WO2013058121A1 - ε－カプロラクタムの製造方法 - Google Patents

ε－カプロラクタムの製造方法 Download PDF

Info

Publication number
WO2013058121A1
WO2013058121A1 PCT/JP2012/075812 JP2012075812W WO2013058121A1 WO 2013058121 A1 WO2013058121 A1 WO 2013058121A1 JP 2012075812 W JP2012075812 W JP 2012075812W WO 2013058121 A1 WO2013058121 A1 WO 2013058121A1
Authority
WO
WIPO (PCT)
Prior art keywords
lower alcohol
caprolactam
moles
gas
reaction
Prior art date
Application number
PCT/JP2012/075812
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
杉田　啓介
哲也 横田
尚己 武田
Original Assignee
住友化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020147010521A priority Critical patent/KR101925168B1/ko
Priority to SG11201401106PA priority patent/SG11201401106PA/en
Priority to CN201280050518.5A priority patent/CN103889950A/zh
Priority to IN2909CHN2014 priority patent/IN2014CN02909A/en
Publication of WO2013058121A1 publication Critical patent/WO2013058121A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D223/00—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06—Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08—Oxygen atoms
    • C07D223/10—Oxygen atoms attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a process for producing ⁇ -caprolactam in which ⁇ -caprolactam is produced from cyclohexanone oxime by a gas phase reaction using a solid catalyst.
  • ⁇ -Caprolactam is an important basic chemical raw material used as a raw material for nylon and the like, and a method for producing ⁇ -caprolactam includes a step of rearranging cyclohexanone oxime (Beckmann rearrangement) by a gas phase reaction using a solid catalyst.
  • a method for improving the reaction rate of cyclohexanone oxime, the selectivity of ⁇ -caprolactam and the catalyst life by carrying out the rearrangement reaction in the presence of a lower alcohol is disclosed (see Patent Document 1). According to this method, even when the reaction rate of cyclohexanone oxime is substantially near 100%, ⁇ -caprolactam can be obtained with extremely high selectivity, and the life of the catalyst is remarkably improved.
  • the lower alcohol used in the rearrangement reaction can be recovered after the reaction and reused, which is an important process for producing ⁇ -caprolactam at low cost. Become.
  • the lower alcohol that is recovered and reused can be a major cause of contamination of the reaction system. Therefore, it is necessary to reduce such impurities.
  • ⁇ -caprolactam can be further improved in yield by reducing the amount of impurities.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing ⁇ -caprolactam having excellent reaction rate and selectivity in the rearrangement reaction of cyclohexanone oxime.
  • the present invention provides a method for producing ⁇ -caprolactam, which produces ⁇ -caprolactam from cyclohexanone oxime by a gas phase reaction using a solid catalyst in the presence of a lower alcohol.
  • a method for producing ⁇ -caprolactam comprising, as alcohol, lower alcohol recovered from the reaction mixture of the gas phase reaction, and adjusting the amounts of water, ammonia and amines to the following values during the gas phase reaction: I will provide a.
  • a gas mainly composed of a lower alcohol is distilled and separated from the reaction mixture, and a part thereof is cooled and condensed, and then further distilled. Is preferably at least part of the recovered lower alcohol.
  • the solid catalyst is preferably a zeolite.
  • the manufacturing method of the epsilon caprolactam excellent in the reaction rate and selectivity in the rearrangement reaction of cyclohexanone oxime can be provided. Further, by reusing the recovered lower alcohol, the amount of industrial waste can be reduced, and the burden on the environment can be reduced.
  • FIG. 3 is a flowchart showing manufacturing steps in a method for manufacturing ⁇ -caprolactam according to an embodiment of the present invention.
  • the method for producing ⁇ -caprolactam according to the present invention is a method for producing ⁇ -caprolactam in which ⁇ -caprolactam is produced from cyclohexanone oxime by a gas phase reaction using a solid catalyst in the presence of a lower alcohol.
  • the lower alcohol to be coexisted includes a lower alcohol recovered from the reaction mixture of the gas phase reaction (hereinafter sometimes referred to as “recovered lower alcohol”), and the amount of water, ammonia and amines during the gas phase reaction. Is adjusted to the following value.
  • the present invention relates to the following.
  • a gas phase reaction in which cyclohexanone oxime is brought into contact with a solid catalyst in the presence of a lower alcohol to convert cyclohexanone oxime to ⁇ -caprolactam, and water, ammonia and amines coexisting in the gas phase reaction system. Adjusting the amount to the following values (1) to (3), wherein the lower alcohol includes a recovered lower alcohol recovered from a reaction mixture obtained by a gas phase reaction: , ⁇ -caprolactam production method.
