JPS63196548A - Production of suberonitrile - Google Patents
Production of suberonitrileInfo
- Publication number
- JPS63196548A JPS63196548A JP62028191A JP2819187A JPS63196548A JP S63196548 A JPS63196548 A JP S63196548A JP 62028191 A JP62028191 A JP 62028191A JP 2819187 A JP2819187 A JP 2819187A JP S63196548 A JPS63196548 A JP S63196548A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- dichlorohexane
- suberonitrile
- concentration
- reactor
- 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.)
- Granted
Links
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 5
- 150000004985 diamines Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 36
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 18
- 229910052708 sodium Inorganic materials 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000012071 phase Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000002497 iodine compounds Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 1
- FXBITRHTKQZLRX-UHFFFAOYSA-N 7-chloroheptanenitrile Chemical compound ClCCCCCCC#N FXBITRHTKQZLRX-UHFFFAOYSA-N 0.000 description 1
- 229910001516 alkali metal iodide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、１，６−ジクロルヘキサンと資化ソーダより
スベロニトリルを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing suberonitrile from 1,6-dichlorohexane and sodium assimilate.
スベロニトリルは農医薬品やジカルボン酸、ジアミンな
どの製造用中間体として、有機化学および生物化学の分
野で有用である。Suberonitrile is useful in the fields of organic chemistry and biochemistry as an intermediate for the production of agricultural drugs, dicarboxylic acids, diamines, etc.
（従来の技術）
スベロニトリルの製造方法は、ケミカルアブストラクト
（ｖｏｌ、９４ Ｐ、４６８０３ｈ）に酸化亜鉛の存在
下、スペリン酸とアンモニアを反応させる方法が記載さ
れており、また、特開昭６１−１２２２５８号には、１
．６−ヘキサンジオールとヨウ化水素またはアルカリ金
属のヨウ化物とを反応させて得られた１、６−ジクロル
ヘキサンを資化ソーダ、背比カリおよび青酸などのシア
ノ化剤と反応させる方法が記載されている。(Prior art) A method for producing suberonitrile is described in Chemical Abstracts (vol, 94 P, 46803h), in which superic acid and ammonia are reacted in the presence of zinc oxide, and also in JP-A No. 61-122258. The number is 1
．． A method is described in which 1,6-dichlorohexane obtained by reacting 6-hexanediol with hydrogen iodide or an alkali metal iodide is reacted with a cyanating agent such as sodium hydroxide, potassium hydroxide, and hydrocyanic acid. has been done.
スペリン酸を原料とする方法は、スペリン酸が高価であ
り、また反応温度が２４０〜３００°Ｃと高く、収率が
低いため工業化が困難である。The method using speric acid as a raw material is difficult to industrialize because speric acid is expensive, the reaction temperature is as high as 240 to 300°C, and the yield is low.
１．６−ヘキサンジオールとヨウ素化合物を反応させ、
シアノ化する方法も、高価なヨウ素化合物が必要である
。またこの方法は反応終了後、エーテル、クロロホルム
などの疎水性有機溶剤で抽出し、更に水洗、乾燥および
減圧蓋部の操作が必要で、精製工程が複雑である。1. Reacting 6-hexanediol and an iodine compound,
The cyanation method also requires expensive iodine compounds. In addition, this method requires extraction with a hydrophobic organic solvent such as ether or chloroform after the reaction is completed, and further requires washing with water, drying, and operating a vacuum lid, making the purification process complicated.
（発明が解決しようとする問題点）
発明者等は先に
炭素数３〜１０のアルキル基を示し、これらは同一でも
異なっていても良い）で表される相間移動触媒の存在下
、１．６−ジクロルヘキサンと背比ソーダ水溶液を反応
させスベロニトリルを製造する方法を提供した。(Problems to be Solved by the Invention) In the presence of a phase transfer catalyst represented by the above-described alkyl group having 3 to 10 carbon atoms, which may be the same or different, 1. A method for producing suberonitrile by reacting 6-dichlorohexane with an aqueous soda solution was provided.
