EP0370920B1 - Procédé de préparation de quinone à partir d'hydroquinone par électrolyse - Google Patents

Procédé de préparation de quinone à partir d'hydroquinone par électrolyse Download PDF

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Publication number
EP0370920B1
EP0370920B1 EP89420383A EP89420383A EP0370920B1 EP 0370920 B1 EP0370920 B1 EP 0370920B1 EP 89420383 A EP89420383 A EP 89420383A EP 89420383 A EP89420383 A EP 89420383A EP 0370920 B1 EP0370920 B1 EP 0370920B1
Authority
EP
European Patent Office
Prior art keywords
hydroquinone
quinone
electrolysis
cosolvent
process according
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
Application number
EP89420383A
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German (de)
English (en)
French (fr)
Other versions
EP0370920A1 (fr
Inventor
Olivier Le Roux
Jean Bachot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Priority to AT89420383T priority Critical patent/ATE87040T1/de
Publication of EP0370920A1 publication Critical patent/EP0370920A1/fr
Application granted granted Critical
Publication of EP0370920B1 publication Critical patent/EP0370920B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation

Definitions

  • the present invention relates to a process for the preparation of quinone from hydroquinone by electrolysis.
  • the present invention presents a new electrolytic process making it possible to prepare, with industrial yields, a quinone by electrolysis of an aqueous medium containing a hydroquinone; this new process is characterized in that one carries out the electrolysis of an aqueous dispersion or emulsion containing, in addition to said aqueous solution of hydroquinone, a stable co-solvent poorly soluble in water which is a good solvent for quinone and a poor solvent for hydroquinone.
  • the cosolvent must allow easy recovery of the quinone produced.
  • relatively high-boiling cosolvents may be of interest, since electrolysis will be possible at high temperatures, it is generally desirable to choose a relatively low-boiling product as co-solvent as this may facilitate the subsequent recovery of the quinone by simple evaporation of the cosolvent.
  • co-solvents having such properties, mention may be made of aromatic carbides (in particular toluene and benzene), cycloalkanes, alkanes and halogenated aliphatic carbides (such as methylene chloride and 1,2-dichloroethane). These halogenated aliphatic carbides seem to be the most interesting solvents.
  • aromatic carbides in particular toluene and benzene
  • cycloalkanes such as methylene chloride and 1,2-dichloroethane
  • halogenated aliphatic carbides seem to be the most interesting solvents.
  • the solubilities of para-benzoquinone in various solvents will be mentioned below, by way of examples: whereas, in these same solvents, hydroquinone is only soluble at a rate of a few g / l. Mixtures of these cosolvents may also be used
  • the relative amounts of water and of cosolvent can vary with the nature of the cosolvent and possibly of the reactants (hydroquinone and quinone).
  • these relative quantities should be adjusted to take into account, on the one hand, the conductivity of the emulsion (which would require a high proportion of aqueous phase) and, on the other hand, the amount of p-benzoquinone to be extracted (which would require a high proportion of organic phase).
  • the ratio, by volume, of the aqueous and organic phases is from 0.1 to 50 and preferably from 0.5 to 10. When said ratio is less than 0.1, the aqueous phase being in very low proportion, the conductivity of the mixture is poor. When said ratio is greater than 50, the possibilities of solubilization of the quinone are insufficient.
  • the "quality" (that is to say in fact the fineness and the stability) of the dispersion of the cosolvent in the aqueous phase can play a role in the yield of the reaction. It will be easy for the specialist, taking into account the preparation processes used to produce the dispersion or the emulsion (for example using a pump or a static mixer), to optimize said dispersion, possibly in it. adding inert emulsifiers or surfactants, to obtain maximum yield.
  • the temperature at which electrolysis takes place has a known influence (the increase in temperature improving the conductivity of the emulsion, improving the solubility of the reagents in their media and improving the kinetics of the reaction); however, if for quinone recovery problems a cosolvent with a relatively low boiling point is used, one will be limited by the boiling point of this cosolvent. In practice, temperatures of 10 to 80 ° C will be used.
  • the concentration of hydroquinone in water does not seem to be a decisive factor concerning the rate of conversion of hydroquinone to quinone with equal electrical yield, but any increase in said concentration (within the limit of the solubility of hydroquinone ) will promote volume yield.
  • the electric current density it is generally of the order of 5 to 40 A / dm2.
  • the reaction is carried out in a conventional electrolysis cell preferably comprising a separator.
  • a separator the latter is preferably of the cationic type such as for example a membrane of registered trademark NAFION.
  • the cathode compartment as known, reduction of water made conductive by an acid such as sulfuric acid is carried out (but it is also possible to carry out, in this cathode compartment any other electrochemical reduction reaction); the cathode must be non-corrodible and with as low an overvoltage as possible.
  • the dispersion or emulsion according to the invention is therefore admitted, comprising therefore an aqueous phase, the conductivity of which has been improved by the addition of an inert acid with respect to the reactants (such as the acid sulfuric, phosphoric acid or nitric acid) and / or a salt and an organic phase dispersed or emulsified in said aqueous phase.
  • the anode is made of a stable material (that is to say non-corrodible) which is advantageously an oxide or an alloy of lead or, preferably, a stop metal such as, for example, titanium whose surface is covered with metals or metal oxides, one or less of which belongs to the platinum family.
  • the structure of the anode can be very diverse; we will use anodes deployed or perforated, or full.
  • hydroquinones which can be used according to the invention can be defined as all those which, in an aqueous medium give rise, in the presence of the corresponding quinone, to a quinhydrone.
  • Examples 1 to 16 were carried out batchwise, that is to say by carrying out the electrolysis of a certain volume of dispersion (or emulsion), this dispersion being either contained in the suitably agitated anode compartment of the electrolyser , or put into circulation in a closed loop on said anode compartment.
  • Example 17 was carried out continuously.
  • a cell comprising a NAFION 423 separation membrane, a catholyte consisting of an aqueous solution of H2SO4 at 0.5 N, an INCOLOY 825 cathode an anode which is either made of coated titanium or of lead ; an amount of cosolvent has always been used in the anolyte such that the ratio, by volume, of the organic phase to the aqueous phase is 0.5, said aqueous phase being at 0.1 N of sulfuric acid.
  • Example 1 The results obtained in the transformation of hydroquinone into para-benzoquinone are collated in Table 1;
  • Example 1 was carried out with a titanium anode coated with solid platinum;
  • Examples 2 to 7 were carried out using an anode in expanded titanium covered with platinum;
  • Examples 8 to 11 were carried out using a perforated titanium anode on which oxides of iridium, cobalt and tantalum were simultaneously deposited;
  • Example 12 was carried out with a perforated lead electrode;
  • Example 13 was carried out with an aperture in palladium titanium covered with platinum-iridium.
  • Example 2 In Examples 2, 3, 5, 6, and 7, the voltage ⁇ V varied during the test from approximately 6 to approximately 8 V; this voltage remained constant and equal to 4.5 V in Example 4; at 4.25 V in Example 8; at 5 V in Example 9; at 2.8 V in Examples 10 and 11; at 4.9 V in Example 12 and at 3.2 V in Example 13.
  • Example 2 The conditions of Example 2 were reproduced using, in place of hydroquinone, toluhydroquinone in a concentration of 10 g / l. The corresponding toluquinone was obtained with a faradic yield of 84% and a chemical yield of 88%.
  • the other experimental conditions are the following:
  • the faradic yield was 85%.
  • a titanium anode coated with platinum and an anolyte were used, the aqueous phase of which has an acidity of 0.1 N in sulfuric acid.
  • the other experimental conditions are the following: Volume ratio of the organic phase to the aqueous phase: 1.2.
  • the faradic yield of the reaction was 68.5% and the chemical yield 100%.
  • the installation includes an electrolyser with two compartments separated by a cationic type separator (NAFION brand membrane).
  • NAFION brand membrane a cationic type separator
  • a mixture of 0.1 N sulfuric acid, dichloromethane (ratio of the organic phase to the aqueous phase of 0.5) and hydroquinone (hydroquinone concentration 20 g / l) is sent.
  • the mixture is decanted, the organic phase is evacuated in order to recover the quinone produced there, and the aqueous phase is recycled (and supplemented by a supply of water, hydroquinone and dichloromethane).
  • the anode is made of titanium coated with platinum and iridium.
  • the temperature is 35 ° C, the current density of 10A / dm2 and the potential difference of 4.25 V.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP89420383A 1988-10-14 1989-10-09 Procédé de préparation de quinone à partir d'hydroquinone par électrolyse Expired - Lifetime EP0370920B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89420383T ATE87040T1 (de) 1988-10-14 1989-10-09 Verfahren zur herstellung von chinon aus hydrochinon durch elektrolyse.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8814361 1988-10-14
FR8814361A FR2637916B1 (fr) 1988-10-14 1988-10-14 Procede de preparation de quinone a partir d'hydroquinone par electrolyse

