seed are 5 ~ 10 heavy %, preferably 6 ~ 9 heavy % of the thick product of ε-caprolactam; 6 ~ 20 object crystal seeds, its add-on is 10 ~ 15 heavy %, preferably 11 ~ 14 heavy % of the thick product of ε-caprolactam.
In method provided by the invention, said halohydrocarbon is selected from one or more the mixture in straight-chain halogenated hydrocarbon, side chain halohydrocarbon, dihalo hydrocarbon or three halohydrocarbon.Said halohydrocarbon has the boiling range of 30 ~ 150 DEG C; Further preferably, said halohydrocarbon solution has the boiling range of 50 ~ 100 DEG C; Further preferred, said halohydrocarbon solution has the boiling range of 60 ~ 90 DEG C.Under the prerequisite of boiling range meeting above-mentioned said halohydrocarbon, further, said halohydrocarbon be selected from but be not limited in positive chloropropane, different chloropropane, n-propylcarbinyl chloride, secondary chlorobutane, different chlorobutane, three grades of chlorobutanes, n-Propyl Bromide, different N-PROPYLE BROMIDE, 1-n-butyl bromide, 2-n-butyl bromide one or more.
In the inventive method, said crystal seed can carry out once with the step of the halohydrocarbon solution contact pairs being in the thick product of ε-caprolactam in Metastable zone, also can carry out repeatedly.
The present invention is on the basis of the crystallization method of the thick product of above-mentioned ε-caprolactam, additionally provide a kind of preparation method of hexanolactam, comprise the mixed solution of ε-caprolactam and the reaction solvent obtained by Beckmann rearrangement through distilling the step obtaining the thick product of ε-caprolactam, the step of crystallization, solvent wash after crystallization, be separated the step obtaining ε-caprolactam crystal, exist at hydrogenation catalyst, make the step that ε-caprolactam contacts with hydrogen, and finally obtain the step of ε-caprolactam finished product, it is characterized in that in the step of said crystallization, comprise crystal seed and the process of halohydrocarbon solution contact pairs being in the thick product of ε-caprolactam in Metastable zone, wherein said halohydrocarbon is selected from straight-chain halogenated hydrocarbon, side chain halohydrocarbon, in dihalo hydrocarbon or three halohydrocarbon-kind or multiple, said crystal seed is 2 ~ 80 object hexanolactam particles.。
In the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1: 1 ~ 10; Preferably, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1: 1.2 ~ 8; Preferred, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1: 2 ~ 5.
The thick product of said ε-caprolactam preferably but be not limited to be that zeolite [molecular sieve by cyclohexanone-oxime and MFI topology carries out vapor phase beckmann rearrangement reaction, then obtains after distilling out reaction solvent.The thick product of said ε-caprolactam refers to the hexanolactam obtained through simple distillation.In the thick product of above-mentioned said ε-caprolactam, usually be the hexanolactam of 99.0 ~ 99.6% containing purity, and tetrahydroazepine-2-ketone, hexanal, pimelinketone, other weight impurity such as cyclonene, 2-heptanone, cyclohexanone-oxime, n-valeramide, n-caproamide, adipimide, dimethyl-aniline, N-methyl-hexanolactam, octahydro acridine, octahydro azophenlyene, tetrahydro naphthylamine, tetrahydro carbazole.
Wherein, said crystal seed is 2 ~ 80 object hexanolactam particles; Preferably, said crystal seed is 20 ~ 60 object hexanolactam particles; Preferred, said crystal seed is 20 ~ 40 object hexanolactam particles.