１．６−ジクロルヘキサンと資化ソーダの反応は、次の
二段階で反応が進行する。The reaction between 1.6-dichlorohexane and sodium assimilate proceeds in the following two steps.
Ｃ１（ＣＨｚ）ｈＣｊ！ ＋ ＮａＣＮ −→Ｃ
Ｎ（ＣＨｇ）ａ Ｃ４！ ＋ＮａＣｊ！ （１）
ＣＮ （Ｃ８ｚ） ６Ｃｌ ＋ ＮａＣＮ −
→ＣＮ （ＣＨｚ） ＆ＣＮ ＋ ＮａＣｌ
（２）（１）の反応での生成物ｌ−シアノ−６−クロル
ヘキサン（以下モノニトリルと称する）とスベロニトリ
ルは沸点が近いので、これを分離するには高性能の蓋部
塔が必要である。またスベロニトリルの収率を高めるた
めには、このモノニトリルを原料系に循環させる必要、
があり、複雑なプロセスとなる。C1(CHz)hCj! + NaCN −→C
N(CHg)a C4! +NaCj! (1)
CN (C8z) 6Cl + NaCN −
→CN (CHZ) &CN + NaCl
(2) Since the product 1-cyano-6-chlorohexane (hereinafter referred to as mononitrile) and suberonitrile have similar boiling points, a high-performance lid column is required to separate them. be. In addition, in order to increase the yield of suberonitrile, it is necessary to circulate this mononitrile into the raw material system.
It is a complex process.
１．６−ジクロルヘキサンに対する資化ソーダのモル比
を高くすればモノニトリルの生成量が少なくなるが、こ
の場合は排水中に多量のＣＮイオンが残留することにな
り、排水処理の費用が増大する。If the molar ratio of sodium assimilate to 1.6-dichlorohexane is increased, the amount of mononitrile produced will be reduced, but in this case, a large amount of CN ions will remain in the wastewater, increasing the cost of wastewater treatment. increase
（問題点を解決するための手段） 発明者等は１，６−ジクロルヘキサンを原料とする。(Means for solving problems) The inventors use 1,6-dichlorohexane as a raw material.
スベロニトリルの製造方法に関しての以上の如き問題点
を解決すべく鋭意検討し、１．６−ジクロルヘキサンと
触媒を直列に配置された複数個の反応器に導き、未反応
の資化ソーダを含む反応液の水層部分を前段の反応器に
戻し反応させることにより、モノニトリル副生量が少な
く、スベロニトリルの収率が上がり、且つ排水中のＣＮ
イオン残量が減少することを見出し本発明に至った。In order to solve the above-mentioned problems regarding the production method of suberonitrile, we conducted intensive studies to introduce 1,6-dichlorohexane and a catalyst into multiple reactors arranged in series, including unreacted sodium assimilate. By returning the aqueous layer of the reaction solution to the previous reactor, the amount of mononitrile by-product is reduced, the yield of suberonitrile is increased, and CN in the waste water is reduced.
The present invention was achieved by discovering that the remaining amount of ions is reduced.
即ち本発明は、
炭素数３〜１０のアルキル基を示し、これらは互いに同
一でもことなっていても良い）で表される相間移動触媒
の存在下、１．６−ジクロルヘキサンと背比ソーダ水溶
液よりスベロニトリルを製造するにし、１．６−ジクロ
ルヘキサンと触媒を直列に配置された複数個の反応器の
最前段に導き、後段の反応器の反応液を反応終了後油層
と水層に分離し、未反応の資化ソーダを含有する水溶液
を前段に導入し反応させることを特徴とするスベロニト
リルの製造法である。That is, the present invention provides a method for combining 1,6-dichlorohexane and sodium chloride in the presence of a phase transfer catalyst represented by an alkyl group having 3 to 10 carbon atoms, which may be the same or different from each other. To produce suberonitrile from an aqueous solution, 1,6-dichlorohexane and a catalyst are introduced into the first stage of multiple reactors arranged in series, and the reaction liquid in the latter reactor is separated into an oil layer and a water layer after the reaction is completed. This is a method for producing suberonitrile, which is characterized in that an aqueous solution containing separated and unreacted sodium assimilate is introduced into the first stage and reacted.
