US3379626A - Process and apparatus for oxidizing olefins - Google Patents

Process and apparatus for oxidizing olefins Download PDF

Info

Publication number
US3379626A
US3379626A US368126A US36812664A US3379626A US 3379626 A US3379626 A US 3379626A US 368126 A US368126 A US 368126A US 36812664 A US36812664 A US 36812664A US 3379626 A US3379626 A US 3379626A
Authority
US
United States
Prior art keywords
anode
metal
cathode
oxidation
electrolyte
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
US368126A
Other languages
English (en)
Inventor
Heuse Otto
Boldt Manfred
Wirtz Rudolf
Theilig Gerhard
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Application granted granted Critical
Publication of US3379626A publication Critical patent/US3379626A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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

  • It consists of an inclined vessel containing the anode, the cathode and a permeable membrane for hydrogen ions and means for conveying the electrolyte through the anode and from the vessel to an external vessel in which an olefin is introduced, and the olefin oxidizing reaction takes place as well as from which the olefin is recovered.
  • the electrolyte is thereafter reconveyed to the electrolytic vessel.
  • the cathode is suitably perforated to allow the hydrogen to pass through and be collected.
  • Other embodiments of the apparatus include using porous oxygen solvent electrode as the cathode and means by which oxygen or air is conveyed therethrough.
  • a further embodiment of the apparatus includes providing for means by which olefin is conveyed through the anode directly.
  • the process aspect of the invention is based on the proper conveyance of the electrolyte through the anode and the reuse of the electrolyte, the contacting of the olefin with the electrolyte outside the electrolytic vessel as well as preventing the hydrogen ions from contacting catalyst metal ions, or if within the vessel, then by conveying the olefin through the anode and the proper conveying of the reaction products away from the vessel.
  • Another process aspect involves the conveying of oxygen or air through the cathode and the conveyance of the electrolyte to the external reaction vessel. lf slowly reacting olefins are involved, surfactants or solution promoters are employed.
  • the present invention relates to a process and apparatus for oxidizing olefins.
  • noble metal compounds for example, compounds of palladium, platinum, silver or copper
  • This reaction is made use of in known processes, for example, in the process described by Smidt in a paper entitled, Katalytician restructuringen von Olefinen and Platinmetall-Veritatien, which has been dealt with in Angewandte Chemie, 71, 1959, pages 176 to 182, and in the process described in Belgian patent specification 569,036.
  • compounds containing olefinic double bonds are in general oxidized in the presence of platinum metal compounds.
  • olefins are oxidized into aldehydes, ketones or the acids corresponding to the aldehydes by contacting them in a neutral or acid medium in the presence of a redox system with an oxidizing agent, water and a compound of a noble metal of group VIII of the Periodic Table.
  • the olefin and the noble metal compound first undergo a stoichiometrical reaction whereby ice complex compound of palladium and ethylene is decomposed, acetaldehyde and palladium form.
  • CuCl2 or another reducible compound has to .be added to the mixture of metal and olefin as a third component in order to convert the metal into the metal compound in the form of which it has initially been used.
  • the addition of the aforesaid third component gives rise to difficulties since in many cases it reacts with the oxidation product of the olefin. This is all the more so when the third component is added in a large excess amount.
  • the third component contains chloride ions. In that case chlorination products form, which are ditiicult to separate from the desired oxidation products and, besides, their separation is expensive.
  • noble metals which are applied to an anode in an electrolyte can be dissolved by applying an electric tension between the anode and a neighbouring cathode.
  • palladium When, for example, palladium is applied to an anode and when an aqueous sulphuric acid solution is used as the electrolyte, palladium can be dissolved in the form of palladium sulphate which is very suitable for use as a catalyst in the oxidation of olefins.
  • the present invention provides a process for the oxidation of olefins by reacting an olefin with an acid solution containing metal ions of the group of platinum and/or of Group I (b) or Group II (b) of the Periodic Table as a catalyst and by subsequently re-oxidizing the catalyst metals that have precipitated in the course of the oxidation into the metal ions acting as a catalyst in the oxidation reaction.
  • the catalyst metal that has precipitated in the course of the oxidation is applied to the surface of a porous electrode of an electrolytic cell, which electrode is insoluble and has the function of an anode and the cata lyst ions that have formed by anodic oxidation and have entered the electrolyte of the electrolytc cell are applied again for the oxidation of the olefins.
