JPH0455430B2 - - Google Patents
Info
- Publication number
- JPH0455430B2 JPH0455430B2 JP28603486A JP28603486A JPH0455430B2 JP H0455430 B2 JPH0455430 B2 JP H0455430B2 JP 28603486 A JP28603486 A JP 28603486A JP 28603486 A JP28603486 A JP 28603486A JP H0455430 B2 JPH0455430 B2 JP H0455430B2
- Authority
- JP
- Japan
- Prior art keywords
- aqueous phase
- reaction
- extraction
- extraction solvent
- recycled
- 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
- 239000008346 aqueous phase Substances 0.000 claims description 35
- 238000000605 extraction Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- YZCLSZPQXZWSCJ-UHFFFAOYSA-L [Na+].[Na+].CCO.[O-]P(=O)OP([O-])=O Chemical compound [Na+].[Na+].CCO.[O-]P(=O)OP([O-])=O YZCLSZPQXZWSCJ-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960004585 etidronic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
〔産業上の利用分野〕
本発明は、１，1′−パーオキシジシクロヘキシ
ルアミンの製造法に関する。更に詳しく述べるな
らば、本発明は、１，1′−パーオキシジシクロヘ
キシルアミンを経済的に製造する方法に関する。
〔従来の技術〕
シクロヘキサノン、過酸化水素およびアンモニ
アを反応させて１，1′−パーオキシジシクロヘキ
シルアミンを製造する方法は公知である（例え
ば、特公昭45−35531、46−15938および46−
16745および特開昭58−18372）。この反応には、
通常、過酸化水素の安定剤としてヒドロキシエタ
ンジホスホン酸のナトリウム塩などが用いられ、
また触媒として酢酸アンモニウムなどが用いられ
る。
〔発明が解決しようとする問題点〕
しかるに、上記の如き従来技術においては、反
応に用いられた水を含む水相を反応液から分離回
収し、これを反応系へ循環して再使用することは
行われておらず、水相に含まれる有効成分や水を
効率的に再利用することができなかつた。
本発明は、かかる従来技術における問題点を解
決しようとするものであり、極めて経済的であ
り、従つて工業的に極めて有利な、１，1′−パー
オキシジシクロヘキシルアミンの製造方法を提供
することを目的とする。
〔問題点を解決するための手段〕
本発明によれば、従つて、シクロヘキサノン、
過酸化水素およびアンモニアを、酢酸アンモニウ
ムなどの触媒の存在下に反応させて、１，1′−パ
ーオキシジシクロヘキシルアミンを製造する方法
が提供されるのであつて、この方法は、反応によ
り得られる反応液を抽出溶媒により抽出して反応
生成物を含有する油相を回収し、一方、酢酸アン
モニウムなどを含有する水相を抽出溶媒により抽
出して不純物を除去した後、不純物の除去された
水相液の少くとも一部を反応系へ循環して再使用
することを特徴とする。
本発明において、反応液を抽出するための抽出
溶媒および水相を抽出するための抽出溶媒のいず
れに対しても、具体例として、トルエン、石油エ
ーテル、シクロヘキサン、シクロヘキサノン、キ
シレン、ベンゼンなどの有機溶媒を挙げることが
できる。反応液の抽出溶媒と水相の抽出溶媒とは
同一であつても、相異つていてもよいが、同一で
あるのが好ましい。
常法に従つてシクロヘキサノン、過酸化水素お
よびアンモニアを反応せしめた後、反応液を上記
の如き抽出溶媒で抽出して反応生成物を含有する
油相を回収する。
これにより分離された水相中には、未反応の原
料のほか、反応により生成した目的生成物や副生
成物、並びに反応に用いられた触媒や添加剤が含
有されている。しかして、本発明においては、油
相と分離された水相を、先ず、上記の抽出溶媒で
抽出して、目的生成物や副生成物等を不純物とし
て除去し、未反応原料、触媒、安定剤の如き添加
剤等を含む水相液を回収し、これを反応系へ循環
して再使用するのである。即ち、不純物を除去し
た後の水相液中には、アンモニア、過酸化水素や
