JPS63270635A - Production of 1,4-naphthoquinone - Google Patents
Production of 1,4-naphthoquinoneInfo
- Publication number
- JPS63270635A JPS63270635A JP10476687A JP10476687A JPS63270635A JP S63270635 A JPS63270635 A JP S63270635A JP 10476687 A JP10476687 A JP 10476687A JP 10476687 A JP10476687 A JP 10476687A JP S63270635 A JPS63270635 A JP S63270635A
- Authority
- JP
- Japan
- Prior art keywords
- naphthoquinone
- ions
- aqueous solution
- naphthalene
- organic solvent
- 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
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 74
- 150000002500 ions Chemical class 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 44
- 239000003960 organic solvent Substances 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 34
- 239000007791 liquid phase Substances 0.000 claims abstract description 20
- 239000012071 phase Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 29
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- -1 cerium ions Chemical class 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000001256 steam distillation Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 238000000605 extraction Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract 3
- 230000001678 irradiating effect Effects 0.000 abstract 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 6
- 229930192627 Naphthoquinone Natural products 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002791 naphthoquinones Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- KHMZDLNSWZGRDB-UHFFFAOYSA-N 1,3,3-trichloroprop-1-ene Chemical compound ClC=CC(Cl)Cl KHMZDLNSWZGRDB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QDQNBKZMEYMOEH-UHFFFAOYSA-H [Ce+3].[Ce+3].OS(O)(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ce+3].[Ce+3].OS(O)(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QDQNBKZMEYMOEH-UHFFFAOYSA-H 0.000 description 1
- NORBXQIIEHGEJA-UHFFFAOYSA-O [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[NH4+].[Ce] Chemical compound [N+](=O)(O)[O-].[N+](=O)([O-])[O-].[NH4+].[Ce] NORBXQIIEHGEJA-UHFFFAOYSA-O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- QZJMONDPQWPMGI-UHFFFAOYSA-N lithium;azane Chemical compound [Li+].N QZJMONDPQWPMGI-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、ナフタリンを第２Ｌｙリウムイオンを含む酸
性水溶液を用いて液相酸化し、１，４−ナフトキノンを
工業的に有利に製造する方法に関する。１，４−ナフト
キノンはアントラキノンの原料等として工業的に有用で
ある。Detailed Description of the Invention <Industrial Application Field> The present invention provides an industrially advantageous method for producing 1,4-naphthoquinone by liquid-phase oxidation of naphthalene using an acidic aqueous solution containing secondary Lyrium ions. Regarding. 1,4-naphthoquinone is industrially useful as a raw material for anthraquinone.
〈従来の技術〉
ナフタリンを第２セリウムイオンを含む酸性水溶液を用
いて液相酸化し、１．４−ナフトキノンを製造する方法
はよく知られている。例えば、■水と混和しない有機溶
媒に溶解したナフタリンを第２セリウムイオン−酸性水
溶液を用いて酸化し、１，４−ナフトキノンを製造する
方法（特公昭４９−３４９７８号公報）、■粉末状のナ
フタリンを分散剤によって第２セリウム塩の水溶液中に
懸濁させることを特徴とする１、４−ナフトキノンの製
造方法（特開昭５６−６１３２７＠公報）等がある。こ
れら酸化反応に用いられる第２セリウムイオンを含む酸
性水溶液としては硝酸セリウムアンモニウム−硝酸水溶
液や硫酸セリウム−硫酸水溶液が一般的に用いられる。<Prior Art> A method for producing 1,4-naphthoquinone by liquid-phase oxidation of naphthalene using an acidic aqueous solution containing ceric ions is well known. For example, ■ a method for producing 1,4-naphthoquinone by oxidizing naphthalene dissolved in an organic solvent that is immiscible with water using a ceric ion-acidic aqueous solution (Japanese Patent Publication No. 34978/1978); There is a method for producing 1,4-naphthoquinone (JP-A-56-61327@), which is characterized by suspending naphthalene in an aqueous solution of ceric salt using a dispersant. As acidic aqueous solutions containing ceric ions used in these oxidation reactions, cerium ammonium nitrate-nitric acid aqueous solutions and cerium sulfate-sulfuric acid aqueous solutions are generally used.
また、従来の第２セリウムイオンによる酸化反応では温
度は通常４０〜８０℃が好ましいとされている。Further, in the conventional oxidation reaction using ceric ions, the temperature is usually preferably 40 to 80°C.
次いで、得られた液相酸化生成物から１，４−ナフトキ
ノンを分離精製する方法としては、一般的には溶媒を濃
縮後、濾過、洗浄、再結晶するなどの方法が行われる。Next, the method for separating and purifying 1,4-naphthoquinone from the obtained liquid phase oxidation product generally involves concentrating the solvent, followed by filtration, washing, and recrystallization.
