JPS6149305B2 - - Google Patents
Info
- Publication number
- JPS6149305B2 JPS6149305B2 JP16010878A JP16010878A JPS6149305B2 JP S6149305 B2 JPS6149305 B2 JP S6149305B2 JP 16010878 A JP16010878 A JP 16010878A JP 16010878 A JP16010878 A JP 16010878A JP S6149305 B2 JPS6149305 B2 JP S6149305B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction product
- toluene
- pxa
- fraction
- thermal decomposition
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- YKHZGLKQBYTRHO-UHFFFAOYSA-N 11-cyanoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCC#N YKHZGLKQBYTRHO-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- -1 cyclic imides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BUOSDFMMAQZHPV-UHFFFAOYSA-N 2-cyanoundecanoic acid Chemical compound CCCCCCCCCC(C#N)C(O)=O BUOSDFMMAQZHPV-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、１，1′―パーオキシジシクロヘキシ
ルアミン（以下、PXAと略記する）の熱分解反
応生成物からε―カプロラクタム（以下、LCと
略記する）を回収する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for recovering ε-caprolactam (hereinafter abbreviated as LC) from a thermal decomposition reaction product of 1,1'-peroxydicyclohexylamine (hereinafter abbreviated as PXA). It is related to.
西ドイツ特許第2038956号明細書には、PXAを
水蒸気とともに300〜1000℃の温度範囲において
熱分解して、ナイロン12の原料中間体である11―
シアノウンデカン酸を得る方法が提案されてい
る。しかしながら、PXAの熱分解反応生成物中
には、11―シアノウンデカン酸の他に、LC、シ
クロヘキサノン、飽和および不飽和のカルボン酸
類およびニトリル類、環状イミド類などが含まれ
ており、この反応生成物は通常、暗黒色ないしは
黒褐色に着色している。 West German Patent No. 2038956 discloses that PXA is thermally decomposed together with water vapor in a temperature range of 300 to 1000°C to produce 11-, which is a raw material intermediate for nylon-12.
A method for obtaining cyanoundecanoic acid has been proposed. However, in addition to 11-cyanoundecanoic acid, the thermal decomposition reaction products of PXA include LC, cyclohexanone, saturated and unsaturated carboxylic acids and nitriles, cyclic imides, etc. The objects are usually dark black or dark brown in color.
そこで、本発明者らは、PXAの熱分解反応生
成物から11―シアノウンデカン酸を主に含む油層
を分離した後の水層から、ナイロン６の原料中間
体として使用可能な高純度のLCを回収する方法
について鋭意検討した結果、本発明に到達した。
すなわち、本発明は、PXAを水蒸気とともに300
〜1000℃の温度範囲で熱分解して得られる反応生
成物からLCを回収する方法において、(A)前記反
応生成物を油層と水層とに分液する工程；(B)前記
油層を水で抽出した抽出液を前記水層と混合する
工程；(C)この混合液を濃縮後、蒸留してLC留分
を得る工程；および(D)得られたLC留分をトルエ
ンより晶析分離する工程；からなることを特徴と
するLCの回収方法に関するものである。 Therefore, the present inventors extracted high-purity LC that can be used as a raw material intermediate for nylon 6 from the aqueous layer after separating the oil layer mainly containing 11-cyanoundecanoic acid from the thermal decomposition reaction product of PXA. As a result of intensive study on the method of recovery, the present invention was arrived at.
That is, the present invention combines PXA with water vapor at 300%
In a method for recovering LC from a reaction product obtained by thermal decomposition in a temperature range of ~1000°C, (A) separating the reaction product into an oil layer and an aqueous layer; (B) separating the oil layer into an aqueous layer; A step of mixing the extracted liquid with the aqueous layer; (C) a step of concentrating this mixed liquid and then distilling it to obtain an LC fraction; and (D) a step of crystallizing and separating the obtained LC fraction from toluene. The present invention relates to a method for recovering LC, characterized by comprising the steps of:
本発明の方法に使用する熱分解反応生成物は、
PXAを水蒸気とともに、場合によつてはトルエ
ンを希釈剤として用いて、300〜1000℃の温度範
囲で熱分解して得られたものであり、前記熱分解
反応生成物中には、PXAの50〜60wt％の収率に
相当する11―シアノウンデカン酸、同じく10〜
20wt％の収率に相当するシクロヘキサノン、同
じく10〜20wt％の収率に相当するLCの他に、同
じく10〜20wt％の収率に相当する飽和および不
飽和のカルボン酸類およびニトリル類、環状イミ
ド類等が含まれている。 The thermal decomposition reaction product used in the method of the present invention is
It is obtained by thermally decomposing PXA together with water vapor and in some cases using toluene as a diluent in the temperature range of 300 to 1000℃, and the thermal decomposition reaction product contains 50% of PXA. 11-cyanoundecanoic acid, corresponding to a yield of ~60 wt%, also 10 ~
Cyclohexanone corresponding to a yield of 20 wt%, LC also corresponding to a yield of 10 to 20 wt%, as well as saturated and unsaturated carboxylic acids and nitrites, cyclic imides corresponding to a yield of 10 to 20 wt%. Contains various types, etc.