  • FIG. 1 is a flowchart showing a production process in a method for producing ⁇ -caprolactam according to an embodiment of the present invention.
  • the first distillation step (3) in which the reaction gas 12 is cooled, the high-boiling component 13 is separated from the reaction solution, and a mixed gas 14 of ⁇ -caprolactam, lower alcohol and inert gas is obtained as the distillate,
  • a lower alcohol separation step (4) in which a lower alcohol and an inert gas are separated from the gas 14 to obtain a crude lower alcohol 15 containing an inert gas and a crude ⁇ -caprolactam mixture 18 mainly composed of crude ⁇ -caprolactam.
  • cyclohexanone oxime is evaporated in the presence of inert gas 8, lower alcohol 9 and water 10 to obtain a raw material gas containing cyclohexanone oxime 7, inert gas 8, lower alcohol 9 and water 10.
  • Evaporation step (1) A gas phase reaction in which the raw material gas is brought into contact with a solid catalyst is performed to convert the cyclohexanone oxime 7 into ⁇ -caprolactam, thereby obtaining a reaction gas 12 containing ⁇ -caprolactam, a lower alcohol and an inert gas.
  • Reaction step (2) The reaction gas 12 is cooled, the high-boiling component 13 as an impurity is separated from the reaction solution obtained by cooling, and a mixed gas 14 containing ⁇ -caprolactam, a lower alcohol and an inert gas is obtained.
  • the 2nd distillation process (5) may be comprised from the some distillation process. More specifically, it is as follows.
  • cyclohexanone oxime 7, inert gas 8, lower alcohol 9 and water 10 are supplied to the evaporator 1, and cyclohexanone oxime 7 is heated and evaporated in the presence of the lower alcohol 9 and water 10, A raw material gas 11 containing cyclohexanone oxime 7 and lower alcohol 9 and water 10 is obtained. At this time, water can be mixed with cyclohexanone oxime in advance.
  • the raw material gas 11 obtained in the evaporation step (1) is supplied to the reactor 2, the raw material gas 11 is brought into contact with the solid catalyst, and cyclohexanone oxime is subjected to a Beckmann rearrangement reaction for gas phase reaction.
  • a reaction gas 12 (hereinafter also referred to as a reaction mixture).
  • the reaction gas 12 includes ⁇ -caprolactam, a lower alcohol, and an inert gas.
  • the gas phase reaction means that cyclohexanone oxime 7 is reacted with a raw material gas containing lower alcohol 9 and water 10 in contact with a solid catalyst, and is a concept different from a liquid phase reaction.
  • the reaction gas 12 obtained in the reaction step (2) is supplied to the first distillation column 3 for cooling, and the reaction solution obtained by cooling is used as a high impurity as an impurity.
  • the boiling point component 13 is separated to obtain a mixed gas 14 containing ⁇ -caprolactam, a lower alcohol and an inert gas.
  • the inert gas includes nitrogen, argon, carbon dioxide and the like.
  • the mixed gas 14 obtained in the first distillation step (3) is supplied to the lower alcohol recovery tower 4, and the crude gas containing the lower alcohol and the inert gas is supplied from the mixed gas 14. Separate the alcohol 15 and the crude ⁇ -caprolactam mixture 18 containing ⁇ -caprolactam.
  • the amount of water contained in the crude lower alcohol 15 containing an inert gas can be adjusted by distillation conditions.
  • the crude ⁇ -caprolactam mixture 18 obtained in the lower alcohol separation step (4) is supplied to the second distillation column 5, and the crude ⁇ -caprolactam mixture 18 is reduced as impurities as impurities.
  • the boiling component 20 and the high boiling component 19 are separated to obtain crude ⁇ -caprolactam 21.
  • the low boiling point component means a component having a boiling point lower than that of ⁇ -caprolactam.
  • the high boiling point component means a component having a boiling point higher than that of ⁇ -caprolactam.
  • a part or the whole amount of the crude lower alcohol 15 obtained in the lower alcohol separation step (4) is supplied to the lower alcohol purification device 6 to remove impurities 16 such as ammonia and amines.
  • impurities 16 such as ammonia and amines.
  • a recovered lower alcohol (purified lower alcohol) 17 containing an inert gas is obtained.
  • the recovered lower alcohol 17 is supplied to the evaporator 1 and reused after the evaporation step (1).
  • FIG. 1 is an example, and this invention is not limited to what is shown in FIG.
  • the present invention will be described focusing on a gas phase reaction using a recovered lower alcohol and a solid catalyst in the presence of the lower alcohol.
  • the solid catalyst is a solid catalyst for producing ⁇ -caprolactam used when cyclohexanone oxime is converted into ⁇ -caprolactam by Beckmann rearrangement reaction in the gas phase.
  • a solid catalyst various types have been conventionally proposed. Among them, zeolite is preferable, pentasil type zeolite is more preferable, and MFI zeolite is particularly preferable.