In method provided by the invention, said crystal seed is 10 ~ 80 object hexanolactam particles, and its add-on is 1 ~ 15 heavy % of the thick product of ε-caprolactam.The order numerical example of said crystal seed is as being 10 ~ 20 orders, and also can be 20 ~ 40 orders, can also be 30 ~ 60 orders, or can be 40 ~ 80 orders.According to the difference of the order number scope of the crystal seed added, the part by weight of crystal seed and the thick product of hexanolactam is also differentiated.Such as, 40 ~ 60 object crystal seeds, it accounts for 1 ~ 5 heavy %, preferably 2 ~ 4 heavy % of the thick product of ε-caprolactam; 20 ~ 40 object crystal seeds account for 5 ~ 10 heavy %, preferably 6 ~ 9 heavy % of the thick product of ε-caprolactam; Crystal seed below 20 orders accounts for 10 ~ 15 heavy %, preferably 11 ~ 14 heavy % of the thick product of ε-caprolactam.
In method provided by the invention, said halohydrocarbon be selected from straight-chain halogenated hydrocarbon, side chain halohydrocarbon, dihalo hydrocarbon or three halohydrocarbon one or more.Said halohydrocarbon has the boiling range of 30 ~ 150 DEG C; Further preferably, said halohydrocarbon solution has the boiling range of 50 ~ 100 DEG C; Further preferred, said halohydrocarbon solution has the boiling range of 60 ~ 90 DEG C.Under the prerequisite meeting above-mentioned boiling range, said halohydrocarbon be selected from but be not limited in positive chloropropane, different chloropropane, n-propylcarbinyl chloride, secondary chlorobutane, different chlorobutane, three grades of chlorobutanes, n-Propyl Bromide, different N-PROPYLE BROMIDE, 1-n-butyl bromide, 2-n-butyl bromide one or more.
In the step of said crystallization, the process of crystal seed and the halohydrocarbon solution contact pairs that is in the thick product of ε-caprolactam between Metastable zone can once, also can be carried out repeatedly.
In the step of said crystallization, crystallization mode can consider the mode such as crystallisation by cooling, evaporative crystallization, vacuum insulation crystallization; Crystallizer can adopt generic crystallization device, as FC type crystallizer, Oslo type crystallizer, DTB type crystallizer, DP type crystallizer, Messo type crystallizer etc.
In the preparation method of hexanolactam provided by the invention, also include comprise ε-caprolactam and the reaction solvent obtained by Beckmann rearrangement mixed solution through distilling the step obtaining crude epsi-caprolactam.Wherein, said reaction solvent is alcohol, and said alcohol is preferably methyl alcohol and/or ethanol.Said distillation, by reaction solvent recycling use after distillation, obtain the water-epsilon-caprolactam mixture containing water, light impurity component, heavy seeds component simultaneously, progressively distillation is dewatered again, removing light constituent and heavy seeds component, obtain the thick product of ε-caprolactam that purity is less than 99.5%.
In the preparation method of hexanolactam provided by the invention, after also including crystallization, solvent wash is separated the step obtaining ε-caprolactam crystal, and said solvent wash generally selects the compound identical with recrystallisation solvent, such as haloalkane, ether or other hydro carbons.The consumption of solvent wash and hexanolactam crystal is generally 0.8 ~ 1.5: 1, at room temperature stirs certain hour, whizzer can be adopted afterwards to carry out solid-liquid separation, obtain hexanolactam crystal, as hydrogenating materials.
In the preparation method of hexanolactam provided by the invention, also include in the presence of a hydrogenation catalyst, the step of the hydrogenation that ε-caprolactam is contacted with hydrogen.We know, fully can not remove the impurity with ε-caprolactam chemical properties similar with the separating and purifying method of extraction, distillation, ion-exchange, or the by product that boiling point and ε-caprolactam are close.At this moment, the method for hydrogenation is taked to be a kind of effectively means.On the one hand, tetrahydroazepine-2-ketone and structure isomeride thereof can be made to be converted into ε-caprolactam by hydrogenation reaction; On the other hand, the potassium permanganate absorption value in product effectively can be improved by hydrogenation reaction.Hexanolactam hydrofining can adopt aqueous solution hydrogenation, and molten state hexanolactam also can be adopted to carry out hydrogenation; The reactor types of hexanolactam hydrofining is not particularly limited, as adopted magnetically stabilized bed reactor device, fixed-bed reactor or slurry bed reactor, fixed-bed reactor can select molten state hexanolactam or caprolactam water solution to carry out hydrofining; Catalyzer can be nickel catalyst, also can be precious metal palladium series catalysts.Hydroconversion condition generally 80 ~ 150 DEG C, carry out under 2 ~ 15atm pressure.