本発明で使用される相間移動触媒の例としては、テトラ
プロピルアンモニウムプロミド、テトラブチルアンモニ
ウムプロミドなどがある。特にテトラブチルアンモニウ
ムプロミドが好適である。Examples of phase transfer catalysts used in the present invention include tetrapropylammonium bromide and tetrabutylammonium bromide. Tetrabutylammonium bromide is particularly suitable.
背比ソーダ水溶液は、工業的に市販されている濃度３０
〜３５χの水溶液をそのまま使用することができ、また
更に必要に応じて濃度を下げて使用することもできる。The aqueous soda solution has a concentration of 30, which is commercially available industrially.
The aqueous solution having a concentration of ~35.chi. can be used as it is, or can be used with a lower concentration if necessary.
本発明により、資化ソーダの全使用量は仕込み１．６−
ジクロルヘキサンに対する資化ソーダのモル比を理論量
の２．０に対し２．１〜２．６程度で良い。According to the present invention, the total amount of sodium hydroxide used is 1.6-
The molar ratio of sodium assimilate to dichlorohexane may be about 2.1 to 2.6 relative to the theoretical amount of 2.0.
二〇モル比が低過ぎる場合は収率が低く、１．６−ジク
ロルヘキサンの損失が太き（なる、またこのモル比が高
過ぎる場合は排水中にＣＮイオンが残留し、排水処理の
費用が増加する。If the molar ratio is too low, the yield will be low and the loss of 1,6-dichlorohexane will be large.If this molar ratio is too high, CN ions will remain in the wastewater, making it difficult to treat wastewater. Costs increase.
相間移動触媒の使用量は１．６−ジクロルヘキサン１モ
ル当たり １．５〜１０ｇ１好ましくは１．５〜６．５
ｇとする。テトラブチルアンモニウムプロミドの使用量
が少なすぎると収率が低（、多い場合は次の精製工程の
負荷が大きくなる。The amount of phase transfer catalyst used is 1.5 to 10 g, preferably 1.5 to 6.5 g, per mole of 1.6-dichlorohexane.
Let it be g. If the amount of tetrabutylammonium bromide used is too small, the yield will be low; if it is too large, the burden of the next purification step will be heavy.
各反応器の反応温度は８０〜１４０ ’Ｃ１好ましくは
９０〜１１０℃とする０反応器度が低いと反応が進行せ
ず、高すぎる場合は収率が低下する。The reaction temperature of each reactor is 80 to 140° C., preferably 90 to 110° C. If the reactor temperature is too low, the reaction will not proceed, and if it is too high, the yield will decrease.
反応圧力は特に制限が無いが、通常は常圧で行う０反応
時間は通常０．５〜８ ｈｒ、好ましくは２〜４ ｈｒ
である。The reaction pressure is not particularly limited, but the reaction time is usually 0.5 to 8 hr, preferably 2 to 4 hr, which is usually carried out at normal pressure.
It is.
次に図面を用いて本発明を説明する。第１図は本発明に
より二個の反応器を直列に配置した場合の例である。Next, the present invention will be explained using the drawings. FIG. 1 is an example of two reactors arranged in series according to the present invention.
図中の１および■は本発明でのスベロニトリル反応器で
あり、各反応器は油相と水相の界面を確認する監視器、
撹拌機、各液の供給口および排出口を有する構造となっ
ている。1 and ■ in the figure are suberonitrile reactors in the present invention, and each reactor has a monitor for checking the interface between the oil phase and the water phase,
It has a structure that includes a stirrer, supply ports and discharge ports for each liquid.