  • the zeolite may be crystalline silica whose skeleton is substantially composed of silicon and oxygen, or a crystalline metallo that further contains elements other than silicon and oxygen, such as metal elements, as elements constituting the skeleton. It may be a silicate or the like.
  • elements other than silicon and oxygen include Be, B, Al, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Ga, Ge, Zr, Nb, Sb, La, Hf, and Bi. Etc., and two or more of these may be included as necessary.
  • the atomic ratio of silicon to these elements is preferably 50 or more, more preferably 500 or more.
  • the zeolite is subjected to hydrothermal synthesis using, for example, a silicon compound, a quaternary ammonium compound, water and, if necessary, a metal compound as a raw material, and the obtained crystals are dried and calcined, and then contacted with ammonia or an ammonium salt. It can be suitably prepared by treating and then drying.
  • the particle size of the solid catalyst is preferably 0.0001 to 5 mm, and more preferably 0.001 to 3 mm.
  • the solid catalyst may be, for example, a molded body substantially consisting of only the catalyst component, or may be one in which the catalyst component is supported on a carrier.
  • the lower alcohol preferably has 6 or less carbon atoms, specifically, methanol, ethanol, 1-propanol (n-propyl alcohol), 2-propanol (isopropyl alcohol), 1-butanol (n-butyl). Alcohol), 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), 1-pentanol (n-pentyl alcohol), 1-hexanol (n-hexyl alcohol), and 2,2 , 2-trifluoroethanol.
  • methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol are preferable, and methanol and ethanol are more preferable because they are particularly excellent in improving selectivity of ⁇ -caprolactam and catalyst life.
  • Methanol and ethanol are most preferable from an industrial viewpoint.
  • the selectivity means the production rate of ⁇ -caprolactam in the reaction product.
  • the lower alcohol to be coexistent may be one kind or two or more kinds. In the case of two or more kinds, the combination and ratio can be arbitrarily selected. However, in consideration of handling properties, the lower alcohol is preferably one kind.
  • the gas phase reaction is carried out, lower alcohol is recovered from the reaction mixture (for example, reaction gas 12 in FIG. 1) obtained thereby, and this recovered lower alcohol (for example, recovered lower alcohol 17 in FIG. ) Is newly used in the gas phase reaction and reused. That is, the lower alcohol that coexists in the gas phase reaction includes recovered lower alcohol.
  • Various kinds of recovered lower alcohols can be used depending on the recovery method, and one kind may be used alone, or two or more kinds may be used in combination. When using 2 or more types together, the combination and ratio can be selected arbitrarily.
  • the recovered lower alcohol may be used, or the recovered lower alcohol and the lower alcohol that is not recovered (for example, the lower alcohol 9 in FIG. 1, hereinafter referred to as “non-recovered lower alcohol”). May be used in combination.
  • the amount of impurities can be easily reduced to the target amount with only the recovered lower alcohol.
  • recovered lower alcohols usually have a higher impurity content than non-recovered lower alcohols, and depending on their purity, more purification operations may be required to reduce these impurities.
  • the amount of impurities during the gas phase reaction can be easily reduced even if the purification operation is omitted or reduced.
  • the recovered lower alcohol can be obtained, for example, by separating a gas mainly containing the lower alcohol (for example, the crude lower alcohol 15 in FIG. 1) from the reaction mixture of the gas phase reaction.
  • the gas mainly composed of lower alcohol can be separated from the reaction mixture by distillation, for example.
  • the lower alcohol obtained by distillation is also referred to as distilled lower alcohol 15.
  • the recovered lower alcohol or the recovered lower alcohol is previously contained using the same reactor.
  • a separate reaction vessel is used to lower alcohol.
  • a gas phase reaction in which cyclohexanone oxime is contacted with a solid catalyst to convert cyclohexanone oxime into ⁇ -caprolactam.
  • the separated gas gas containing a lower alcohol as a main component
  • the gas 15 containing lower alcohol as a main component can be purified by reducing impurities by distillation after being introduced into a gas absorption tower or the like and condensed by cooling, for example.
  • Condensing means that a gas mainly composed of lower alcohol is made into a liquid mixture mainly composed of lower alcohol.
  • the recovered lower alcohol is preferably used by mixing the crude lower alcohol 15 and the purified lower alcohol 17 obtained by condensation and distillation as described above.
