JPH0529341B2 - - Google Patents
Info
- Publication number
- JPH0529341B2 JPH0529341B2 JP10476687A JP10476687A JPH0529341B2 JP H0529341 B2 JPH0529341 B2 JP H0529341B2 JP 10476687 A JP10476687 A JP 10476687A JP 10476687 A JP10476687 A JP 10476687A JP H0529341 B2 JPH0529341 B2 JP H0529341B2
- Authority
- JP
- Japan
- Prior art keywords
- naphthoquinone
- ions
- ceric
- aqueous solution
- naphthalene
- 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 - Lifetime
Links
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 82
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 54
- 239000003960 organic solvent Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001256 steam distillation Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 34
- 238000007254 oxidation reaction Methods 0.000 description 30
- 230000002378 acidificating effect Effects 0.000 description 25
- 239000007791 liquid phase Substances 0.000 description 15
- 239000012071 phase Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052684 Cerium Inorganic materials 0.000 description 10
- -1 cerium ions Chemical class 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 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 4
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 4
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 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
- 238000000605 extraction 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
- 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
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 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
- 150000004716 alpha keto acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 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 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 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
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000000746 purification Methods 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
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance 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)
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 ceric 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
分散剤によつて第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56−61321号公報）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。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。<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, there is a method for producing 1,4-naphthoquinone by oxidizing naphthalene dissolved in an organic solvent that is immiscible with water using a ceric ion-acid aqueous solution (Japanese Patent Publication No. 34978/1983), There is a method for producing 1,4-naphthoquinone characterized by suspending it in an aqueous solution of a ceric salt using a dispersant (Japanese Patent Application Laid-open No. 1983-61321).
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. 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、過、洗浄、再結晶するな
どの方法が行われる。 Then, from the obtained liquid phase oxidation product, 1,4-
As a method for separating and purifying naphthoquinone, methods such as concentrating the solvent, filtering, washing, and recrystallization are generally performed.
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
濃度であるほど、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、硫酸第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、硫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。従つて、工業的には反応速度を上げることに
よる生産性と１，４−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。<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, normally It is advantageous that the higher the concentration of 2cerium ions or the higher the oxidation reaction temperature, the faster the reaction rate becomes. On the other hand, from the viewpoint of selectivity for the target 1,4-naphthoquinone, it is important that the concentration of ceric ions in the acidic aqueous solution containing ceric ions is low, or that the oxidation reaction temperature is low. is preferred. In addition, when a sulfuric acid aqueous solution of ceric sulfate is used as the acidic aqueous solution containing ceric ions, the solubility of cerous sulfate produced by the oxidation reaction with ceric sulfate is low, so the sulfuric acid aqueous solution However, when a nitric acid aqueous solution of ceric ammonium sulfate is used, the solubility of ceric ammonium nitrate is high, resulting in a slow reaction rate. Although this method is advantageous, it has disadvantages in terms of selectivity and the production of large amounts of by-products. Therefore, from an industrial perspective, acidic aqueous solutions containing ceric ions are considered as a compromise between productivity by increasing the reaction rate and complexity of the purification process and product quality by selectivity of 1,4-naphthoquinone. Conditions such as the type of cerium ion, 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、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つたり、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, filtering, 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
電解酸化における電流効率の低下や電極寿命の低
下などをもたらす。従つて、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, the recovered acidic aqueous solution containing cerous ions is electrolytically oxidized to convert the cerous ions into secondary cerium ions.
In the case of regenerating cerium ions, 1,4-naphthoquinone dissolved in the acidic aqueous solution causes a decrease in current efficiency in electrolytic oxidation and a decrease in electrode life. Therefore, when recovering an acidic aqueous solution containing cerous ions, it is necessary to ensure that 1,4-naphthoquinone is not substantially contained therein.
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つ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 when the concentration of ceric ions is low. As a result, the selectivity of the target product can be increased and the produced 1 , 4-naphthoquinone to obtain high purity products.
〈問題点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
討の結果、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、低い反応温度であつて
も、あるいは第２セリウムイオンの濃度が低濃度
であつ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、(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剤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 Problems> As a result of intensive study on the shortcomings 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-naphthoquinone is selected. I found out that it can be obtained with good performance. 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 provides (a) electrolytic oxidation of an acidic aqueous solution containing cerous ions, converting the cerous ions in the aqueous solution into ceric ions, and supplying the first step to the second step of the agent.