触媒として用いた酢酸アンモニウム等がかなり多
量に含有されており、これを反応系に再循環する
ことでこれらの薬剤の有効利用が図れるととも
に、水の節約にもなる。
上記の反応の間に生ずる水によつて、一般に
は、水相は過剰となり、かかる場合には残余の水
相は系外に排出されてもよい。
尚、水相中に含まれる反応副生物等の不純物を
抽出除去することなく、油相と分離された水相
をそのまま再循環使用する場合には、反応が阻害
されたり、次第に目的物の選択率が低下したりす
る。
本発明の方法において、循環再使用される水相
液の量は、反応系における水相対油相の容量比が
１：２〜２：１になるように調整されるのが好ま
しい。また、得られる反応液の水相中のアンモニ
ア濃度は、一般に、５〜20重量％であるのがよ
い。さらに、水相の抽出に用いられる抽出溶媒の
量は、抽出溶媒対水相の重量比が少くとも0.01：
１〜３：１、特に好ましくは0.1：１〜２：１と
なるような量であるのが好ましい。
〔発明の効果〕
本発明によれば、反応に有用な触媒成分などの
薬剤を主として含む水相液を有効に再循環使用す
ることができ、しかも再循環された水相液によつ
て１，1′−パーオキシジシクロヘキシルアミンの
選択率が低下しないので、極めて効率的かつ経済
的に１，1′−パーオキシジシクロヘキシルアミン
を連続的に長期間にわたり安定に製造することが
でき、工業的に極めて有利である。
〔実施例〕
以下、具体例を挙げて本発明を更に説明する
が、本発明がこれらの例によつて限定されるべき
ものでないことは言うまでもないことである。
実施例 １
第１図に示すプロセスフローにより、下記の操
作に従つて、４週間にわたり連続して本発明の方
法を実施した。
シクロヘキサノン660Kg／hr、60％過酸化水素
水175Kg／hr、アンモニアガス120Nm3／hr、並び
に触媒として酢酸を50Kg／hrおよび過酸化水素の
安定剤としてヒドロキシエタンジホスホン酸ナト
リウムを0.5Kg／hrで反応槽２へ連続的に供給す
る１。同時に、油相と分離されて連続的に反応槽
へ再循環される水相８を680Kg／hrの量で供給し、
常圧下に30〜35℃の温度で反応させる。反応槽に
おける滞留時間は９時間であつた。反応液にトル
エン３を50Kg／hrで供給し、分離槽４に移した
後、分離槽において油相５と水相６とに分離し、
油相を回収する。
得られた油相５の組成（４週間にわたり毎日測
定したデータの平均値）を下記の表１に、そして
反応成績を表２に示す。
分離槽４で分離された水相６中には、１，1′−
パーオキシジシクロヘキシルアミン、シクロヘキ
サノンおよび微量のピリミジン誘導体が含有され
ている。これを、抽出塔７において、トルエンを
用い、トルエン対水相の重量比１：１において、
抽出してトルエン可溶性成分９を除去する。抽出
前の水相６と抽出後の水相８における各成分の含
有率の測定により得られた、抽出塔での抽出除去
の結果（４週間にわたり毎日測定したデータの平
均値）は、表３に示す通りであつた。
抽出後の水相８を、上記したように680Kg／hr
の量で、反応槽へ再循環し、残余の水相を必要に
より系外へ排出する１０。この水相８中には、表
４に示すように、アンモニア、過酸化水素および
酢酸アンモニウムが多量に含まれており（４週間
にわたり毎日測定したデータの平均値）、再循環
することによりこれらを有効に再利用することが
できる。
[Industrial Field of Application] The present invention relates to a method for producing 1,1'-peroxydicyclohexylamine. More specifically, the present invention relates to an economical process for producing 1,1'-peroxydicyclohexylamine. [Prior Art] A method for producing 1,1'-peroxydicyclohexylamine by reacting cyclohexanone, hydrogen peroxide and ammonia is known (for example, Japanese Patent Publications No. 45-35531, No. 46-15938 and No. 46-
16745 and Japanese Unexamined Patent Publication No. 58-18372). This reaction has
Usually, sodium salt of hydroxyethane diphosphonic acid is used as a stabilizer for hydrogen peroxide.