  • the gaseous hydrogen forming at the counter-electrode which has the function of a cathode is prevented lfrom mixing with the electrolyte containing the metal ions serving as a catalyst by separating the spaces around the electrodes, which in this specification are called anode space and cathode space, by means of a membrane that is permeable to hydrogen ions but largely impermeable to the catalyst metal ions and/ or lby using an oxygen solvent electrode as the catalyst.
  • a membrane which is arranged between the anode and the cathode and which is permeable to hydrogen ions and impermeable to the metal ions.
  • cation exchange membranes which have been described, for example, by Helfferich in Ionens, pages 55 to 56, published by Verlag Chemie Weinheim (1959). It is known that these membranes are impermeable to anions but permeable to cations. But in addition to this fact it has now ⁇ been found that they are much less permeable to heavy than to light cations.
  • the membrane separating the electrode spaces is at least 5 times, preferably more than 20 times, as permeable to hydrogen ions as to the metal ions serving as the catalyst and formed in the electrolyte at the anode.
  • Another possibility to avoid the detrimental effect of the hydrogen which forms is to use a cathode in the form of a so-called oxygen solvent electrode as is known from fuel cells.
  • the hydrogen is oxidized by the oxygen dissolving at the cathode while it simultaneously absorbs an electron and is thus converted into water.
  • An oxygen solvent electrode is an electrode which has the form of a porous membrane and to the one side of which an oxidizing agent, for example, gaseous oxygen, if desired in the form of air, is fed and the other side of which is wetted by the electrolyte.
  • the oxygen solvent electrode may be made up of a metal oxide, for example, nickel oxide, or coal that has been impregnated with a special catalyst, for example, a spinel or a noble metal. Finely divided metals, for example, Raney metals, in particular Raney silver are also suitable for this purpose.
  • the mode of carrying out the process of the invention offers the advantage that the energy which is set free when hydrogen is lburnt with oxygen is available in the form of electric energy, so -that under certain conditions no additional electric energy is required in the whole course of the reaction. No additional electric energy is required when in the cell the energy required for the formation of the metal ion plus the losses due to electrical resistance and the other losses is smaller than the energy set free 'by the oxidation of hydrogen. Even if this is not the case the amount of electric energy to be supplied from outside is smaller than in the first-mentioned mode of carrying out the process of the invention in which a membrane is used.
  • acid or neutral aqueous solutions as are usually applied in electrolysis may be used as electrolyte solutions, aqueous sulphuric acid, aqueous phosphoric acid and aqueous ammonium sulphate solutions being preferably used.
  • the normality of these solutions is in general within the range of 1 to 10, preferably l to 5. Solutions having a conductivity of more than 0.05 ohm*1-cm.-1, preferably of more than 0.2 ohmfl-cml, are preferred. Electrolyte mixtures may also 'be used.
  • the electrode consists of a material which is generally used for the preparation of electrodes.
  • the material must, of course, 'be inert towards the reactants.
  • Both the anode and the cathode are suitably made of porous coal, porous graphite or another porous conductor such as a sintered metal, for example, sintered nickel.
  • the cathode may likewise be constituted by a metal grid.
  • noble metals may be used that are capable of forming complex compounds with olens, in particular the noble metals of Group VIII, but also those of Groups I and II of the Periodic Table.
  • the noble metals of Group ViII palladium is particularly suitable while silver and mercury are the most suitable noble metals of Groups I and II of the Periodic Table.
  • cation exchange resins based on polystyrene or copolymers of styrene.
  • olelins which can be oxidized by the process according to the invention there may be mentioned aliphatic monoand polyoletins, cycloaliphatic or araliphatic olefins, for example, cyclohexene or styrene and their homologues, substituted olens, for example, unsaturated carboxylic acids and other unsaturated oxygen compounds such as aldehydes, esters, ethers and ltetones, as have been mentioned in the paper by Smidt cited above.
  • the olenic compounds may be substituted, for example, by halogen atoms, amino groups, nitrile groups, nitro groups or amide groups. Mixtures of these compounds may also be used.
  • the process according to the invention may also be used for converting olens into aldehydes, ketones or the acids corresponding to the aldehydes by the process described in Belgian Patent 569,036 according to which in particular low aliphatic olefms containing 2 to l2, preferably 2 to 6 carbon atoms, for example, ethylene, propylene, butene-l, butene-Z or pentene, are used as starting compounds.