In the preparation method of hexanolactam provided by the invention, also include the step obtaining ε-caprolactam finished product, if the product that hexanolactam hydrofining obtains is containing relatively large water, then need to carry out triple effect evaporation and (decompression) distillation, finally obtain qualified caprolactam product; If hexanolactam hydrofining adopts molten state hexanolactam, then directly carry out (decompression) distillation and can obtain qualified caprolactam product.
Below by embodiment, the invention will be further described, but therefore do not limit content of the present invention.
In embodiment, by the purity of 6890 type gas chromatographs (Agilent company) analyzing crystal; Crystal boundary is characterized with opticmicroscope (SG2-6XB-PC type) 40 times of enlargement ratios.
The desk-top centrifugal filter of TD5LG type, Saite Hunan, Hunan Instrument Ltd..
S7401-II type stepless time adjustment electric mixer, Juancheng, Shandong Yongxing instrument plant.
Mastersizer-2000 type particles distribution instrument.
Embodiment 1
Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement is carried out in 80ml fixed-bed reactor, the internal diameter of reactor is 28mm, the molecular sieve catalyst loadings of high silica alumina ratio MFI structure is 9.45g (Ф 1.8mm bar shaped catalyst), reaction pressure 0.1MPa, catalyst bed reaction temperature 365 DEG C-385 DEG C, carrier gas flux is 3.0L/gcat/hr, and cyclohexanone-oxime WHSV is 2h
-1, the partial pressure range of mixture: cyclohexanone-oxime 5.5kPa-11.6kPa, methyl alcohol (solvent) 36.9kPa-70.6kPa, nitrogen (carrier gas) 19.4kPa-52.6kPa.Reaction product is passed through-5 DEG C of ethylene glycol solution circulating coolings and is collected, and obtains the reaction product containing ε-caprolactam.
First adopt the method for simple distillation to distill this reaction mixture, removing methyl alcohol, lower-boiling impurity and high-boiling-point impurity, finally obtain crude epsi-caprolactam.On Agilent company 6890 type gas chromatograph, (hydrogen flame ionization sensor, PEG20M capillary chromatographic column, column length 50m) analyzes crude epsi-caprolactam, and it mainly consists of: 99.2% ε-caprolactam.
Get the crude epsi-caprolactam that 130g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, then add 130g n-propylcarbinyl chloride recrystallisation solvent, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 53 DEG C from 70 DEG C, and the hexanolactam crystal adding 2.5g16 ~ 40 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 57 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 45 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve is shown in the curve 2 of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 106.6g99.96% hexanolactam crystal and centrifuge mother liquor ether, yield reaches 81%.Centrifuge mother liquor n-propylcarbinyl chloride solvent can carry out recycling.100g hexanolactam crystal is turned back in 500ml there-necked flask, add 100g n-propylcarbinyl chloride cleaning solvent, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.97% ε-caprolactam crystal and n-propylcarbinyl chloride cleaning solvent, yield reaches about 94.5%.N-propylcarbinyl chloride cleaning solvent reclaims.The PM value of the ε-caprolactam obtained is 160s, E value < 0.5.
Hydrogenation reaction: get the 99.97% hexanolactam crystal of 100g after n-propylcarbinyl chloride solvent wash, be added in 500ml reactor, add water 250g, then add 0.5g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 42000s, E value < 0.03, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Comparative example 1
This comparative example illustrates under same crystallization condition, without the impact of crystal seed on Lens capsule.