また、前記液相酸化反応のプロセスとしては液相酸化反
応後に生成する第１セリウムイオンの第２セリウムイオ
ンへの再生法として電気化学的再生法の工程が含まれる
のが通常である。Further, the liquid phase oxidation reaction process usually includes an electrochemical regeneration process for regenerating cerium ions produced after the liquid phase oxidation reaction into cerium ions.
〈発明が解決しようとする問題点〉
前述した従来の第２セリウムイオンを含む酸性水溶液を
用いる液相酸化による１、４−ナフトキノンの製造法で
は、通常第２セリウムイオンを含む酸性水溶液中の第２
セリウムイオンの濃度が高Ｉ！度であるほど、あるいは
酸化反応温度が高温であるほど反応速度が速くなる点で
有利である。反面、目的とする１、４−ナフトキノンの
選択性の面からは、第２セリウムイオンを含む酸性水溶
液中の第２セリウムイオンの濃度が低濃度であること、
あるいは酸化反応温度が低温であることが好ましい。ま
た、第２セリウムイオンを含む酸性水溶液として、硫酸
セリウムの硫酸水溶液を用いた場合には、５Ａ′Ｍ第２
セリウムによる酸化反応で生成する硫酸第１セリウムの
溶解度が小さいために必然的に該硫酸水溶液中の第２セ
リウムイオンの濃度が低濃度になり反応速度が遅くなる
欠点を有し、一方、硝酸セリウムアンモニウムの硝酸水
溶液を用いた場合には、硝酸セリウムアンモニウムの溶
解度が高くて反応速度の点では有利であるが副生成物の
生成量が多く選択性の点で欠点がある。<Problems to be Solved by the Invention> In the conventional method for producing 1,4-naphthoquinone by liquid phase oxidation using an acidic aqueous solution containing ceric ions, it is common to 2
High concentration of cerium ions! It is advantageous that the higher the temperature or the higher the oxidation reaction temperature is, the faster the reaction rate becomes. On the other hand, from the viewpoint of selectivity for the target 1,4-naphthoquinone, the concentration of ceric ions in the acidic aqueous solution containing ceric ions is low;
Alternatively, it is preferable that the oxidation reaction temperature is low. In addition, when a sulfuric acid aqueous solution of cerium sulfate is used as the acidic aqueous solution containing ceric ions, 5A'M 2
Since the solubility of cerous sulfate produced in the oxidation reaction with cerium is low, the concentration of ceric ions in the sulfuric acid aqueous solution inevitably becomes low, resulting in a slow reaction rate. When an aqueous solution of ammonium in nitric acid is used, the solubility of ceric ammonium nitrate is high and the reaction rate is advantageous, but the amount of by-products produced is large and the selectivity is disadvantageous.
従って、工業的には反応速度を上げることによる生産性
と７．４−ナフトキノンの選択性による精製工程の複雑
さや製品品質とを考慮し、それらの妥協点において第２
セリウムイオンを含む酸性水溶液の種類、第２セリウム
イオンの濃度、酸化反応温度等の条件が設定される。更
には、温度が高すぎると第２セリウム塩の加水分解が生
じるうえ生成物の着色、あるいは装置の腐蝕性の面から
不利を生じる。これらの結果として前述の如く、酸化反
応温度は通常４０〜８０℃が好ましいとされている。Therefore, from an industrial perspective, considering the productivity by increasing the reaction rate and the complexity of the purification process and product quality due to the selectivity of 7.4-naphthoquinone, the second
Conditions such as the type of acidic aqueous solution containing cerium ions, the concentration of ceric ions, and the oxidation reaction temperature are set. Moreover, if the temperature is too high, hydrolysis of the ceric salt occurs, which is disadvantageous in terms of coloration of the product and corrosion of the equipment. As a result of these, as mentioned above, the oxidation reaction temperature is usually preferably 40 to 80°C.
次いで、生成した１、４−ナフトキノンを精製するには
単に溶媒を濃縮後、濾過、洗浄するなどの方法では未反
応のナフタリンや副生物の除去が充分になされず、満足
できる純度のものは得られず、再結晶が不可欠で工程が
複雑になったり、収率の低下が避けられない。Next, in order to purify the produced 1,4-naphthoquinone, methods such as simply concentrating the solvent, filtration, and washing do not sufficiently remove unreacted naphthalene and byproducts, making it impossible to obtain a product of satisfactory purity. However, recrystallization is essential, which complicates the process and unavoidably lowers the yield.