Publications (2)

Publication Number Publication Date
EP0370920A1 EP0370920A1 (fr) 1990-05-30
EP0370920B1 true EP0370920B1 (fr) 1993-03-17

Family

ID=9371546

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89420383A Expired - Lifetime EP0370920B1 (fr) 1988-10-14 1989-10-09 Procédé de préparation de quinone à partir d'hydroquinone par électrolyse

Country Status (9)

Country Link
US (1) US4963234A (ja)
EP (1) EP0370920B1 (ja)
JP (1) JPH02141592A (ja)
AT (1) ATE87040T1 (ja)
CA (1) CA1330773C (ja)
DE (1) DE68905443T2 (ja)
ES (1) ES2041436T3 (ja)
FR (1) FR2637916B1 (ja)
IE (1) IE893306L (ja)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023161206A1 (en) * 2022-02-25 2023-08-31 Dsm Ip Assets B.V. A process for producing benzoquinones

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3897319A (en) * 1971-05-03 1975-07-29 Carus Corp Recovery and recycle process for anodic oxidation of benzene to quinone
JPS57134581A (en) * 1981-02-13 1982-08-19 Shigeru Torii Production of 1, 4-naphthoquinone derivative
JPS57198283A (en) * 1981-05-27 1982-12-04 Asahi Glass Co Ltd Electrolytic oxidation method for organic compound

Also Published As

Publication number Publication date
JPH034625B2 (ja) 1991-01-23
US4963234A (en) 1990-10-16
ES2041436T3 (es) 1993-11-16
JPH02141592A (ja) 1990-05-30
ATE87040T1 (de) 1993-04-15
FR2637916B1 (fr) 1990-12-07
DE68905443D1 (de) 1993-04-22
IE893306L (en) 1990-04-14
CA1330773C (fr) 1994-07-19
EP0370920A1 (fr) 1990-05-30
FR2637916A1 (fr) 1990-04-20
DE68905443T2 (de) 1993-06-24

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