(A) 工程
このような成分組成を有するPXAの熱分解反
応生成物を、11―シアノウンデカン酸を主に含有
する油層と、LCを主に含有する水層とに分液す
る。なお前記水層中に含まれるPXAの熱分解反
応生成物の副生物であるシクロヘキサノンは、場
合によつてはトルエンのような有機溶剤で抽出、
除去してもよい。(A) Process The thermal decomposition reaction product of PXA having such a component composition is separated into an oil layer mainly containing 11-cyanoundecanoic acid and an aqueous layer mainly containing LC. Note that cyclohexanone, which is a byproduct of the thermal decomposition reaction product of PXA contained in the aqueous layer, may be extracted with an organic solvent such as toluene in some cases.
May be removed.
(B) 工程
(A)工程で分液された11―シアノウンデカン酸を
主に含有する油層を水と接触させ、前記油層中に
含まれる少量のLCを抽出し、この抽出液を(A)工
程で分液されたLCを主に含有する水層と混合す
る。(B) Step (A) The oil layer containing mainly 11-cyanoundecanoic acid separated in step (A) is brought into contact with water, a small amount of LC contained in the oil layer is extracted, and this extract is added to (A). The LC separated in the process is mixed with an aqueous layer mainly containing the LC.
(C) 工程
(B)工程で得られたLCを主に含有する混合液を
加熱して、混合液中に含まれる微量の低沸点物お
よび水を蒸発、除去し、前記混合液を濃縮する。
濃縮に必要な熱量は熱分解生成物と熱交換させる
のが経済的である。さらに、この濃縮液から実質
的に水を除去するためには、10〜100cmHgの減圧
下で80〜150℃に加熱する。このようにして、主
にLCを含有する缶液を得、ついでこの缶液を２
〜10mmHgの減圧下で120〜200℃に加熱してLCを
留出させる。(C) Step (B) Heat the mixed liquid mainly containing LC obtained in step (B) to evaporate and remove trace amounts of low-boiling substances and water contained in the mixed liquid, and concentrate the mixed liquid. .
It is economical to exchange the heat required for concentration with the thermal decomposition product. Furthermore, in order to substantially remove water from this concentrate, it is heated to 80-150° C. under a reduced pressure of 10-100 cmHg. In this way, a can liquid containing mainly LC is obtained, and then this can liquid is
The LC is distilled off by heating to 120-200 °C under a vacuum of ~10 mmHg.
(D) 工程
(C)工程で得られたLC留分にトルエンを加えて
０〜30℃に保持して晶析させLCを結晶として分
離し、トルエンで洗浄をする。晶析に使用するト
ルエン量は、LC留分１重量部に対して0.2〜２重
量部の割合が適当である。また、一旦、LCの晶
析に使用したトルエン母液を回収して、再びLC
留分の晶析に循環使用することができる。このよ
うにトルエン母液を繰返し使用すること、および
トルエン洗浄を行うことはLC結晶の品質および
回収量の向上に有効である。(D) Step Toluene is added to the LC fraction obtained in step (C) and kept at 0 to 30° C. to crystallize, and LC is separated as crystals and washed with toluene. The appropriate amount of toluene used for crystallization is 0.2 to 2 parts by weight per 1 part by weight of the LC fraction. In addition, once the toluene mother liquor used for LC crystallization is recovered, the LC crystallization is performed again.
It can be recycled for crystallization of the fraction. Repeated use of the toluene mother liquor and washing with toluene in this manner are effective in improving the quality and recovery amount of LC crystals.
本発明の方法を実施することによつて、PXA
の熱分解反応により11―シアノウンデカン酸を生
成する際に得られる反応生成物から、ナイロン６
の原料中間体として使用し得る純度を有するLC
を回収、取得することができる。 By carrying out the method of the present invention, PXA
Nylon 6 is produced from the reaction product obtained when 11-cyanoundecanoic acid is produced by the thermal decomposition reaction of
LC with a purity that can be used as a raw material intermediate for
can be collected and obtained.
次に実施例において、後記図面に従つて本発明
の方法をさらに具体的に説明する。 Next, in Examples, the method of the present invention will be explained in more detail with reference to the drawings described later.
実施例
PXAを水蒸気によつて熱分解して得た次の成
分組成を有する反応生成物１を、LCを主に含有
する水層２と、11―シアノウンデカン酸を主に含
有する油層３とに分液した。Example A reaction product 1 having the following component composition obtained by thermally decomposing PXA with steam is separated into an aqueous layer 2 mainly containing LC and an oil layer 3 mainly containing 11-cyanoundecanoic acid. It was separated into two liquids.