  • the purified lower alcohol is obtained by distilling a reaction mixture obtained by a gas phase reaction, separating a gas containing the lower alcohol as a main component, cooling and condensing a part of the gas, After obtaining the liquid mixture which has a main component, it is preferable to manufacture by the method further including distilling the said liquid mixture and obtaining distilled lower alcohol.
  • a gas mainly composed of a lower alcohol is separated from the reaction mixture of the gas phase reaction by distillation, and after cooling and condensing a part thereof, the gas obtained by further distillation is obtained. It is preferable to use at least a part of the recovered lower alcohol.
  • the lower alcohol has a mass ratio to the cyclohexanone oxime (the amount of lower alcohol (mass) / the amount of cyclohexanone oxime (mass)) in the gas phase reaction, preferably 0.1 to 20, more preferably 0.1 to 10. In particular, it is preferable to coexist in the reaction system so as to be 0.3 to 8.
  • the molar percentage of ammonia (a) ([ammonia (number of moles) / lower alcohol (number of moles)] ⁇ 100) in the reaction system during the gas phase reaction is 0 or more and less than 14, and 13 or less. Is preferred.
  • the mole percentage (b) of water ([water (number of moles) / lower alcohol (number of moles)] ⁇ 100) in the reaction system during the gas phase reaction is greater than 0 and less than 11, and 10 or less. It is preferable. Further, water is a necessary component for smoothly proceeding the rearrangement reaction. From such a viewpoint, the amount of water in the reaction system during the gas phase reaction is preferably 0.06 mol or more with respect to 1 mol of cyclohexanone oxime.
  • the amines are those in which a hydrogen atom of ammonia (NH 3 ) is substituted with a hydrocarbon group, and may be any of primary amines, secondary amines and tertiary amines, and any of monoamines and polyamines. Good. Representative amines include monomethylamine for primary amines, dimethylamine for secondary amines, and trimethylamine for tertiary amines.
  • ammonia is produced at the time of hydrolysis of cyclohexanone oxime, and amines are expected to react with ammonia and lower alcohols.
  • the mole percentage (c) of amines ([amines (number of moles) / lower alcohol (number of moles)] ⁇ 100) in the reaction system during the gas phase reaction is 0 or more and less than 7.5, 7 The following is preferable.
  • the amount of water, ammonia and amines in the reaction system can be easily adjusted by adjusting the amount or purity of the recovered lower alcohol.
  • the mixing ratio of recovered lower alcohol and non-recovered lower alcohol is preferably 10: 0 to 10:10, and 10: 0 to 10: 2 is more preferable.
  • the gas of non-recovered lower alcohol is appropriately supplied into the reaction system while detecting the amounts of water, ammonia and amines.
  • the method of adjusting the quantity of water, ammonia, and amines etc. is mentioned.
  • the amount of water can be measured by a known method such as the Karl Fischer method, and the amounts of ammonia and amines can be measured by an ion chromatography method.
  • a molecular oxygen-containing gas may coexist in the reaction system. It is economical and preferable to use air as the molecular oxygen-containing gas.
  • the molecular oxygen concentration is preferably outside the explosion composition range.
  • the amount of molecular oxygen in the reaction system during the gas phase reaction is preferably 0.1 to 10 mol, more preferably 0.3 to 5 mol, per 1 mol of cyclohexanone oxime.
  • the gas phase reaction can be carried out by a normal fixed bed type, fluidized bed type or moving bed type gas phase contact reaction.
  • the raw material cyclohexanone oxime reacts when brought into contact with the catalyst layer in a gaseous state, but the lower alcohol may be preliminarily mixed with cyclohexanone oxime in the gaseous state, or the cyclohexanone oxime is supplied separately to the reactor. May be.
  • the molecular oxygen-containing gas can be supplied by mixing with a lower alcohol and cyclohexanone oxime, or mixed with a lower alcohol, and more reactive than cyclohexanone oxime. It may be supplied upstream.
  • the gas phase reaction may be performed in the presence of a vapor of a compound inert to the reaction, such as benzene, cyclohexane, or toluene, as a diluent gas, or in the presence of an inert gas such as nitrogen or carbon dioxide. May be.
  • a compound inert to the reaction such as benzene, cyclohexane, or toluene
  • an inert gas such as nitrogen or carbon dioxide. May be.
  • the gas phase reaction is preferably performed under atmospheric pressure or under reduced pressure below atmospheric pressure.
  • the reaction temperature during the gas phase reaction is preferably 250 to 500 ° C., more preferably 300 to 450 ° C., and particularly preferably 300 to 400 ° C.