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 immiscible with water and not oxidized to ceric ions. A second step of extracting 1,4-naphthoquinone using an organic solvent and separating the organic solvent phase from an acidic aqueous phase containing unreacted ceric ions and cerous ions generated by the oxidation reaction; ) Naphthalene, 1,4-naphthoquinone and the organic solvent are separated and purified from the organic solvent phase obtained in the second step to obtain 1,4-naphthoquinone as a product, while naphthalene and the organic solvent are each recovered and used in the first step. This is a method for producing 1,4-naphthoquinone characterized by comprising a third step of returning it to 1,4-naphthoquinone. 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１セリウ
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、硫酸等を単独あ
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、新規の仕込みや補充分
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有する。電解酸
化は従来行なわれている一般的な方法を用いるこ
とができる。 As the acidic aqueous solution containing ceric ions used in the first step of the present invention, various acidic aqueous solutions of various ceric salts such as ceric ammonium nitrate, ceric nitrate, or ceric 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, sulfuric acid, etc. can be used alone or in combination. can be used. This step mainly has the role of regenerating the cerous ions generated in the liquid phase oxidation of naphthalene in the second step and supplying them again to the second step. It also has the role of oxidizing into ions and supplying them to the second step. Electrolytic oxidation can be performed using conventional methods.
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。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／、
より好ましくは0.1〜３モル／の範囲である。
濃度が低す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つて不利であ
る。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諸操作に支障をきたす恐れ
が生じる。また、該酸化水溶液中の酸濃度につい
ては、酸濃度が低過ぎると第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／、更に好ましくは0.7〜2.0モ
ル／とする。 The obtained acidic aqueous solution containing ceric ions is supplied to the second step and used in the liquid phase oxidation reaction of naphthalene. Here, the ceric ion concentration in the acidic aqueous solution is preferably 0.05 to 6 mol/,
More preferably it is in the range of 0.1 to 3 mol/.
If the concentration 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. On the other hand, if it is too high, the above-mentioned problems and the viscosity of the liquid may increase, which may interfere with various process operations. Regarding the acid concentration in the oxidizing aqueous solution, if the acid concentration 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. Due to this disadvantage, the acid concentration in the acidic aqueous solution is preferably between 0.3 and 10 mol/, more preferably between 0.7 and 2.0 mol/.
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
り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、低い反応温度であつても、ある
いは第２セリウムイオンの濃度が低濃度であつて
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15〜35℃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10KHz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 of 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. More advantageously, by performing the reaction at 15 to 35°C, 1.
The selectivity of 4-naphthoquinone can be increased. The ultrasonic waves used in the present invention may have a frequency of 10 KHz or higher, and the irradiation method may be either an external irradiation method or an internal irradiation method,
Further, devices having individual frequencies and outputs can be used as the ultrasonic generator, and the ultrasonic radiator may be of any type such as a flat plate type, ring type, or disk 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、ターシヤリーブチル
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、クロルメチル、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。これらの有機溶媒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 substances thereof, and cyclohexane. , n-hexane,
Examples include organic solvents such as aliphatic hydrocarbons such as n-pentane and n-octane, and chlorinated aliphatic hydrocarbons such as carbon tetrachloride, chloromethyl, and dichloroethane. These organic solvents include naphthalene and 1,
In the operation of thoroughly dissolving 4-naphthoquinone and extracting and separating the organic solvent phase and the acidic aqueous solution phase after the second step, the concentration of 1,4-naphthoquinone in the acidic aqueous solution phase is reduced. 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 substantially eliminates 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。 In the third step of the present invention, naphthalene, 1,4-naphthoquinone and the organic solvent are separated and purified from the organic solvent phase obtained in the second step to obtain 1,4-naphthoquinone as a product. are collected and returned to the second step.
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。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
洗浄や再結晶を行つてもよい。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。 As a method for separating and purifying naphthalene, 1,4-naphthoquinone and the organic solvent from the organic solvent phase, conventional methods can be used. However, steam distillation under reduced pressure utilizing the vapor pressure difference between the organic solvent, naphthalene, and 1,4-naphthoquinone in the organic solvent phase 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。 The following description will be made based on 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.
〈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１
９を経て抽出塔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、一方第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 is then passed through line 1
9 and into an extraction tower 5, where the 1,4-naphthoquinone in the reaction mixture is extracted using the organic solvent introduced from the solvent tank 7 through line 30. The organic solvent phase in which 1,4-naphthoquinone is dissolved passes through line 20 to distillation column 6, while the first
The acidic aqueous phase containing cerium ions is line 21
The anolyte is sent to the anolyte tank 3.
〈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
によつ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> The organic solvent phase in which 1,4-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 at 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 organic solvents can be almost completely removed by steam distillation, yielding highly pure 1,4-naphthoquinone.