原料の１，６−ジクロルヘキサンと相間移動触媒は先ず
原料液供給管１より供給し、撹拌機により撹拌される。The raw materials 1,6-dichlorohexane and the phase transfer catalyst are first supplied from the raw material liquid supply pipe 1 and stirred by a stirrer.
資化ソーダ水溶液は、本発明においては後段の反応器■
からの配管６より供給する。原料液を撹拌しながら資化
ソーダ水溶液を供給し、スベロニトリル生成反応が行わ
れる。反応が終了した後、撹拌機を停止し静置すること
により反応液は油相と水相に分離され、上部の油相には
スベロニトリル、モノニトリルおよび未反応の１，６−
ジクロルヘキサンが含まれ、下部の水相には反応生成物
のＮａＣｌと未反応の背比ソーダが含まれる。In the present invention, the sodium hydroxide aqueous solution is
It is supplied from piping 6 from . While stirring the raw material liquid, an aqueous sodium assimilate solution is supplied to carry out the suberonitrile production reaction. After the reaction is completed, the stirrer is stopped and the reaction solution is left standing to separate into an oil phase and an aqueous phase, and the upper oil phase contains suberonitrile, mononitrile, and unreacted 1,6-
Dichlorohexane is contained, and the lower aqueous phase contains the reaction product NaCl and unreacted soda.
この水相液は配管４より排水として放出される。This aqueous phase liquid is discharged from the pipe 4 as waste water.
油相の部分は、配管３により後段の反応器■に移され、
撹拌されながら、配管２より供給される原料の資化ソー
ダ水溶液によりスベロニトリル生成反応が行われる。反
応生成液は静置により油相と水相に分離され、油相は配
管５より取り出されて、スベロニトリルが精製分離され
る。水相は配管６より前段の反応器Ｉに供給され、未反
応の背比ソーダが原料の１．６−ジクロ）Ｌ＜ヘキサン
と反応し、その排水中の背比ソーダが減少する。 本発
明は反応器Ｉと■との間に、更に反応器を設置しても良
い。The oil phase portion is transferred to the rear reactor ■ via piping 3,
While being stirred, the suberonitrile production reaction is carried out using the sodium assimilate aqueous solution as a raw material supplied from the pipe 2. The reaction product liquid is separated into an oil phase and an aqueous phase by standing still, and the oil phase is taken out from the pipe 5 to purify and separate suberonitrile. The aqueous phase is supplied to the reactor I at the upstream stage via piping 6, and unreacted sodium chloride reacts with the raw material 1,6-dichloro)L<hexane, reducing the sodium chloride in the waste water. In the present invention, an additional reactor may be installed between reactors I and (2).
（作用および効果）
本発明によれば、油相液が後段の反応器において背比ソ
ーダの過剰な状態で反応することになるから、未反応１
．６−ジクロルヘキサンおよびモノニトリルの反応が促
進され、１，６−ジクロルヘキサンの反応率およびスベ
ロニトリルの選択率が向上する。また水相液は前段の反
応器で１．６−ジクロルヘキサンが過剰の状態で未反応
青化ソーダと接することになるから、水相中の背比ソー
ダが減少し、排水中のＣＮイオン濃度が低下するから、
排水処理の費用が削減される。(Functions and Effects) According to the present invention, since the oil phase liquid reacts in the latter stage reactor with an excess amount of soda, the unreacted 1
．． The reaction between 6-dichlorohexane and mononitrile is promoted, and the reaction rate of 1,6-dichlorohexane and the selectivity of suberonitrile are improved. In addition, since the aqueous phase liquid comes into contact with unreacted soda cyanide in the reactor at the front stage with an excess of 1,6-dichlorohexane, the amount of sodium cyanide in the aqueous phase decreases, resulting in CN ions in the waste water. Because the concentration decreases,
The cost of wastewater treatment is reduced.
即ち本発明の方法により、スベロニトリルの収率および
選択率が向上すると共に、排水処理の費用が減少するの
でその工業的意義が大きい。That is, the method of the present invention improves the yield and selectivity of suberonitrile and reduces the cost of wastewater treatment, so it has great industrial significance.