Condition is with embodiment 1, and difference is not add crystal seed.The caprolactam product quality obtained, PM value is 46000s, E value < 0.03.This quality product is no problem, but particle is thin, does not have intensity, is industrially difficult to carry out solid-liquid separation.
The Lens capsule curve of products obtained therefrom is shown in the curve 1 of Fig. 2.
Find out from the Lens capsule curve of Fig. 2, add with do not add crystal seed condition under the Lens capsule obvious difference that obtains.In comparative example 1, do not add the most Probable distrebution of crystal grain after seeded crystallization at 650 μm of places, and the most Probable distrebution of embodiment 1 crystal size after adding seeded crystallization is at 950 μm of places, crystal grain obviously increases, most Probable distrebution adds 300 μm, and wherein large crystal grain is greater than 2000 μm.Illustrate that adding crystal seed at Metastable zone can control crystallisation process in low degree of supersaturation region, be conducive to the number controlling nucleus, be more conducive to the growth of crystal.
Comparative example 2
Condition, with embodiment 1, adds the crystal seed of more than 80 orders, because seed particles is too thin, is dissolved very soon, and does not add coming to the same thing of crystal seed.
Embodiment 2
As described in Example 1, get the crude epsi-caprolactam that 130g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add the different chlorobutane recrystallisation solvent of 130g again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 53 DEG C from 70 DEG C, and the hexanolactam crystal adding 2.6g16 ~ 40 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 58 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 35 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 114g99.95% hexanolactam crystal and centrifuge mother liquor, yield reaches 86%.The different chlorobutane solvent of centrifuge mother liquor can carry out recycling.110g hexanolactam crystal is turned back in 500ml there-necked flask, add the different chlorobutane cleaning solvent of 110g, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.96% ε-caprolactam crystal and washing mother liquor, yield reaches about 95%.Different chlorobutane cleaning solvent reclaims.The PM value of the ε-caprolactam obtained is 126s, E value < 0.6.
Hydrogenation reaction: get the 99.96% hexanolactam crystal of 100g after different chlorobutane solvent wash, be added in 500ml reactor, add water 250g, then add 0.5g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 40000s, E value < 0.04, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Embodiment 3
As described in Example 1, get the crude epsi-caprolactam that 65g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add 130g trichloromethane recrystallisation solvent again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 52 DEG C from 70 DEG C, and the hexanolactam crystal adding 2.6g16 ~ 40 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 58 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 43 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 52g99.94% hexanolactam crystal and centrifuge mother liquor, yield reaches 79%.Centrifuge mother liquor trichloromethane solvent can carry out recycling.50g hexanolactam crystal is turned back in 500ml there-necked flask, add 50g trichloromethane cleaning solvent, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.96% ε-caprolactam crystal and washing mother liquor, yield reaches about 92%.Trichloromethane cleaning solvent reclaims.The PM value of the ε-caprolactam obtained is 120s, E value < 0.7.
Hydrogenation reaction: get 99.96% hexanolactam crystal after 40g trichloromethane solvent wash, be added in 200ml reactor, add water 100g, then add 0.2g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 36000s, E value < 0.05, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Embodiment 4
As described in Example 1, get the crude epsi-caprolactam that 130g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add the different chlorobutane recrystallisation solvent of 130g again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 54 DEG C from 70 DEG C, and the hexanolactam crystal adding 10g6 ~ 10 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 58 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 44 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 113g99.95% hexanolactam crystal and centrifuge mother liquor, yield reaches 81%.The different chlorobutane solvent of centrifuge mother liquor can carry out recycling.100g hexanolactam crystal is turned back in 500ml there-necked flask, add the different chlorobutane cleaning solvent of 80g, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.96% ε-caprolactam crystal and washing mother liquor, yield reaches about 95%.Different chlorobutane cleaning solvent reclaims.The PM value of the ε-caprolactam obtained is 150s, E value < 0.6.