  • the process according to the invention may be carried out in such a manner that only the oxidation of the catalyst metal which results in the formation of the metal ions accelerating the oxidation reaction takes place in the electrolytic cell and the oxidation of the oleins by means of the ions of the catalyst metal takes place in a reaction vessel which is separate from the electrolytic cell.
  • T he oxidation of the olefins in the presence of the catalyst metal ions may also be carried out in the electrolytic cell itself for example by pressing the olen to be oxidized through the pores of a porous anode, reacting it with the catalyst metal deposited on the anode and withdrawing the oxidation products formed from the cell.
  • solution promoters or surfactants are added to the electrolyte in the electrolytic cell.
  • Such compounds are added in particular in cases in which slowly reacting olerins are to be reacted.
  • solution promoters may be used, for example, low aliphatic alcohols, ketones or ethers and as surfactants may be used taurines or similar substances.
  • the disturbing substances may be eliminated by an appropriate known measure carried out at an appropriate place in the cycle, for example, by stripping, heating or extraction.
  • FIG. 1 is an elevation in section of a rst embodiment.
  • FIGS. 2 and 3 are elevations in section of further embodiments of the invention.
  • FIGURES l to 3 illustrate various methods of carrying out the process of the invention.
  • a feature that is common to all three of the methods is that the electrodes are inclined to the horizontal. Such a disposition of the electrodes is suitable because in this way the maintenance of the cycle and the Withdrawal of the gas are best ensured.
  • the aforesaid arrangement is, however, not absolutely necessary for the success ofthe process.
  • the angle of inclination between the electrodes and the horizontal is preferably within the range of about to 70. When the angle is smaller than 10 0r wider than 70 it is suitable to provide for a mechanical mixing of the electrolyte solution in order to prevent undissolved reactants from accumulating at the bottom of the electrolytic cell.
  • an ion exchange membrane is used and the reaction of the metal compound with the olefin is carried out in a separate reaction vessel.
  • an oxygen solvent electrode serving for the oxidation of the hydrogen is used.
  • no separate reaction vessel is used, the reaction of the metal compound with the olen taking place between the electrodes.
  • equal numbers refer to parts of the apparatus having equal functions.
  • FIGURE l shows a vessel 1 for electrolysis which is made of an inert material and in which two electrodes, viz an anode Z and a cathode 3, are arranged opposite one another.
  • the cathode 3 is suitably perforated in order to enable the hydrogen 4 that has formed to pass through it in the form of bubbles.
  • electric conductors 5 and 6 for the cathode and the anode.
  • a membrane 7 which is permeable to H+ ions but impermeable to the metal ions.
  • the metal 8 is applied to the anode.
  • the space 9 between the anode 2 and the membrane 7, the space 10 below the anode, the connecting tubes 11, 12 and 13, the pump 14 and the reaction vessel 15 are filled with the aqueous electrolyte solution.
  • the space 10 between the membrane 7 and the upper part of the vessel is likewise lilled with an electrolyte. Both electrolytes may be identical with regard to their kind and concentration, but this is not necessary. If between the anode 2 and the cathode 3 an electric tension is applied which is sutiicient to dissolve the metal, the metal that has been applied to the anode dissolves in the form of ions.
  • the metal used is, for example, palladium and the electrolyte used is aqueous sulphuric acid the aqueous solution contains palladium sulphate.
  • This solution is sucked off through the pores of the anode 2 by means of the pump 14 and conveyed into the reaction vessel 15.
  • the oleiin to be oxidized is introduced through an opening 17 into the reaction vessel 1S through which it passes in the form of bubbles. It reacts with the metal compound whereby the metal is reduced, the metal precipitating in general in the form of a ne slime.
  • the oxidation product of the olefin is withdrawn through an outlet 18.
  • the electrolyte charged with the metal slime passes through the connecting pipe 13 and arrives in the space 9 in which the slime deposits anew on the anode.
  • the cycle is closed.
  • the gaseous hydrogen formed at the cathode rises in the space 16 in the form of bubbles, it is withdrawn through an outlet 19 and may be applied for any desired purpose.
  • the aforesaid method oters the particular ladvantage that the nascent hydrogen which forms at the cathode and which, as is known, is particularly reactive can directly be used in space 16 for hydrogenation purposes.
  • Its Ehydrogenating property Can 'be further improved by using a cathode made of an appropriate material, for example, fby using a cathode made of a material having a catalytic ttect in the hydrogenation, for example, platinum or palladium. In that case the electrolyte in space 16 has to be brought into contact at the cathode with the substance to be hydrogenated.