（実施例）
次に実施例により本発明を説明する。次の実施例は反応
器を二段とした場合についてであり、実施例１と実施例
２の相互の関係から実施例が具体的に示される。(Example) Next, the present invention will be explained with reference to Examples. The next example concerns a case where the reactor is arranged in two stages, and the example will be specifically shown based on the mutual relationship between Example 1 and Example 2.
災隻斑上
」１．６−ジクロルヘキサン１５５．０ｇ （１，０モ
ル）、５０χテトチブチルアンモニウムブロミド水溶液
６．６ｇ（純分０．０１モル）を還流冷却器、撹拌機、
温度計の付いた反応器Ｉに仕込み、激しく撹拌しなから
１１０°Ｃまで加熱した。その後３４．３χ青化ソーダ
水溶液２２８．６ｇ（ＮａＣＮ純分１．６０モル）を約
９０分かけて滴下した。更に１１０″Ｃで２時間撹拌し
ながら反応させた。常温まで冷却した後、水１９０ｇを
加えて食塩を溶解した。分液漏斗に移して静置すること
により上層と下層に分離し、上層液１４４．２ｇ、下層
液４３３．４ｇを得た。上層液をガスクロマトグラフィ
ーで分析したところ、１．６−ジクロルヘキサン濃度６
．７９χ、反応率９３．７χ、モノニトリル濃度３１．
６χ、収率３１．３χであった。また下層液中の資化ソ
ーダ濃度は０．２０χであった。A reflux condenser, a stirrer,
The mixture was charged to reactor I equipped with a thermometer and heated to 110° C. with vigorous stirring. Thereafter, 228.6 g of a 34.3χ aqueous sodium cyanide solution (NaCN purity: 1.60 mol) was added dropwise over about 90 minutes. The reaction was further stirred at 110"C for 2 hours. After cooling to room temperature, 190 g of water was added to dissolve the salt. Transfer to a separatory funnel and leave to stand to separate into upper and lower layers. 144.2g and 433.4g of lower layer liquid were obtained.When the upper layer liquid was analyzed by gas chromatography, it was found that the concentration of 1.6-dichlorohexane was 6.
．． 79χ, reaction rate 93.7χ, mononitrile concentration 31.
The yield was 31.3χ. Further, the concentration of sodium assimilate in the lower layer liquid was 0.20χ.
１段 反応器Ｉで得た上層液１４４．２ｇを、還流冷却
器、撹拌機、温度計の付いた反応器■に仕込み、激しく
撹拌しなから１１０°Ｃまで加熱した。その後３４．３
χ青化ソーダ水溶液３５９．８ｇ（ＮａＣＮ純分２．５
２モル）を約９０分かけて滴下した。更に１１０″Ｃで
１時間撹拌しながら反応させた。常温まで冷却した後、
水７０ｇを加えて食塩を溶解した。分液漏斗に移して静
置することにより上層と下層に分離し、上層液１３８．
３ｇ、下層液４３５．７ｇを得た。上層液を分析したと
ころ、１．６−ジクロルヘキサン濃度０．０７χ、反応
率９９．９χ、モノニトリル濃度０．２０χ、収率０．
２χ、スベロニトリル濃度９２．０χ、収率９３．６χ
であった。下層液中の資化ソーダ濃度は１７．８χであ
った。144.2 g of the upper layer liquid obtained in the first-stage reactor I was charged into a reactor II equipped with a reflux condenser, a stirrer, and a thermometer, and heated to 110°C while stirring vigorously. Then 34.3
χ Sodium cyanide aqueous solution 359.8g (NaCN purity 2.5
2 mol) was added dropwise over about 90 minutes. The reaction was further stirred at 110"C for 1 hour. After cooling to room temperature,
70 g of water was added to dissolve the salt. Transfer to a separatory funnel and leave to stand to separate into upper and lower layers, upper layer liquid 138.