Hydrogenation reaction: get the 99.96% hexanolactam crystal of 80g after different chlorobutane solvent wash, be added in 500ml reactor, add water 200g, then add 0.4g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 42000s, E value < 0.03, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Embodiment 5
As described in Example 1, get the crude epsi-caprolactam that 90g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add 130g n-propylcarbinyl chloride recrystallisation solvent again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 52 DEG C from 70 DEG C, and the hexanolactam crystal adding 2.6g16 ~ 40 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 58 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 40 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 113.3g99.95% hexanolactam crystal and centrifuge mother liquor, yield reaches about 84%.Centrifuge mother liquor n-propylcarbinyl chloride solvent can carry out recycling.100g hexanolactam crystal is turned back in 500ml there-necked flask, add 80g n-propylcarbinyl chloride cleaning solvent, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.97% ε-caprolactam crystal and washing mother liquor, yield reaches about 90%.N-propylcarbinyl chloride solvent wash solvent reclaims.The PM value of the ε-caprolactam obtained is 150s, E value < 0.8.
Hydrogenation reaction: get the 99.97% hexanolactam crystal of 80g after n-propylcarbinyl chloride solvent wash, be added in 500ml reactor, add water 200g, then add 0.4g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 42000s, E value < 0.04, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Embodiment 6
As described in Example 1, get the crude epsi-caprolactam that 90g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add 130g trichloromethane solvent again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 51.5 DEG C from 70 DEG C, adds 5.2g40 ~ 60 object hexanolactam crystal in there-necked flask, and maintain 15 minutes at 50 ~ 58 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 40 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 76.3g99.95% hexanolactam crystal and centrifuge mother liquor, yield reaches about 80%.Centrifuge mother liquor trichloromethane solvent can carry out recycling.Turned back in 500ml there-necked flask by 70g hexanolactam crystal, add 70g trichloromethane solvent, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.96% ε-caprolactam crystal and washing mother liquor, yield reaches about 92%.Trichloromethane solvent wash solvent reclaims.The PM value of the ε-caprolactam obtained is 150s, E value < 0.6.
Hydrogenation reaction: get the 99.96% hexanolactam crystal of 60g after trichloromethane solvent wash, be added in 300ml reactor, add water 150g, then add 0.3g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 40000s, E value < 0.03, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Embodiment 7
As described in Example 1, get the crude epsi-caprolactam that 70g is obtained by above-mentioned simple distillation method, add in 500ml there-necked flask, add the different chlorobutane recrystallisation solvent of 260g again, be heated to 60 ~ 70 DEG C, stir 10 minutes, ε-caprolactam is dissolved in this solvent completely.Continue to cool while stirring, temperature is cooled to about 51 DEG C from 70 DEG C, and the hexanolactam crystal adding 8.0g6 ~ 10 mesh sieve mesh number is in there-necked flask, and maintain 15 minutes at 50 ~ 56 DEG C, stirring velocity remains unchanged, and has macrobead hexanolactam to generate; Continue to cool while stirring, to about 35 DEG C, macrobead hexanolactam is separated out completely, and gained Lens capsule curve has curve 2 feature of Fig. 2.Stop stirring, take out there-necked flask, centrifugation, obtain 67.1g99.96% hexanolactam crystal and centrifuge mother liquor, yield reaches about 86%.The different chlorobutane solvent of centrifuge mother liquor can carry out recycling.50g hexanolactam crystal is turned back in 500ml there-necked flask, add the different chlorobutane cleaning solvent of 65g, at room temperature agitator treating 10 minutes, and then carry out centrifugation, obtain 99.98% ε-caprolactam crystal and washing mother liquor, yield reaches about 94%.Different chlorobutane cleaning solvent reclaims.The PM value of the ε-caprolactam obtained is 180s, E value < 0.6.