The 4-naphthoquinone crystals can also be washed with a fresh organic solvent in a filter 8 and dried in a drier 10 to produce a product.
〈第１工程〉
電解槽２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１７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 electrolytic cell 2 is equipped with an ion exchange membrane diaphragm in the center, which separates an anode chamber and a 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, and is introduced into the anolyte tank 3 via line 17.
circulates. On the other hand, a catholyte consisting of an electrolyte solution is supplied from a catholyte tank 1 to an electrolytic tank 2 through a line 14.
is introduced into the catholyte chamber of the catholyte chamber and circulated to the catholyte tank 1 via 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基設置してあ
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を詳細に説明する
が、本発明はこの実施例に限定されるものではな
い。<Example> 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
陽極に白金メツキチタン電極、陰極にSUS
316L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／で
あつた。Example 1 Platinum-plated titanium electrode for anode, SUS for cathode
A sulfuric acid aqueous solution of ceric sulfate was electrolyzed in a two-chamber electrolytic cell separated by an ion exchange membrane at a current density of 15 A/dm 2 using a 316L electrode. The ceric ion concentration in the obtained sulfuric acid aqueous solution was 0.20 mol/.
この第２セリウムイオンを含む硫酸水溶液
88680Kgとシクロヘキサン517Kgに溶解したナフタ
リン300Kgとを反応器に仕込み、28KHz、400W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
12990Kg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℃、400mmHgにて減圧蒸留
し、約50倍に濃縮した後、60℃、150mmHgにて水
蒸気蒸留を行なつた。水180Kgを添加し終わつた
時点で水蒸気蒸留を終えた。 Aqueous sulfuric acid solution containing this ceric ion
88680Kg and 300Kg of naphthalene dissolved in 517Kg of cyclohexane were charged into a reactor, internally irradiated with 28KHz, 400W ultrasonic waves, and reacted at 25°C for about 40 minutes. The reaction mixture was sent to an extraction column and cyclohexane
Using 12990Kg, undissolved 1,4-naphthoquinone was dissolved, and 1,4-naphthoquinone dissolved in the aqueous phase was dissolved.
4-naphthoquinone was extracted. The cyclohexane phase was sent to a distillation column, distilled under reduced pressure at 60°C and 400 mmHg, concentrated approximately 50 times, and then subjected to steam distillation at 60°C and 150 mmHg. Steam distillation was completed when 180 kg of water had been added.
次に、残つた１，４−ナフトキノンの結晶を乾
燥器に送り、80℃、300mmHgで３時間乾燥して純
度99.2％の結晶342.9Kg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 342.9 kg of crystals with a purity of 99.2%.
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.
１ 一般式R1X（R1はアリール基、アルケニル及
び複素環基の中から選ばれる有機基を示し、該有
機基は置換基を有していてもよく、Ｘはハロゲン
原子を示す）で表される有機ハロゲン化物を、塩
基性無機化合物及びパラジウム含有触媒の存在下
に水及び一酸化炭素と反応させることを特徴とす
る一般式R1COCOOH（R1は前記と同じ）で表さ
れるα−ケト酸類の製法。
1 With the general formula R 1 The organic halide represented by the general formula R 1 COCOOH (R 1 is the same as above) is reacted with water and carbon monoxide in the presence of a basic inorganic compound and a palladium-containing catalyst. Method for producing α-keto acids.
Claims (1)
の製造法。 ２ 第３工程において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
精製する操作を水蒸気蒸留によつて行うことを特
徴とする特許請求の範囲１に記載の方法。The third step is to collect the water and return it to the second step. A method for producing 1,4-naphthoquinone, characterized by comprising: 2. The method according to claim 1, wherein in the third step, the operation of separating and purifying naphthalene, 1,4-naphthoquinone, and the organic solvent from the organic solvent phase is performed 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 JPS63270635A (en) | 1988-11-08 |
| JPH0529341B2 true 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) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0647469B2 (en) * | 1988-10-28 | 1994-06-22 | 同和鉱業株式会社 | Ferrite powder for high density recording |
| 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 |
| CN103483174B (en) * | 2013-09-12 | 2016-03-23 | 四川省银河化学股份有限公司 | A kind of ultrasonic wave promotes the method for producing β-vitamin k4 |
| CN112626547B (en) * | 2020-12-25 | 2021-10-15 | 浙江工业大学 | A method for the indirect electrosynthesis of quinone compounds using ultrasonic assistance |
-
1987
- 1987-04-30 JP JP10476687A patent/JPS63270635A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63270635A (en) | 1988-11-08 |
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