更に、回収した第１セリウムイオンを含む酸性水溶液を
電解酸化し、第１セリウムイオンを第２セリウムイオン
に再生する場合において、該酸性水溶液中に溶解してい
る１、４−ナフトキノンは電解酸化におけるＮ流動帯の
低五や電極寿命の低下などをもたらす。従って、第１セ
リウムイオンを含む酸性水溶液を回収するときに１．４
−ナフトキノンが実質的に含まれない程度にしなければ
ならない。Furthermore, when the recovered acidic aqueous solution containing cerous ions is electrolytically oxidized to regenerate the cerous ions into ceric ions, the 1,4-naphthoquinone dissolved in the acidic aqueous solution is This results in low N flow zone and shortened electrode life. Therefore, when recovering an acidic aqueous solution containing cerous ions, 1.4
- Must be substantially free of naphthoquinone.
本発明は上記の欠点を解消し、第２セリウムイオンの濃
度が低濃度であっても反応速度を促進することが可能で
あり、その結果、目的物の選択性を高め得るとともに、
生成した１、４−ナフトキノンから高純度の製品を得る
方法を提供するものである。The present invention solves the above-mentioned drawbacks, and can accelerate the reaction rate even at a low concentration of ceric ions. As a result, the selectivity of the target product can be increased, and
The present invention provides a method for obtaining a highly purified product from the produced 1,4-naphthoquinone.
〈問題を解決するための手段〉
本発明者等は前記従来法の欠点について鋭意検肘の結果
、ナフタリンを第２セリウムイオンを含む酸性水溶液を
用いて酸化し１，４−ナフトキノンを得る方法において
、超音波照射下に液相酸化反応を行なうことにより、低
い反応温度であっても、あるいは第２セリウムイオンの
濃度が低濃度であっても反応速度が促進され、１，４−
ナフトキノンが選択性よく得られることを見出した。そ
して更に該液相酸化反応から１，４−ナフトキノンを抽
出するのに使用する有機溶媒や１，４−ナフトキノンの
分離精製法についても検討を重ねた結果、本発明を完成
したものである。即ち本発明は、ω第１セリウムイオン
を含む酸性水溶液を電解酸化し、該水溶液中の第１セリ
ウムイオンを第２セリウムイオンにして第２工程に供給
する第１工程、０第１工程で得られた第２セリウムイオ
ンを含む酸性水溶液を用いて超音波照射下にナフタリン
を液相酸化し、次いで水と非混和性でか゛つ第２セリウ
ムイオンに酸化されない有機溶媒を用いて１．４−ナフ
トキノンを抽出し、有機溶媒相と未反応の第２セリウム
イオンおよび酸化反応により生成した第１セリウムイオ
ンを含む酸性水溶液相とを分離する第２工程、（ハ）第
２工程で得られた有機溶媒相からナフタリン、１．４−
ナフトキノンおよび有機溶媒を分離精製し、１，４−ナ
フトキノンを製品として得る一方、ナフタリンおよび１
１機溶媒を各々回収して第１工程に戻す第３工程、から
なることを特徴とする１、４−ナフトキノンの製造法で
ある。以下に詳しく説明する。<Means for Solving the Problem> As a result of intensive investigation into the drawbacks of the conventional method, the present inventors have developed a method for obtaining 1,4-naphthoquinone by oxidizing naphthalene using an acidic aqueous solution containing ceric ions. By carrying out the liquid phase oxidation reaction under ultrasonic irradiation, the reaction rate is accelerated even at low reaction temperatures or at low concentrations of ceric ions, and 1,4-
It has been found that naphthoquinone can be obtained with good selectivity. Furthermore, as a result of repeated studies on the organic solvent used to extract 1,4-naphthoquinone from the liquid phase oxidation reaction and the method for separating and purifying 1,4-naphthoquinone, the present invention was completed. That is, the present invention electrolytically oxidizes an acidic aqueous solution containing ω cerium ions, converts the cerium ions in the aqueous solution into cerium ions, and supplies the cerium ions to the second step. Naphthalene was oxidized in a liquid phase under ultrasonic irradiation using an acidic aqueous solution containing ceric ions, and then 1.4- a second step of extracting naphthoquinone and separating the organic solvent phase from an acidic aqueous phase containing unreacted ceric ions and cerous ions generated by the oxidation reaction; (iii) the organic solvent obtained in the second step; Naphthalene from the solvent phase, 1.4-
Naphthoquinone and the organic solvent are separated and purified to obtain 1,4-naphthoquinone as a product, while naphthalene and
This method for producing 1,4-naphthoquinone is characterized by comprising a third step in which each solvent is recovered and returned to the first step. This will be explained in detail below.