Hydrogenation reaction: get the 99.98% hexanolactam crystal of 40g after different chlorobutane solvent wash, be added in 200ml reactor, add water 100g, then add 0.2g amorphous nickel hydrogenation catalyst (the industrial trade mark is SRNA-4, and Hunan Jianchang Petrochemical Co., Ltd produces), be heated to about 90 DEG C, pass into hydrogen, hydrogen flowing quantity controls at 0.6L/min, and reaction pressure maintains 7atm, the epsilon-caprolactam water solution that crystallization is gone out contacts with hydrogen, reacts 1 hour.Triple effect evaporation, and underpressure distillation under about 1mmHg condition, obtain caprolactam product.Analyze the caprolactam product quality obtained, PM value is 45000s, E value < 0.03, is the hexanolactam finished product of purity more than 99.995%, meets Industrial products requirement.
Claims (30)
1. the method for the thick product of crystallization ε-caprolactam, it is characterized in that the method comprises and will contain the halohydrocarbon solution of the thick product of ε-caprolactam and the step of crystal seed contact pairs, said contact pairs 45 ~ 62 DEG C of temperature range constant temperature in the Metastable zone of the halohydrocarbon solution containing the thick product of ε-caprolactam carry out, obtain hexanolactam crystal grain, again through solid-liquid separation, reclaim hexanolactam crystal, wherein said halohydrocarbon is selected from positive chloropropane, different chloropropane, n-propylcarbinyl chloride, secondary chlorobutane, different chlorobutane, three grades of chlorobutanes, n-Propyl Bromide, different N-PROPYLE BROMIDE, 1-n-butyl bromide, one or more in 2-n-butyl bromide, said crystal seed is 2 ~ 80 object hexanolactam particles of 1 ~ 15 heavy % accounting for the thick product of ε-caprolactam.
2., according to the process of claim 1 wherein, in the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1:1 ~ 10.
3. according to the method for claim 2, wherein, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1:1.2 ~ 8.
4. according to the method for claim 3, wherein, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1:2 ~ 5.
5. according to the method for one of Claims 1 to 4, wherein, the thick product of said ε-caprolactam carries out vapor phase beckmann rearrangement reaction by the zeolite [molecular sieve of cyclohexanone-oxime and MFI topology, then obtain after distilling out reaction solvent.
6., according to the method for one of Claims 1 to 4, wherein, in the thick product of said ε-caprolactam, hexanolactam purity is 99.0 ~ 99.6 heavy %.
7., according to the process of claim 1 wherein, said crystal seed is 10 ~ 60 object hexanolactam particles.
8., according to the process of claim 1 wherein, said crystal seed is 20 ~ 40 object hexanolactam particles.
9. according to the process of claim 1 wherein, said crystal seed is 40 ~ 60 object hexanolactam particles, accounts for 1 ~ 5 heavy % of the thick product of ε-caprolactam.
10. according to the method for claim 9, wherein, said crystal seed accounts for 2 ~ 4 heavy % of the thick product of ε-caprolactam.
11. according to the process of claim 1 wherein, said crystal seed is 20 ~ 40 object hexanolactam particles, accounts for 5 ~ 10 heavy % of the thick product of ε-caprolactam.
12. according to the method for claim 11, and wherein, said crystal seed accounts for 6 ~ 9 heavy % of the thick product of ε-caprolactam.
13. according to the process of claim 1 wherein, said crystal seed is 6 ~ 20 object hexanolactam particles, and it accounts for 10 ~ 15 heavy % of the thick product of ε-caprolactam.
14. according to the method for claim 13, and wherein, said crystal seed accounts for 11 ~ 14 heavy % of the thick product of ε-caprolactam.
15. according to the process of claim 1 wherein, saidly the step of crystal seed with the halohydrocarbon solution contact pairs that is in the thick product of ε-caprolactam in Metastable zone carried out repeatedly.