3 g and 435.7 g of lower layer liquid were obtained. Analysis of the upper layer liquid revealed that the 1,6-dichlorohexane concentration was 0.07χ, the reaction rate was 99.9χ, the mononitrile concentration was 0.20χ, and the yield was 0.
2χ, suberonitrile concentration 92.0χ, yield 93.6χ
Met. The concentration of sodium assimilate in the lower layer liquid was 17.8χ.
ｚ隻斑主
」 実施例１の１段において、背比ソーダ水溶液の代わ
りに■段で得た下層液４３５．７ｇ（資化ソーダ濃度１
７．８！ 、純分１．５８モル）を用いた外は全く同じ
操作で反応を行い上層液１４６．８ｇ、下層液６３７ｇ
を得た。上層液を分析したところ、１．６−ジクロルヘ
キサン濃度６．９５χ、反応率９３．４χ、モノニトリ
ル濃度３１．３χ、収率３１．６χ、スベロニトリル濃
度５２．９χ、収率５７．１χであった。下層液中の資
化ソーダ濃度は０．１６χであった。In the 1st stage of Example 1, 435.7 g of the lower layer liquid obtained in the
7.8! , purity 1.58 mol) was used, but the reaction was carried out in exactly the same manner, and the upper layer liquid was 146.8 g, and the lower layer liquid was 637 g.
I got it. Analysis of the upper layer liquid revealed that 1,6-dichlorohexane concentration was 6.95χ, reaction rate was 93.4χ, mononitrile concentration was 31.3χ, yield was 31.6χ, suberonitrile concentration was 52.9χ, and yield was 57.1χ. there were. The concentration of sodium assimilate in the lower layer liquid was 0.16χ.
１１段で得た上層液！４６．８．を用いて実施例１の■
段と全く同じ操作で反応を行い、上層液１４０．１ｇ、
下層液４３５ｇを得た。上層液を分析したところ、１．
６−ジクロルヘキサン濃度０．２９χ、反応率９９．７
χ、モノニトリル濃度０．２０！ 、収率０．２０χ、
スベロニトリル濃度９２．３χ、収率９５．１χであっ
た。The upper layer liquid obtained in the 11th stage! 46.8. ■ of Example 1 using
The reaction was carried out in exactly the same manner as in step 1, and 140.1 g of the upper layer liquid was obtained.
435 g of lower layer liquid was obtained. When the upper layer liquid was analyzed, 1.
6-dichlorohexane concentration 0.29χ, reaction rate 99.7
χ, mononitrile concentration 0.20! , yield 0.20χ,
The suberonitrile concentration was 92.3χ and the yield was 95.1χ.
下層液中の資化ソーダ濃度は１７．５χであった。The concentration of sodium assimilate in the lower layer liquid was 17.5χ.
ル較班１
１．６−ジクロルヘキサン１５５．０ｇ（１，０モル）
、５０χテトラブチルアンモニウムプロミド水溶液６．
６ｇ（純分０．０ｒモル）を還流冷却器、撹拌機、温度
計の付いた反応器に仕込み、激しく撹拌しなから１１０
°Ｃまで加熱した。その後３４．５χ青化ソーダ水溶液
２８４．７ｇ（ＮａＣＮ純分２．０モル）を２時間３０
分かけて滴下し、その後１１０°Ｃで４時間撹拌しなが
ら反応させた。常温まで冷却した後、水４６５ｇを加え
て食塩を溶解した。分液漏斗に移して静置することによ
り上層と下層に分離し、上層液１３８ｇ、下層液７７０
ｇを得た。上層液を分析したところ、１．６−ジクロル
ヘキサン濃度０．６２χ、反応率９９．４Ｘ 、モノニ
トリル濃度９．１１χ、収率８．６χ、スベロニトリル
濃度８４．０χ、収率８５．２χであった。下層液中の
資化ソーダ濃度は０．１１χであった。Comparison group 1 1,6-dichlorohexane 155.0g (1.0 mol)
, 50χ tetrabutylammonium bromide aqueous solution 6.