本発明の第１工程において用いる第１セリウムイオンを
含む酸性水溶液としては硝酸第１ｔ？リウムアンモニウ
ム、硝酸第１セリウムまたは硫酸第１セリウム等の各種
の第１セリウム塩の各種酸性水溶液が使用できる。酸と
しては、上記第１セリウムイオン供給源を形成する陰イ
オンに対応する酸を使用することができるが、それ以外
の酸を添加することもでき、例えば硫酸、硝酸等を単独
あるいは混合して使用することができる。該工程は主と
して第２工程のナフタリンの液相酸化で生成した第１セ
リウムイオンを再生し再度第２工程に供給する役割を有
するが、新規の仕込みゃ補充分の第１セリウムイオンを
第２セリウムイオンに酸化し第２工程に供給する役割を
も右する。電解酸化は従来性なわれている一般的な方法
を用いることができる。The acidic aqueous solution containing ceric ions used in the first step of the present invention is nitric acid 1t? Various acidic aqueous solutions of various cerous salts such as lithium ammonium, cerous nitrate or cerous sulfate can be used. As the acid, an acid corresponding to the anion forming the above-mentioned cerium ion source can be used, but other acids can also be added. For example, sulfuric acid, nitric acid, etc. can be used alone or in combination. can be used. This step mainly has the role of regenerating the ceric ions generated in the liquid phase oxidation of naphthalene in the second step and supplying them again to the second step. It also plays the role of oxidizing into ions and supplying them to the second process. For electrolytic oxidation, conventional methods can be used.
得られた第２セリウムイオンを含む酸性水溶液は第２工
程に供給されナフタリンの液相酸化反応に使用される。The obtained acidic aqueous solution containing ceric ions is supplied to the second step and used in the liquid phase oxidation reaction of naphthalene.
ここで該酸性水溶液中の第２セリウムイオン°濃度は好
ましくは０．０５〜６モル／１、より好ましくは０．１
〜３モル／１の範囲である。Here, the concentration of ceric ion in the acidic aqueous solution is preferably 0.05 to 6 mol/1, more preferably 0.1
It is in the range of ~3 mol/1.
ｍ度が低ずぎると酸化力が弱く、反応速度が遅くなるだ
けでなく反応液量も大となって不利である。If the m degree is too low, the oxidizing power will be weak, which will not only slow down the reaction rate but also increase the amount of reaction liquid, which is disadvantageous.
逆に高すぎると、前述の問題や、液の粘度が上昇してプ
ロセス上の開操作に支障をきたす恐れが生じる。また、
該酸性水溶液中の酸濃度については、Ｂ−ＩＡ度が低過
ぎると第２セリウムイオンが不安定になり、酸濃度が高
過ぎると第２セリウムイオンの溶解度が低下したり装置
の腐蝕の面から不利であるため、酸性水溶液中の酸濃度
は好ましくは０．３〜１０モル／１、更に好ましくは０
．７〜２．０モル／ｉとする。On the other hand, if it is too high, the above-mentioned problem or the viscosity of the liquid may increase, which may interfere with the opening operation in the process. Also,
Regarding the acid concentration in the acidic aqueous solution, if the B-IA degree is too low, the ceric ions will become unstable, and if the acid concentration is too high, the solubility of the ceric ions will decrease and the equipment will be corroded. Since this is disadvantageous, the acid concentration in the acidic aqueous solution is preferably 0.3 to 10 mol/1, more preferably 0.
．． The amount should be 7 to 2.0 mol/i.
本発明において、第２工程の液相酸化反応は超音波照射
下に行われる。液相酸化反応は、従来法では通常撹拌機
、外部循環、ガスの吹込み等による強制撹拌下に行なわ
れるが、本発明においては超音波照射下に、好ましくは
強制撹拌を組合せて行うことにより、低い反応温度であ
っても、あるいは第２セリウムイオンの濃度が低濃度で
あっても充分な反応速度が保持できる。その結果、第２
工程の液相酸化反応は好ましくは０〜８０℃、更に好ま
しくは１５〜３５℃で行われる。８０℃以上の温度では
前述の第２セリウム塩の加水分解、副反応生成物の混入
や着色、あるいは装置の腐蝕性の面から問題になること
が起こりうるし、０℃以下の温度では反応速度の減少を
きたす他、冷却のための費用がかかる。更に有利には１
５〜３５℃で反応させることにより、適度な反応速度を
維持しつつ１．４−ナフトキノンの選択性を高めること
ができる。本発明において用いられる超音波は１０ＫＨ
ｚ以上の周波数のものであればよく、その照射方式は外
部照射方式、内部照射方式のいずれでもよく、また超音
波発生装置としても個々の周波数、出力を有する装置が
使用でき、超音波放射体としては平板型、リング型、円
板型等のいずれの型式でもよい。In the present invention, the liquid phase oxidation reaction in the second step is performed under ultrasonic irradiation. In conventional methods, the liquid phase oxidation reaction is usually carried out under forced stirring using a stirrer, external circulation, gas blowing, etc., but in the present invention, it is carried out under ultrasonic irradiation, preferably in combination with forced stirring. Even if the reaction temperature is low or the concentration of ceric ions is low, a sufficient reaction rate can be maintained. As a result, the second
The liquid phase oxidation reaction in the step is preferably carried out at 0 to 80°C, more preferably at 15 to 35°C. At temperatures above 80°C, problems may arise from the aforementioned hydrolysis of the ceric salt, contamination and coloring of side reaction products, and corrosion of the equipment, while at temperatures below 0°C, the reaction rate may be reduced. In addition to this, cooling costs are incurred. Even more advantageously 1
By performing the reaction at 5 to 35°C, selectivity for 1,4-naphthoquinone can be increased while maintaining a suitable reaction rate. The ultrasonic wave used in the present invention is 10KH
The irradiation method may be either an external irradiation method or an internal irradiation method, and devices with individual frequencies and outputs can be used as ultrasonic generators. It may be of any type, such as a flat plate type, ring type, or disc type.