Also, ammonium acetate or the like is used as a catalyst. [Problems to be Solved by the Invention] However, in the above-mentioned prior art, it is necessary to separate and recover the aqueous phase containing water used in the reaction from the reaction liquid and circulate it to the reaction system for reuse. was not carried out, and it was not possible to efficiently reuse the active ingredients and water contained in the aqueous phase. The present invention aims to solve the problems in the prior art, and provides a method for producing 1,1'-peroxydicyclohexylamine that is extremely economical and therefore industrially advantageous. With the goal. [Means for solving the problem] According to the present invention, therefore, cyclohexanone,
Provided is a method for producing 1,1'-peroxydicyclohexylamine by reacting hydrogen peroxide and ammonia in the presence of a catalyst such as ammonium acetate, the method comprising: The liquid is extracted with an extraction solvent to recover the oil phase containing the reaction products, while the aqueous phase containing ammonium acetate etc. is extracted with the extraction solvent to remove impurities, and the aqueous phase from which the impurities have been removed is recovered. It is characterized in that at least a part of the liquid is recycled to the reaction system for reuse. In the present invention, organic solvents such as toluene, petroleum ether, cyclohexane, cyclohexanone, xylene, and benzene are used as specific examples for both the extraction solvent for extracting the reaction solution and the extraction solvent for extracting the aqueous phase. can be mentioned. The extraction solvent of the reaction solution and the extraction solvent of the aqueous phase may be the same or different, but are preferably the same. After reacting cyclohexanone, hydrogen peroxide, and ammonia in accordance with a conventional method, the reaction solution is extracted with the above-mentioned extraction solvent to recover an oil phase containing the reaction product. The aqueous phase thus separated contains, in addition to unreacted raw materials, target products and byproducts produced by the reaction, as well as catalysts and additives used in the reaction. Therefore, in the present invention, the aqueous phase separated from the oil phase is first extracted with the above extraction solvent to remove target products and by-products as impurities, and unreacted raw materials, catalysts, and stabilized The aqueous phase liquid containing additives such as reagents is recovered and recycled to the reaction system for reuse. In other words, the aqueous phase liquid after removing impurities contains a considerable amount of ammonia, hydrogen peroxide, ammonium acetate used as a catalyst, etc., and these chemicals can be removed by recycling this into the reaction system. In addition to making effective use of water, it also saves water. The water produced during the above reaction will generally result in an excess of the aqueous phase, in which case the remaining aqueous phase may be discharged from the system. In addition, if the aqueous phase separated from the oil phase is recycled as it is without extracting and removing impurities such as reaction by-products contained in the aqueous phase, the reaction may be inhibited or the target product may gradually become unselectable. rate may decrease. In the method of the present invention, the amount of aqueous phase liquid to be recycled and reused is preferably adjusted so that the volume ratio of water to oil phase in the reaction system is 1:2 to 2:1. Further, the ammonia concentration in the aqueous phase of the resulting reaction solution is generally preferably 5 to 20% by weight. Additionally, the amount of extraction solvent used for extraction of the aqueous phase should be such that the weight ratio of extraction solvent to aqueous phase is at least 0.01:
The amount is preferably 1 to 3:1, particularly preferably 0.1:1 to 2:1. [Effects of the Invention] According to the present invention, it is possible to effectively recycle and use the aqueous phase liquid that mainly contains chemicals such as catalyst components useful in the reaction, and moreover, the recycled aqueous phase liquid can be used to achieve 1. Since the selectivity of 1'-peroxydicyclohexylamine does not decrease, 1,1'-peroxydicyclohexylamine can be produced continuously and stably over a long period of time in an extremely efficient and economical manner. It's advantageous. [Example] Hereinafter, the present invention will be further explained by giving specific examples, but it goes without saying that the present invention should not be limited to these examples. Example 1 According to the process flow shown in FIG. 1, the method of the present invention was carried out continuously for four weeks according to the following operations. Cyclohexanone 660Kg/hr, 60% hydrogen peroxide solution 175Kg/hr, ammonia gas 120Nm 3 /hr, acetic acid as a catalyst at 50Kg/hr, and sodium hydroxyethane diphosphonate as a hydrogen peroxide stabilizer at 0.5Kg/hr. 1 which is continuously supplied to the reaction tank 2; At the same time, an aqueous phase 8, which is separated from the oil phase and continuously recycled to the reaction tank, is supplied in an amount of 680 Kg/hr.
The reaction is carried out at a temperature of 30-35°C under normal pressure. The residence time in the reaction tank was 9 hours. Toluene 3 was supplied to the reaction solution at a rate of 50 kg/hr, and the mixture was transferred to a separation tank 4, and then separated into an oil phase 5 and an aqueous phase 6 in the separation tank.