Charge 6 g (0.0 r mol of pure content) into a reactor equipped with a reflux condenser, stirrer, and thermometer, and stir vigorously until 110
Heated to °C. After that, 284.7 g of 34.5χ aqueous sodium cyanide solution (2.0 mol of NaCN purity) was added for 2 hours and 30 minutes.
The mixture was added dropwise over a period of minutes, and then the mixture was reacted at 110°C for 4 hours with stirring. After cooling to room temperature, 465 g of water was added to dissolve the salt. Transfer to a separatory funnel and let stand to separate into upper and lower layers, 138 g of upper layer liquid and 770 g of lower layer liquid.
I got g. Analysis of the upper layer liquid revealed that the 1,6-dichlorohexane concentration was 0.62χ, the reaction rate was 99.4X, the mononitrile concentration was 9.11χ, the yield was 8.6χ, the suberonitrile concentration was 84.0χ, and the yield was 85.2χ. there were. The concentration of sodium assimilate in the lower layer liquid was 0.11χ.
ル較員１
１．６−ジクロルヘキサン１５５．０ｇ（１，０モル）
、５０χテトラブチルアンモニウムプロミド水溶液３．
３ｇ（純分０．０１モル）、３４．５χ青化ソーダ水溶
液５６８．１ｇ（ＮａＣＮ純分４．０モル）を還流冷却
器、撹拌機、温度針の付いた反応器に仕込み、激しく撹
拌しながら１１０℃まで加熱した。引続き１１０″Ｃで
２時間撹拌しながら反応させた。常温まで冷却した後、
水４６０ｇを加えて食塩を溶解した０分液漏斗に移して
静置することにより上層と下層に分離し、上層液１３６
、７ｇ、下層液１０４８．７ｇを得た。上層液の分析結
果より、１．６−ジクロルヘキサン濃度０．１χ、反応
率９９．９Ｘ 、−１：／ ニドＩＪ ７Ｌ／濃度１．
１１％ 、収率ｉ、ｏｘ、スベロニトリル濃度９１．２
χ、収率９１．７χであり、下層液中の資化ソーダ濃度
は６．５７２であった。1 1,6-dichlorohexane 155.0 g (1.0 mol)
, 50χ tetrabutylammonium bromide aqueous solution 3.
3g (purity 0.01 mol) and 568.1g (NaCN purity 4.0 mol) of a 34.5χ aqueous sodium cyanide solution were charged into a reactor equipped with a reflux condenser, a stirrer, and a temperature needle, and stirred vigorously. while heating to 110°C. The reaction was continued with stirring at 110"C for 2 hours. After cooling to room temperature,
Add 460 g of water and dissolve salt in a 0-separation funnel and leave to stand to separate into an upper layer and a lower layer.
, 7 g, and 1048.7 g of lower layer liquid were obtained. From the analysis results of the upper layer liquid, the 1.6-dichlorohexane concentration was 0.1χ, the reaction rate was 99.9X, -1:/ Nido IJ 7L/concentration 1.
11%, yield i, ox, suberonitrile concentration 91.2
The yield was 91.7χ, and the sodium assimilate concentration in the lower layer liquid was 6.572.
これらの実施例および比較例から、本発明の方法により
二段反応器で反応させた場合は、１．６−ジクロルヘキ
サン反応率９９．７χで、スベロニトリル収率９５．ｌ
χであり、排液中の、資化ソーダ濃度が０゜１６χに低
下する（実施例２）のに対し、通常の一段で反応を行う
場合は、１．６−ジクロルヘキサン反応率９９．４χで
、スベロニトリル収率８５．２χであり、スベロニトリ
ル生成液中に濃度９．１１χのモノニトリルが生成する
（比較例１）ため高性能の蒸留塔が必要である。From these Examples and Comparative Examples, when the reaction was carried out in a two-stage reactor according to the method of the present invention, the 1,6-dichlorohexane reaction rate was 99.7χ and the suberonitrile yield was 95. l
χ, and the sodium assimilate concentration in the waste liquid decreases to 0°16χ (Example 2), whereas when the reaction is carried out in a normal one stage, the 1,6-dichlorohexane reaction rate is 99. 4χ, the suberonitrile yield is 85.2χ, and mononitrile with a concentration of 9.11χ is produced in the suberonitrile production liquid (Comparative Example 1), so a high-performance distillation column is required.