  • Such a hydrogenation reaction which takes place in the cathode space does not disturb the oxidation reaction which takes place below the membrane 7, provided that the membrane 7 is impermeable to the material to be hydrogenated and to the hydrogenation product, which in general is the case.
  • the cathode 20 used is a porous oxygen solvent electrode.
  • the oxidizing agent which advantageously is oxygen or air is introduced through an inlet 22 into the space 21. It passes through the pores of the membrane-like electrode 2) and at the limit between space 9 and the cathode 2t) it reacts with the hydrogen ions arriving there. This reaction is promoted by suitable catalyst of known type with which the electrode is provided. Since the hydrogen reacts with the oxygen passing through the pores of the membrane and yields Iwater no hydrogen forms at the cathode which would reduce the metal salt that has formed.
  • the space 23 below the anode Z which is also made of a porous conductive material is filled with the olelin to be oxidized.
  • the oleiin is pressed in through an inlet 25 and passes in the form of bubbles through the pores of the anode into a space 26 situated between the anode 2 and the membrane 7 and lled with electrolyte Vand metal compound.
  • this space 26 both the migration of ions, which is caused by electrolysis and leads to the formation of the metal cornpounds, and the reaction which, on the one hand, leads to the reduction of the metal and, on the other hand, to the oxidation of the olefin takes place.
  • the olefin and its oxidation product a-re withdrawn through an outlet 27.
  • the apparatus in which the aforesaid method is carried out may be provided with devices serving to remove portions of the olefin or its oxidation product that are dissolved in the electrolyte, if such are present, by heating, stripping or another method, such devices being, however, not shown in FIGURE 3.
  • the apparatus according to FIGURE 3 offers the further advantage that if metal suspensions are present that iare still separated from the anode, these suspensions cannot be lost in tubes, reaction vessels or other parts of the apparatus but after a short time come again into contact with the anode. This is particularly important when valuable noble metals are used.
  • the apparatus shown in FIGURE 3 may be varied in such a manner that the olen is not introduced through the anode 24 itself but through another inlet, for example, through a frit arranged, for example, at the lower left side of the electrolytic space 26.
  • the membrane separating the electrode spaces is a cation exchange membrane which is at least live times Ias permeable to hydrogen ions as to the catalyst metal ions formed in the electrolyte at the anode.
  • a process as claimed in claim 1 wherein the membrane separating the electrode spaces is a cation exchange membrane which is lmore than twenty times as permeable to hydrogen ions as to the catalyst metal ions formed in the electrolyte at the anode.
  • a process as claimed in claim 1 wherein the electrolyte used in the electrolytic cell is a member selected from the group consisting of aqueous sulphuric acid, aqueous phosphoric acid and aqueous ammonium sulphate.
  • An apparatus for oxidizing olefins which comprises -an electrolytic Vessel; a porous anode which extends over the whole cross-sectional area of the electrolytic vessel; a cathode which is arranged above the anode and which likewise extends over the whole cross-sectional area of the electrolytic vessel; a membrane which is arranged between the anode and the cathode, which likewise extends lover the whole cross-sectional area of the electrolytic vessel and which is permeable to hydrogen ions -but largely impermeable to the catalyst metal ions; a reaction vessel serving for the oxidation of the olefins and arranged so as to be separate from the electrolytic vessel, the lower end of which reaction vessel is connected via a conduit with the space limited by the anode and the membrane and the upper end of which is connected via a conduit and a circulating pump in the conduit with the space below the anode and which reaction vessel is provided with an inlet serving for the introduction of the olefin to be
  • the membrane is made of a cation exchange resin based on polystyrene.
  • each of the anode and the cathode is made of porous carbon.
  • each of the anode and the cathode is made of a porous graphite.
  • An apparatus for oxidizing olefins which comprises an electrolytic vessel; a porous anode which extends over the whole cross-sectional area of the electrolytic vessel; a cathode membrane co-mprised of a porous oxygen solvent electrode and arranged above the anode a-nd extending over the whole cross-sectional area of the electrolytic vessel; an inlet for introducing air or oxygen into the cathode space; an external reaction vessel for the oxidation of the olefins and arranged so as to be joined to the electrolytic vessel by conduits, the lower end of the external reaction vessel lbeing connected Via a conduit with the space limited by the cathode, and the anode and the upper end of the external reaction vessel being connected via a conduit and a circulating pump in the conduit with the space below the anode, said vessel being provided with an inlet for introduction of the olefin to be oxidized and an outlet for the withdrawal of the olefin oxidation product.