本発明の第２工程において用いる水と非混和性でかつ第
２セリウムイオンに酸化されない有機溶媒の例としては
、ベンゼン、ターシャリ−ブチルベンゼン、クロルベン
ゼン等の芳香族炭化水素又はその置換体、シクロヘキサ
ン、ｎ−ヘキサン、ｎ−ペンタン、ｎ−オクタン等の脂
肪族炭化水素、四塩化炭素、クロルメチレン、ジクロル
エタン等の塩素化脂肪族炭化水素等の有機溶媒が挙げら
れる。これらの有機溶剤はナフタリンおよび１，４−ナ
フトキノンを良く溶解し、第２工程後段の有機溶媒相と
酸性水溶液相とを抽出分離する操作において、酸性水溶
液相中の１，４−ナフトキノン濃度を低下せしめる。酸
性水溶液相中に含まれる酸化反応により生成した第１セ
リウムイオンは第１工程にて電解酸化し第２セリウムイ
オンに再生して循環使用されるが、前述した第１工程に
おける酸性水溶液相中の１．４−ナフトキノンの存在に
よる電解酸化時の電流効率低下や電極寿命低下なども実
質的に問題なくなる。Examples of organic solvents that are immiscible with water and are not oxidized to ceric ions used in the second step of the present invention include aromatic hydrocarbons such as benzene, tert-butylbenzene, and chlorobenzene, or substituted products thereof, and cyclohexane. , n-hexane, n-pentane, n-octane, and other organic solvents, and carbon tetrachloride, chlorinated aliphatic hydrocarbons such as chlormethylene, dichloroethane, and other organic solvents. These organic solvents dissolve naphthalene and 1,4-naphthoquinone well, and reduce the concentration of 1,4-naphthoquinone in the acidic aqueous solution phase in the operation of extracting and separating the organic solvent phase and the acidic aqueous solution phase at the latter stage of the second step. urge The ceric ions generated by the oxidation reaction contained in the acidic aqueous solution phase are electrolytically oxidized in the first step, regenerated into ceric ions, and recycled for use. The presence of 1.4-naphthoquinone does not substantially cause problems such as a decrease in current efficiency during electrolytic oxidation and a decrease in electrode life.
ナフタリンを第２セリウムイオンを含む酸性水溶液で酸
化する場合に、ナフタリンをこれらの有機溶媒に溶解せ
しめて酸化させても、あるいは溶媒を用いずに酸化させ
後から有機溶媒を添加してナフタリンおよび酸化生成物
の１，４−ナフトキノンを有機溶媒に溶解せしめてもよ
く、また該系は液状でもスラリー状でもよい。When naphthalene is oxidized with an acidic aqueous solution containing ceric ions, the naphthalene can be dissolved in these organic solvents and oxidized, or the naphthalene can be oxidized without using a solvent and an organic solvent can be added afterwards. The product 1,4-naphthoquinone may be dissolved in an organic solvent, and the system may be in the form of a liquid or a slurry.
本発明の第３工程においては、第２工程で得られた有機
溶媒相からナフタリン、１，４−ナフトキノンおよび有
機溶媒を分１１１ｉ精製し、１．／１−ナフトキノンを
製品として得る一方、ナフタリンおよび有機溶媒を各々
回収して第２工程に戻１゜有機溶媒相からナフタリン、
１．４−ナフトキノンおよび有機溶媒を分離精製する方
法としては、従来より行なわれている方法をとることが
できる。In the third step of the present invention, naphthalene, 1,4-naphthoquinone and the organic solvent are purified by 111i from the organic solvent phase obtained in the second step, and 1. /1-Naphthoquinone is obtained as a product, while naphthalene and organic solvent are each recovered and returned to the second step.Naphthalene,
As a method for separating and purifying 1,4-naphthoquinone and the organic solvent, conventional methods can be used.