スベロニトリルの収率を上げるため、資化ソーダを倍量
とすれば、スベロニトリルの収率が９１．７χに上昇す
るが、排液中の資化ソーダが６．５７χに増加しく比較
例２）、排液処理の費用が大きくなる。In order to increase the yield of suberonitrile, if the amount of sodium assimilate is doubled, the yield of suberonitrile increases to 91.7χ, but the amount of sodium assimilate in the waste liquid increases to 6.57χ. Comparative Example 2) The cost of wastewater treatment increases.
本発明の方法によれば、高いスベロニトリル収率が得ら
れると共に、排液中の資化ソーダ濃度が著しく低下する
から、実装置での利点が大きい。According to the method of the present invention, a high yield of suberonitrile can be obtained, and the concentration of sodium assimilate in the waste liquid is significantly reduced, so it has great advantages in actual equipment.
第１図は本発明により、二個の反応器を直列に配置した
場合の説明図である。FIG. 1 is an explanatory diagram of two reactors arranged in series according to the present invention.
Claims (1)
１〜Ｒ＿４は炭素数３〜１０のアルキル基を示し、これ
らは互いに同一でも異なっていても良い）で表される相
間移動触媒の存在下、１，６−ジクロルヘキサンと青化
ソーダ水溶液を反応させてスベロニトリルを製造するに
際し、１，６−ジクロルヘキサンと触媒を直列に配置さ
れた複数個の反応器の最前段に導き、後段の反応器の反
応液を反応終了後油層と水層に分離し、未反応の青化ソ
ーダを含有する水溶液を前段に導入し反応させることを
特徴とするスベロニトリルの製造法[Claims] The general formula is [▲There are mathematical formulas, chemical formulas, tables, etc.▼] (R_
1 to R_4 represent an alkyl group having 3 to 10 carbon atoms, and these may be the same or different from each other), 1,6-dichlorohexane and an aqueous sodium cyanide solution are When reacting to produce suberonitrile, 1,6-dichlorohexane and a catalyst are introduced into the first stage of multiple reactors arranged in series, and the reaction liquid in the latter reactor is separated into an oil layer and an aqueous layer after the reaction is completed. A method for producing suberonitrile, which is characterized in that an aqueous solution containing unreacted soda cyanide is introduced into the first stage and reacted.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028191A JPH0832669B2 (en) | 1987-02-12 | 1987-02-12 | Suberonitrile manufacturing method |
| AU17837/88A AU1783788A (en) | 1987-01-22 | 1988-05-24 | Powder mixing method and apparatus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62028191A JPH0832669B2 (en) | 1987-02-12 | 1987-02-12 | Suberonitrile manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63196548A true JPS63196548A (en) | 1988-08-15 |
| JPH0832669B2 JPH0832669B2 (en) | 1996-03-29 |
Family
ID=12241795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62028191A Expired - Lifetime JPH0832669B2 (en) | 1987-01-22 | 1987-02-12 | Suberonitrile manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0832669B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138074A (en) * | 2000-10-27 | 2002-05-14 | Japan Hydrazine Co Inc | Method for producing 1,6-dicyanohexane |
-
1987
- 1987-02-12 JP JP62028191A patent/JPH0832669B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002138074A (en) * | 2000-10-27 | 2002-05-14 | Japan Hydrazine Co Inc | Method for producing 1,6-dicyanohexane |
| JP4571740B2 (en) * | 2000-10-27 | 2010-10-27 | 株式会社日本ファインケム | Method for producing 1,6-dicyanohexane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0832669B2 (en) | 1996-03-29 |
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