  • the reaction rate is improved, and the selectivity for ⁇ -caprolactam is further improved.
  • the amount lower than the upper limit value thermal decomposition of cyclohexanone oxime is suppressed, and the selectivity of ⁇ -caprolactam is further improved.
  • the space velocity (WHSV) of cyclohexanone oxime during the gas phase reaction is preferably 0.1 to 40 h ⁇ 1 (that is, the supply rate of cyclohexanone oxime per kg of catalyst is 0.1 to 40 kg / h), More preferably, it is 2 to 20 h ⁇ 1 , and particularly preferably 0.5 to 10 h ⁇ 1 .
  • the ⁇ -caprolactam produced by the gas phase reaction can be separated from the reaction mixture by a known method.
  • the reaction product gas is cooled and condensed, and then separated by extraction, distillation, crystallization, or the like, whereby purified ⁇ -caprolactam is obtained.
  • the solid catalyst can remove and burn (burn) the carbonaceous material adhering in the gas phase reaction at a temperature of 200 to 600 ° C. with an oxygen-containing gas. it can.
  • the carbonaceous material may be removed in the presence of alcohol in an oxygen-containing gas.
  • the combustion treatment with the oxygen-containing gas may be performed at a temperature of 200 to 600 ° C. under a constant temperature condition or a condition where the temperature is raised in multiple stages.
  • oxygen-containing gas air is usually preferable, but air or oxygen diluted with an inert gas such as nitrogen, argon or carbon dioxide may be used.
  • the oxygen concentration in the oxygen-containing gas is preferably 1 to 30% by volume, more preferably 5 to 25% by volume.
  • the present invention is premised on the reuse of the recovered product from the reaction product of the rearrangement reaction as a raw material for the rearrangement reaction of cyclohexanone oxime. Then, paying attention to the impurities that can occur in the rearrangement reaction of cyclohexanone oxime, ammonia, water, and amines are identified as impurities that can inhibit this rearrangement reaction when they are excessively present, and the amount mixed in these reaction systems Are all limited to a limited range.
  • the conventional method for producing ⁇ -caprolactam in which the rearrangement reaction of cyclohexanone oxime is carried out is industrially excellent in terms of high yield.
  • the space velocity WHSV (h ⁇ 1 ) was calculated by dividing the cyclohexanone oxime supply rate (g / h) by the catalyst weight (g).
  • analysis of cyclohexanone oxime and ⁇ -caprolactam was performed by gas chromatography.
  • the reaction rate of cyclohexanone oxime and the selectivity of ⁇ -caprolactam were the number of moles of cyclohexanone oxime supplied, and the number of moles of unreacted cyclohexanone oxime.
  • Example 1 0.75 g of a silica glass reaction tube having an inner diameter of 1 cm is packed as a solid catalyst with particles having a particle size of 0.3 mm or less mainly composed of crystalline silica MFI zeolite (Si / Al atomic ratio: 147000). Then, a catalyst layer was formed and pre-heated at 340 ° C. for 1 hour under a nitrogen gas flow of 0.72 L / h.
  • Example 2 As shown in Table 1, ⁇ -caprolactam was produced in the same manner as in Example 1 except that the molar percentage (a) of ammonia was changed to 5.9 instead of 0. The yield of ⁇ -caprolactam was 95.0%.
  • Example 3 As shown in Table 1, ⁇ -caprolactam was produced in the same manner as in Example 1 except that the molar percentage (a) of ammonia was changed to 8.7 instead of 0. The yield of ⁇ -caprolactam was 95.1%.
  • Example 5 As shown in Table 1, ⁇ -caprolactam was produced in the same manner as in Example 4 except that the molar percentage (b) of water was changed to 8.3 instead of 6.4. The yield of ⁇ -caprolactam was 95.3%.
  • Example 7 As shown in Table 1, ⁇ -caprolactam was produced in the same manner as in Example 6 except that trimethylamine was used as the amine and the molar percentage (c) was 3.6 instead of 0. did. The yield of ⁇ -caprolactam was 95.6%.
  • ammonia, water and amines are selected as impurities that define the amount of contamination in the reaction system, and by limiting these amounts to a limited range, the reaction in the cyclohexanone oxime rearrangement reaction It was confirmed that the rate and selectivity can be maintained at a very high level.
  • the present invention can be used for the production of ⁇ -caprolactam by a gas phase reaction using a solid catalyst.
  • ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the epsilon caprolactam excellent in the selectivity in the rearrangement reaction of cyclohexanone oxime can be provided. Further, by reusing the recovered lower alcohol, the amount of industrial waste can be reduced, and the burden on the environment can be reduced.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Other In-Based Heterocyclic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Catalysts (AREA)
PCT/JP2012/075812 2011-10-17 2012-10-04 ε－カプロラクタムの製造方法 WO2013058121A1 (ja)