しかし、有機溶媒相中の有機溶媒、ナフタリンおよび１
．４−ナフトキノンの蒸気圧差を利用して減圧下で水蒸
気蒸留することにより、各成分が容易に分離でき好まし
い方法である。水蒸気蒸留により、有機溶媒およびナフ
タリンはほぼ完全に除去され、高純度の１，４−ナフト
キノンを得ることができる。勿論、更に純度を上げるた
め洗浄や再結晶を行ってもよい。一方、有機溶媒および
ナフタリンは回収し、第２工程に戻され、再利用される
。However, the organic solvent, naphthalene and 1
．． Steam distillation under reduced pressure utilizing the vapor pressure difference of 4-naphthoquinone is a preferred method because each component can be easily separated. By steam distillation, the organic solvent and naphthalene are almost completely removed, and highly pure 1,4-naphthoquinone can be obtained. Of course, washing and recrystallization may be performed to further increase purity. On the other hand, the organic solvent and naphthalene are recovered, returned to the second step, and reused.
本発明の方法を第１工程から第３工程まで連続的に実施
する場合の一実施態様を示すフローシート図（第１図）
に基づき、以下に説明する。A flow sheet diagram (Fig. 1) showing an embodiment in which the method of the present invention is carried out continuously from the first step to the third step.
The following is an explanation based on the following.
く第２工程〉
ナフタリンタンク１３よりライン３５を経てナフタリン
を、陽極液タンク３よりライン１８を経て陽極液を反応
器４に仕込み、超音波照射下に液相酸化反応を行う。次
いで反応混合物をライン１９ケ経て抽出塔５に導入し、
該抽出塔にて溶媒タンク７よりライン３０を経て導入さ
れた有機溶媒により反応混合物中の１，４−ナフトキノ
ンの抽出を行う。１゜４−ナフトキノンを溶解した有機
溶媒相はライン２０を経て蒸留塔６へ、一方策１セリウ
ムイオンを含む酸性水溶液相はライン２１を経て陽極液
タンク３へ送る。Second Step> Naphthalene is charged from the naphthalene tank 13 via line 35, and anolyte is charged from the anolyte tank 3 via line 18 to the reactor 4, and a liquid phase oxidation reaction is performed under ultrasonic irradiation. The reaction mixture was then introduced into the extraction column 5 through 19 lines,
In the extraction tower, 1,4-naphthoquinone in the reaction mixture is extracted with an organic solvent introduced from the solvent tank 7 through the line 30. The organic solvent phase in which 1.4-naphthoquinone is dissolved is sent to the distillation column 6 via line 20, while the acidic aqueous phase containing 1.1 cerium ions is sent to the anolyte tank 3 via line 21.
く第３工程〉
１．４−ナフトキノンを溶解した有機溶媒相はまず蒸留
塔６で有機溶媒相中に溶解したナフタリンが析出しない
程度に濃縮する。留出した有機溶媒は熱交換器２２で冷
却し、溶媒タンク７に回収する。蒸留は常圧でもよいが
、１．４−ナフトキノンが８０〜９０℃にて変質するた
め、使用する溶媒によっては減圧下に蒸留するのが好ま
しい。次に、純水タンク１２からライン３４を経て水を
蒸留塔６に添加して水蒸気蒸留を行う。留分は熱交換器
２２で冷却して分離タンク１１に貯蔵し、ここで水相と
ナフタリン及び有機溶媒からなる油相とに分離する。水
相はライン３３を経て純水タンク１２に、油相はライン
３２を経てナフタリンタンク１３にそれぞれ回収する。Third Step> 1. The organic solvent phase in which the 4-naphthoquinone is dissolved is first concentrated in a distillation column 6 to such an extent that naphthalene dissolved in the organic solvent phase does not precipitate. The distilled organic solvent is cooled by a heat exchanger 22 and collected into a solvent tank 7. Distillation may be carried out under normal pressure, but since 1,4-naphthoquinone deteriorates at 80 to 90°C, it is preferable to distill under reduced pressure depending on the solvent used. Next, water is added to the distillation column 6 from the pure water tank 12 via the line 34 to perform steam distillation. The fraction is cooled by a heat exchanger 22 and stored in a separation tank 11, where it is separated into an aqueous phase and an oil phase consisting of naphthalene and an organic solvent. The aqueous phase is collected into the pure water tank 12 via line 33, and the oil phase is collected into the naphthalene tank 13 via line 32.
水蒸気蒸留によりナフタリン及び有機溶媒はほぼ完全に
除去でき、高純度の１，４−ナフトキノンが得られるが
、更に純度を上げるため、該１．４−ナフトキノンの結
晶を新しい有機溶媒を用いて濾過器８で洗浄し、乾燥器
１０で乾燥し、製品とすることもできる。Naphthalene and the organic solvent can be almost completely removed by steam distillation, yielding highly pure 1,4-naphthoquinone. However, in order to further increase the purity, the 1,4-naphthoquinone crystals are filtered using fresh organic solvent. 8 and dried in a drier 10 to produce a product.