The preparation method of 16. 1 kinds of hexanolactams, comprises the mixed solution of ε-caprolactam and the reaction solvent obtained by Beckmann rearrangement through distilling the step obtaining the thick product of ε-caprolactam, the step of crystallization, solvent wash after crystallization, be separated the step obtaining ε-caprolactam crystal, exist at hydrogenation catalyst, make the step that ε-caprolactam contacts with hydrogen, and finally obtain the step of ε-caprolactam finished product, it is characterized in that in the step of said crystallization, comprise crystal seed and halohydrocarbon solution 45 ~ 62 DEG C of temperature range constant temperature contact pairs being in the thick product of ε-caprolactam in Metastable zone, obtain hexanolactam crystal grain, again through solid-liquid separation, reclaim the process of hexanolactam crystal, wherein said halohydrocarbon is selected from positive chloropropane, different chloropropane, n-propylcarbinyl chloride, secondary chlorobutane, different chlorobutane, three grades of chlorobutanes, n-Propyl Bromide, different N-PROPYLE BROMIDE, 1-n-butyl bromide, one or more in 2-n-butyl bromide, said crystal seed is 2 ~ 80 object hexanolactam particles of 1 ~ 15 heavy % accounting for the thick product of ε-caprolactam.
17. according to the method for claim 16, and wherein, in the halohydrocarbon solution of the thick product of said ε-caprolactam, the part by weight of the thick product of ε-caprolactam and halohydrocarbon is 1:1 ~ 10.
18. according to the method for claim 17, and wherein, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1:1.2 ~ 8.
19. according to the method for claim 18, and wherein, the part by weight of the thick product of said ε-caprolactam and halohydrocarbon is 1:2 ~ 5.
20. according to the method for claim 16, and wherein, the thick product of said ε-caprolactam carries out vapor phase beckmann rearrangement reaction by the zeolite [molecular sieve of cyclohexanone-oxime and MFI topology, then obtain after distilling out reaction solvent.
21. according to the method for claim 16, and wherein, in the thick product of said ε-caprolactam, hexanolactam purity is 99.0 ~ 99.6 heavy %.
22. according to the method for claim 16, and wherein, said crystal seed is 20 ~ 60 object hexanolactam particles.
23. according to the method for claim 22, and wherein, said crystal seed is 20 ~ 40 object hexanolactam particles.
24. according to the method for claim 16, and wherein, said crystal seed is 40 ~ 60 object hexanolactam particles, accounts for 1 ~ 5 heavy % of the thick product of ε-caprolactam.
25. according to the method for claim 24, and wherein, said crystal seed accounts for 2 ~ 4 heavy % of the thick product of ε-caprolactam.
26. according to the method for claim 16, and wherein, said crystal seed is 20 ~ 40 object hexanolactam particles, accounts for 5 ~ 10 heavy % of the thick product of ε-caprolactam.
27. according to the method for claim 26, and wherein said crystal seed accounts for 6 ~ 9 heavy % of the thick product of ε-caprolactam.
28. according to the method for claim 16, and wherein, said crystal seed is 6 ~ 20 object hexanolactam particles, accounts for 10 ~ 15 heavy % of the thick product of ε-caprolactam.
29. according to the method for claim 28, and wherein, said crystal seed accounts for 11 ~ 14 heavy % of the thick product of ε-caprolactam.
30. according to the method for claim 16, wherein, saidly the process that crystal seed contacts with the halohydrocarbon solution of the thick product of the ε-caprolactam be in Metastable zone to be carried out repeatedly.
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| WO2005030730A1 (en) * | 2003-09-29 | 2005-04-07 | Yamakawa Chemical Industry Co., Ltd. | PROCESS FOR PRODUCING OPTICALLY ACTIVE α-AMINO-ϵ-CAPROLACTAM OR SALT THEREOF AND INTERMEDIATE FOR THE PRODUCTION |
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