PXAの熱分解反応生成物の成分組成
11―シアノウンデカン酸 352部
LC 93
シクロヘキサノン 177
水 2717 その他 123
計 3462部
前記油層３に水４を加え、油層中に含まれてい
るLCを抽出し、この抽出液を前記水層２と混合
した。この混合液５を加熱して水を蒸発後、80
℃／80mmHg、ついで80〜120℃／10mmHgで減圧
蒸留して水およびシクロヘキサノン等の低沸点物
６を留去し、缶液として濃縮LC７110部を得た。
この濃縮LCを180℃／５mmHgで減圧蒸留してLC
留分９85部と釜残９に分離した。このLC留分に
トルエン１０68部を加えて60℃で溶解後、約１時
間かけて10℃に冷却し、晶析して、生じるスラリ
ー液を遠心分離機にかけLC結晶１２とトルエン
母液１１に分離した。前記LC結晶は遠心分離機
中に残し、５℃に保持されたトルエン43部で洗浄
し、このようにして得られたLC結晶を50℃／２
mmHgで６時間乾燥した。なお、前記トルエン母
液はさらにLC留分を溶解、晶析するために循環
した。 Component composition of thermal decomposition reaction product of PXA 11-Cyanoundecanoic acid 352 parts LC 93 Cyclohexanone 177 Water 2717 Others 123 total 3462 parts Water 4 is added to the oil layer 3 to extract the LC contained in the oil layer. The extract was mixed with the aqueous layer 2. After heating this mixture 5 to evaporate water,
C/80 mmHg and then distilled under reduced pressure at 80-120 C/10 mmHg to remove water and low-boiling substances 6 such as cyclohexanone to obtain 7110 parts of concentrated LC as a bottom liquid.
This concentrated LC was distilled under reduced pressure at 180℃/5mmHg and LC
It was separated into 985 parts of fraction and 9 parts of bottom. Add 1068 parts of toluene to this LC fraction, dissolve at 60°C, cool to 10°C over about 1 hour, crystallize, and centrifuge the resulting slurry liquid to separate it into LC crystals 12 and toluene mother liquor 11. did. The LC crystals were left in the centrifuge and washed with 43 parts of toluene kept at 5°C, and the LC crystals thus obtained were washed at 50°C/2
Dry at mmHg for 6 hours. The toluene mother liquor was further circulated to dissolve and crystallize the LC fraction.
乾燥したLC結晶の純度は次のとおりである。 The purity of the dried LC crystals is as follows.
凝固点 67〜68℃ 揮発性塩基類含有量 30ppm 紫外線透過率 98％ 0.1N過マンガン酸カリ消費量 25c.c.／KgFreezing point 67-68℃ Volatile base content 30ppm UV transmittance 98% 0.1N potassium permanganate consumption 25c.c./Kg
図面は本発明の方法を示す系統図である。 The drawing is a system diagram illustrating the method of the invention.
Claims (1)
を水蒸気とともに300〜1000℃の温度範囲で熱分
解して得られる反応生成物からε―カプロラクタ
ムを回収する方法において、(A)前記反応生成物を
油層と水層とに分液する工程；(B)前記油層を水で
抽出した抽出液を前記水層と混合する工程；(C)こ
の混合液を濃縮後、蒸留してε―カプロラクタム
留分を得る工程；および(D)得られたε―カプロラ
クタム留分をトルエンより晶析分離する工程；か
らなることを特徴とするε―カプロラクタムの回
収方法。1. In a method for recovering ε-caprolactam from a reaction product obtained by thermally decomposing 1,1'-peroxydicyclohexylamine together with water vapor at a temperature range of 300 to 1000°C, (A) the reaction product is combined with an oil layer. (B) A step of extracting the oil layer with water and mixing the extract with the aqueous layer; (C) Concentrating this mixture and then distilling it to obtain an ε-caprolactam fraction and (D) crystallizing and separating the obtained ε-caprolactam fraction from toluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16010878A JPS5587767A (en) | 1978-12-27 | 1978-12-27 | Recovery of epsilon-caprolactam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16010878A JPS5587767A (en) | 1978-12-27 | 1978-12-27 | Recovery of epsilon-caprolactam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5587767A JPS5587767A (en) | 1980-07-02 |
| JPS6149305B2 true JPS6149305B2 (en) | 1986-10-29 |
Family
ID=15708016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16010878A Granted JPS5587767A (en) | 1978-12-27 | 1978-12-27 | Recovery of epsilon-caprolactam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5587767A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01227608A (en) * | 1988-03-07 | 1989-09-11 | Nippon Telegr & Teleph Corp <Ntt> | Cable connecting double box |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678754B (en) * | 2017-10-19 | 2021-09-07 | 万华化学集团股份有限公司 | Preparation method of 11-cyanoundecanoic acid |
-
1978
- 1978-12-27 JP JP16010878A patent/JPS5587767A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01227608A (en) * | 1988-03-07 | 1989-09-11 | Nippon Telegr & Teleph Corp <Ntt> | Cable connecting double box |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5587767A (en) | 1980-07-02 |
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