く第１工程〉
電解１ｆｆ２は中央にイオン交換膜の隔膜を備えており
、これを境に陽極室と陰極室とが隔てられている。陽極
液タンク３から第１セリウムイオンを含む酸性水溶液を
ライン１６を経て電解槽２の陽極室に導入し、ライン１
７を経て陽極液タンク３に循環する。一方、陰極液タン
ク１から電解質の溶液からなる陰極液をライン１４を経
て電解槽２の陰極室に導入し、ライン１５を経て陰極液
タンク１に循環する。電解槽２に電気を通じ、第１セリ
ウムイオンを電解酸化して第２セリウムイオンに酸化す
る。First Step> The electrolysis 1ff2 is equipped with an ion exchange membrane diaphragm in the center, which separates the anode chamber and the cathode chamber. An acidic aqueous solution containing cerium ions is introduced from the anolyte tank 3 into the anode chamber of the electrolytic cell 2 via line 16.
7 and circulates to the anolyte tank 3. On the other hand, a catholyte consisting of an electrolyte solution is introduced from the catholyte tank 1 through a line 14 into the cathode chamber of the electrolytic cell 2, and is circulated into the catholyte tank 1 through a line 15. Electricity is passed through the electrolytic bath 2 to electrolytically oxidize the first cerium ions to the second cerium ions.
第１図の場合、陽極液タンクは１基設置しであるだけで
あるが、２基設置して電解酸化前の液と電解酸化後の液
とを別々のタンクに分けて貯蔵してもよい。In the case of Figure 1, only one anolyte tank is installed, but it is also possible to install two anolyte tanks and store the liquid before electrolytic oxidation and the liquid after electrolytic oxidation in separate tanks. .
〈実施例〉
次に、実施例により本発明の詳細な説明するが、本発明
はこの実施例に限定されるものではない。<Examples> Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
陽極に白金メッキチタン電極、陰極に５ＩＩＳ ３１６
１電極を用い、電流密度１５Ａ／ｄｍ２にてイオン交換
膜で隔てられた２室型電解槽で硫酸第１セリウムの硫酸
水溶液を電解した。得られた硫酸水溶液中の第２セリウ
ムイオン濃度は０．２０モル／ｆ！であった。Example 1 Platinum-plated titanium electrode for anode, 5IIS 316 for cathode
A sulfuric acid aqueous solution of cerous sulfate was electrolyzed in a two-chamber electrolytic cell separated by an ion exchange membrane at a current density of 15 A/dm2 using one electrode. The ceric ion concentration in the obtained sulfuric acid aqueous solution was 0.20 mol/f! Met.
この第２セリウムイオンを含む硫酸水溶液８８．６８０
Ｋｇとシクロヘキサン５１７Ｋｇに溶解したナフタリン
３００ Ｋｇとを反応器に仕込み、２８Ｋｌ−１ｚ１４
００Ｗの超音波を内部照射し、２５℃にて約４０分間反
応させた。反応混合物を抽出塔に送り、シクロヘキサン
１２．９９（ｌｙを用いて未溶解の１．４−ナフトキノ
ンを溶解するとともに、水相中に溶解している１、４−
ナフトキノンを抽出した。シクロヘキサン相を蒸留塔へ
送り、６０℃、４００ ｉｍＨｇにて減圧蒸留し、約５
０倍に濃縮した後、６０℃、１５０ ｌｌｌｍＨｇにて
水蒸気蒸留を行なった。水１８０Ｋｇを添加し終わった
時点で水蒸気蒸留を終えた。Sulfuric acid aqueous solution containing this ceric ion 88.680
Kg and 300 Kg of naphthalene dissolved in 517 Kg of cyclohexane were charged into a reactor, and 28 Kl-1z14
Internal irradiation with 00W ultrasonic waves was carried out, and the reaction was carried out at 25°C for about 40 minutes. The reaction mixture is sent to an extraction column, and undissolved 1,4-naphthoquinone is dissolved using cyclohexane 12.99 (ly), and 1,4-naphthoquinone dissolved in the aqueous phase is dissolved.
Naphthoquinone was extracted. The cyclohexane phase was sent to a distillation column and distilled under reduced pressure at 60°C and 400 imHg to give a
After concentrating to 0 times, steam distillation was performed at 60° C. and 150 llmHg. Steam distillation was completed when 180 kg of water had been added.
次に、残った１、４−ナフトキノンの結晶を乾燥器に送
り、８０℃、３００ ｍｍＨｇで３時間乾燥して純度９
９．２％の結晶３４２．９ Ｋｙを得た。Next, the remaining 1,4-naphthoquinone crystals were sent to a dryer and dried at 80°C and 300 mmHg for 3 hours to obtain a purity of 9.