Priority Applications (4)

Application Number Priority Date Filing Date Title
KR1020147010521A KR101925168B1 (ko) 2011-10-17 2012-10-04 ε-카프로락탐의 제조 방법
SG11201401106PA SG11201401106PA (en) 2011-10-17 2012-10-04 PRODUCTION METHOD FOR e-CAPROLACTAM
CN201280050518.5A CN103889950A (zh) 2011-10-17 2012-10-04 ε-己内酰胺的制造方法
IN2909CHN2014 IN2014CN02909A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2011-10-17 2012-10-04

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011-228142 2011-10-17
JP2011228142 2011-10-17

Publications (1)

Publication Number Publication Date
WO2013058121A1 true WO2013058121A1 (ja) 2013-04-25

Family

ID=48140773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/075812 WO2013058121A1 (ja) 2011-10-17 2012-10-04 ε－カプロラクタムの製造方法

Country Status (6)

Country Link
JP (1) JP6004884B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
KR (1) KR101925168B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CN (1) CN103889950A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IN (1) IN2014CN02909A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
SG (1) SG11201401106PA (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO2013058121A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114478310B (zh) * 2022-02-24 2024-07-30 江苏扬农化工集团有限公司 一种环己酮肟的气化方法及己内酰胺的制备方法
CN114507170B (zh) * 2022-02-24 2024-06-04 江苏扬农化工集团有限公司 制备己内酰胺的方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02275850A (ja) * 1989-01-26 1990-11-09 Sumitomo Chem Co Ltd ε―カプロラクタムの製法
JPH05201966A (ja) * 1991-11-27 1993-08-10 Sumitomo Chem Co Ltd ε−カプロラクタムの製造法
JPH05201965A (ja) * 1991-11-27 1993-08-10 Sumitomo Chem Co Ltd ε−カプロラクタムの製法
JPH06107627A (ja) * 1992-10-01 1994-04-19 Sumitomo Chem Co Ltd ε−カプロラクタムの製造法及び触媒寿命向上方法
JP2002105039A (ja) * 2000-09-29 2002-04-10 Sumitomo Chem Co Ltd シクロヘキサノンオキシムの蒸発方法とこれに使用する蒸発器、ならびにε−カプロラクタムの製造方法とその製造装置
JP2002284752A (ja) * 2001-03-28 2002-10-03 Sumitomo Chem Co Ltd シクロヘキサノンオキシムの蒸発方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4968793A (en) * 1989-01-26 1990-11-06 Sumitomo Chemical Company, Limited Process for producing ε-caprolactam
KR100224333B1 (ko) * 1991-11-27 1999-10-15 고오사이 아끼오 ε-카프로락탐의 제조방법
TW213896B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1991-11-27 1993-10-01 Sumitomo Chemical Co