Collect the oil phase. The composition of the obtained oil phase 5 (average value of data measured daily over 4 weeks) is shown in Table 1 below, and the reaction results are shown in Table 2. The aqueous phase 6 separated in the separation tank 4 contains 1,1'-
Contains peroxydicyclohexylamine, cyclohexanone and trace amounts of pyrimidine derivatives. This was extracted in the extraction column 7 using toluene at a weight ratio of toluene to aqueous phase of 1:1.
The toluene soluble component 9 is removed by extraction. The results of extraction removal in the extraction tower (average values of data measured daily over 4 weeks) obtained by measuring the content of each component in aqueous phase 6 before extraction and aqueous phase 8 after extraction are shown in Table 3. It was as shown in. The aqueous phase 8 after extraction was heated to 680 Kg/hr as described above.
The amount of water phase is recycled to the reaction tank, and the remaining aqueous phase is discharged from the system if necessary. As shown in Table 4, this aqueous phase 8 contains large amounts of ammonia, hydrogen peroxide, and ammonium acetate (average values of data measured daily over 4 weeks), and these can be removed by recycling. Can be effectively reused.
【表】【table】
【表】
ジシクロヘキシル
アミン選択率
[Table] Dicyclohexyl
Amine selectivity
Claims (1)
ニアを酢酸アンモニウムなどの触媒の存在下に水
中で反応させ、得られる反応液を抽出溶媒により
抽出して反応生成物を含有する油相を回収し、一
方、酢酸アンモニウムなどを含有する水相を抽出
溶媒により抽出して不純物を除去した後、不純物
の除去された水相液の少くとも一部を反応系へ循
環して再使用することを特徴とする、１，1′−パ
ーオキシジシクロヘキシルアミンの製造法。 ２ 抽出溶媒がそれぞれトルエン、石油エーテ
ル、シクロヘキサン、シクロヘキサノン、キシレ
ンおよびベンゼンから選ばれる、特許請求の範囲
第１項記載の方法。 ３ 反応系へ循環される水相液の量が、反応系に
おける水相対油相の容量比が0.5〜２：１になる
ような量である、特許請求の範囲第１項記載の方
法。 ４ 水相の抽出に用いられる抽出溶媒対水相の重
量比が少くとも0.01：１である、特許請求の範囲
第１項記載の方法。 ５ 反応液の水相中のアンモニア濃度が５〜20重
量％である、特許請求の範囲第１項記載の方法。[Claims] 1. Cyclohexanone, hydrogen peroxide, and ammonia are reacted in water in the presence of a catalyst such as ammonium acetate, and the resulting reaction solution is extracted with an extraction solvent to recover an oil phase containing the reaction product. However, on the other hand, after extracting the aqueous phase containing ammonium acetate etc. with an extraction solvent to remove impurities, at least a part of the aqueous phase liquid from which impurities have been removed is recycled to the reaction system for reuse. A characterized method for producing 1,1'-peroxydicyclohexylamine. 2. The method of claim 1, wherein the extraction solvents are each selected from toluene, petroleum ether, cyclohexane, cyclohexanone, xylene and benzene. 3. The method according to claim 1, wherein the amount of aqueous phase liquid recycled to the reaction system is such that the volume ratio of water to oil phase in the reaction system is 0.5 to 2:1. 4. The method of claim 1, wherein the weight ratio of extraction solvent to aqueous phase used for extraction of the aqueous phase is at least 0.01:1. 5. The method according to claim 1, wherein the ammonia concentration in the aqueous phase of the reaction solution is 5 to 20% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28603486A JPS63139177A (en) | 1986-12-02 | 1986-12-02 | Production of 1,1'-peroxydicyclohexylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28603486A JPS63139177A (en) | 1986-12-02 | 1986-12-02 | Production of 1,1'-peroxydicyclohexylamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63139177A JPS63139177A (en) | 1988-06-10 |
| JPH0455430B2 true JPH0455430B2 (en) | 1992-09-03 |
Family
ID=17699116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28603486A Granted JPS63139177A (en) | 1986-12-02 | 1986-12-02 | Production of 1,1'-peroxydicyclohexylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63139177A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115504939B (en) * | 2021-06-22 | 2024-02-02 | 万华化学集团股份有限公司 | Preparation method of 1,1' -dicyclohexylamine peroxide |
-
1986
- 1986-12-02 JP JP28603486A patent/JPS63139177A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63139177A (en) | 1988-06-10 |
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