9.2% crystals of 342.9 Ky were obtained.
第１図は、本発明の方法を第１工程から第３工程まで連
続的に実施する場合の一実施態様を示すフローシート図
である。FIG. 1 is a flow sheet diagram showing an embodiment in which the method of the present invention is carried out continuously from the first step to the third step.
Claims (2)
液を用いて液相酸化する１，４−ナフトキノンの製造法
において、 （イ）第１セリウムイオンを含む酸性水溶液を電解酸化
し、該水溶液中の第１セリウムイオンを第２セリウムイ
オンにして第２工程に供給する第１工程。 （ロ）第１工程で得られた第２セリウムイオンを含む酸
性水溶液を用いて超音波照射下にナフタリンを液相酸化
し、次いで水と非混和性でかつ第２セリウムイオンに酸
化されない有機溶媒を用いて１，４−ナフトキノンを抽
出し、有機溶媒相と未反応の第２セリウムイオンおよび
酸化反応により生成した第１セリウムイオンを含む酸性
水溶液相とを分離する第２工程。 （ハ）第２工程で得られた有機溶媒相からナフタリン、
１，４−ナフトキノンおよび有機溶媒を分離精製し、１
，４−ナフトキノンを製品として得る一方、ナフタリン
および有機溶媒を各々回収して第２工程に戻す第３工程
。 からなることを特徴とする１，４−ナフトキノンの製造
法。(1) In a method for producing 1,4-naphthoquinone in which naphthalene is oxidized in a liquid phase using an acidic aqueous solution containing ceric ions, (a) an acidic aqueous solution containing ceric ions is electrolytically oxidized, and the A first step in which the first cerium ions are converted into second cerium ions and supplied to the second step. (b) Liquid-phase oxidation of naphthalene under ultrasonic irradiation using the acidic aqueous solution containing ceric ions obtained in the first step, and then an organic solvent that is immiscible with water and not oxidized to ceric ions. A second step of extracting 1,4-naphthoquinone using a solvent and separating an organic solvent phase from an acidic aqueous solution phase containing unreacted ceric ions and ceric ions produced by an oxidation reaction. (c) naphthalene from the organic solvent phase obtained in the second step;
Separate and purify 1,4-naphthoquinone and organic solvent,
, 4-naphthoquinone as a product, while recovering naphthalene and the organic solvent and returning them to the second step. A method for producing 1,4-naphthoquinone, characterized by comprising:
，４−ナフトキノンおよび有機溶媒を分離精製する操作
を水蒸気蒸留によって行うことを特徴とする特許請求の
範囲（１）に記載の方法。(2) In the third step, naphthalene, 1
, 4-naphthoquinone and the organic solvent are separated and purified by steam distillation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10476687A JPS63270635A (en) | 1987-04-30 | 1987-04-30 | Production of 1,4-naphthoquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10476687A JPS63270635A (en) | 1987-04-30 | 1987-04-30 | Production of 1,4-naphthoquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63270635A true JPS63270635A (en) | 1988-11-08 |
| JPH0529341B2 JPH0529341B2 (en) | 1993-04-30 |
Family
ID=14389601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10476687A Granted JPS63270635A (en) | 1987-04-30 | 1987-04-30 | Production of 1,4-naphthoquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63270635A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120237A (en) * | 1988-10-28 | 1990-05-08 | Dowa Mining Co Ltd | Ferrite powder for high density recording having small temperature dependency of coercive force |
| JPH02120235A (en) * | 1988-10-28 | 1990-05-08 | Dowa Mining Co Ltd | Ferrite powder for high density recording |
| CN103483174A (en) * | 2013-09-12 | 2014-01-01 | 四川省银河化学股份有限公司 | Method for promoting beta-menadione production through ultrasonic waves |
| CN112626547A (en) * | 2020-12-25 | 2021-04-09 | 浙江工业大学 | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance |
-
1987
- 1987-04-30 JP JP10476687A patent/JPS63270635A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02120237A (en) * | 1988-10-28 | 1990-05-08 | Dowa Mining Co Ltd | Ferrite powder for high density recording having small temperature dependency of coercive force |
| JPH02120235A (en) * | 1988-10-28 | 1990-05-08 | Dowa Mining Co Ltd | Ferrite powder for high density recording |
| JPH0647469B2 (en) * | 1988-10-28 | 1994-06-22 | 同和鉱業株式会社 | Ferrite powder for high density recording |
| CN103483174A (en) * | 2013-09-12 | 2014-01-01 | 四川省银河化学股份有限公司 | Method for promoting beta-menadione production through ultrasonic waves |
| CN112626547A (en) * | 2020-12-25 | 2021-04-09 | 浙江工业大学 | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0529341B2 (en) | 1993-04-30 |
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