JP2010047499A (ja) * 2008-08-20 2010-03-04 Univ Of Tokyo ε−カプロラクタムの製造方法及びペンタシル型ゼオライトの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02275850A (ja) * 1989-01-26 1990-11-09 Sumitomo Chem Co Ltd ε―カプロラクタムの製法
JPH05201966A (ja) * 1991-11-27 1993-08-10 Sumitomo Chem Co Ltd ε−カプロラクタムの製造法
JPH05201965A (ja) * 1991-11-27 1993-08-10 Sumitomo Chem Co Ltd ε−カプロラクタムの製法
JPH06107627A (ja) * 1992-10-01 1994-04-19 Sumitomo Chem Co Ltd ε−カプロラクタムの製造法及び触媒寿命向上方法
JP2002105039A (ja) * 2000-09-29 2002-04-10 Sumitomo Chem Co Ltd シクロヘキサノンオキシムの蒸発方法とこれに使用する蒸発器、ならびにε−カプロラクタムの製造方法とその製造装置
JP2002284752A (ja) * 2001-03-28 2002-10-03 Sumitomo Chem Co Ltd シクロヘキサノンオキシムの蒸発方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MARUZEN CO., LTD.: "5 Process System no Kosei", KAGAKU PROCESS KOGAKU, 1969, pages 84 - 119 *

Also Published As

Publication number Publication date
KR20140090605A (ko) 2014-07-17
JP6004884B2 (ja) 2016-10-12
IN2014CN02909A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 2015-07-03
SG11201401106PA (en) 2014-10-30
JP2013100274A (ja) 2013-05-23
CN103889950A (zh) 2014-06-25
KR101925168B1 (ko) 2018-12-04

Similar Documents

Publication Publication Date Title
US7449600B2 (en) Process for producing cyclohexanone oxime
US6433166B2 (en) Process for producing ε-caprolactam
WO2016148200A1 (ja) ε－カプロラクタムの製造方法
US5354859A (en) ε-caprolactam
JP2616088B2 (ja) ε―カプロラクタムの製法
JP6004884B2 (ja) ε−カプロラクタムの製造方法
WO2016068061A1 (ja) アセトニトリルの製造方法
JP3254753B2 (ja) ε−カプロラクタムの製造法
JP2676895B2 (ja) ε―カプロラクタムの製造法
WO1997003956A1 (fr) PROCEDE DE PREPARATION DE ε-CAPROLACTAME
JP2002097177A (ja) イソフタロニトリルの製造方法
CN100369895C (zh) ε-己内酰胺的制造方法
EP2617680B1 (en) Method for manufacturing zeolite and method for manufacturing epsilon-caprolactam
KR100287085B1 (ko) E-카프로락탐의 제조방법
JP3221021B2 (ja) ε−カプロラクタムの製造方法
JP2971428B2 (ja) アルキルビニルエーテルの回収方法
JP3968802B2 (ja) ε−カプロラクタムの製造法
JP4239288B2 (ja) ε−カプロラクタムの製造方法
JP2008229403A (ja) ε−カプロラクタム製造用触媒の再生方法及びε−カプロラクタムの製造方法
TW200418802A (en) Purification of caprolactam
WO1994021594A1 (fr) Procede de production d'aminophenol a double substitution n,n
JPH072735A (ja) 酢酸イソプロピルの製造方法
JP2007296437A (ja) ε−カプロラクタム製造用触媒の再生方法及びε−カプロラクタムの製造方法
JPH0940640A (ja) ε−カプロラクタムの製造方法
JPH09241236A (ja) ε−カプロラクタムの製造法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12841474

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20147010521

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 12841474

Country of ref document: EP

Kind code of ref document: A1