Landscapes

  • 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)
US368126A 1963-05-21 1964-05-18 Process and apparatus for oxidizing olefins Expired - Lifetime US3379626A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEF39805A DE1211617B (de) 1963-05-21 1963-05-21 Verfahren und Vorrichtung zur Oxydation von Olefinen

Publications (1)

Publication Number Publication Date
US3379626A true US3379626A (en) 1968-04-23

Family

ID=7097953

Family Applications (1)

Application Number Title Priority Date Filing Date
US368126A Expired - Lifetime US3379626A (en) 1963-05-21 1964-05-18 Process and apparatus for oxidizing olefins

Country Status (4)

Country Link
US (1) US3379626A (enrdf_load_stackoverflow)
BE (1) BE648212A (enrdf_load_stackoverflow)
DE (1) DE1211617B (enrdf_load_stackoverflow)
GB (1) GB1054119A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419207A (en) * 1981-06-08 1983-12-06 Bindon Jeffrey P Electrolytic halogen generators
US4450055A (en) * 1983-03-30 1984-05-22 Celanese Corporation Electrogenerative partial oxidation of organic compounds
US4602986A (en) * 1983-09-29 1986-07-29 The British Petroleum Company P.L.C. Electrochemical conversion of olefins to oxygenated products
US4698144A (en) * 1986-05-15 1987-10-06 The Dow Chemical Company Apparatus for balancing electrolytic cell gas with circulating electrolyte
US4753718A (en) * 1986-11-20 1988-06-28 Fmc Corporation Hydrogen peroxide electrolytic cell

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0297738B1 (en) * 1987-06-29 1992-03-25 United Kingdom Atomic Energy Authority A method for the treatment of waste matter
GB8829703D0 (en) * 1988-12-20 1989-02-15 Atomic Energy Authority Uk A method of oxidation

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636851A (en) * 1949-07-09 1953-04-28 Ionics Ion-exchange materials and method of making and using the same
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds
US3247085A (en) * 1963-06-14 1966-04-19 Exxon Research Engineering Co Electrochemical process for making methyl-ethyl ketone
US3248312A (en) * 1963-01-21 1966-04-26 Union Oil Co Electrolytic oxidation of olefins to unsaturated esters

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT209887B (de) * 1958-06-27 1960-06-25 Hoechst Ag Verfahren zur Herstellung von Aldehyden, Ketonen oder den Aldehyden entsprechenden Säuren
DE544387C (de) * 1930-03-26 1932-02-17 I G Farbenindustrie Akt Ges Herstellung von Mercurisulfatloesung auf elektrolytischem Wege
GB892157A (en) * 1957-10-30 1962-03-21 Consortium Elektrochem Ind Process for the continuous manufacture of aldehydes and ketones
NL236930A (enrdf_load_stackoverflow) * 1958-03-12

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2636851A (en) * 1949-07-09 1953-04-28 Ionics Ion-exchange materials and method of making and using the same
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds
US3248312A (en) * 1963-01-21 1966-04-26 Union Oil Co Electrolytic oxidation of olefins to unsaturated esters
US3247085A (en) * 1963-06-14 1966-04-19 Exxon Research Engineering Co Electrochemical process for making methyl-ethyl ketone

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4419207A (en) * 1981-06-08 1983-12-06 Bindon Jeffrey P Electrolytic halogen generators
US4450055A (en) * 1983-03-30 1984-05-22 Celanese Corporation Electrogenerative partial oxidation of organic compounds
US4602986A (en) * 1983-09-29 1986-07-29 The British Petroleum Company P.L.C. Electrochemical conversion of olefins to oxygenated products
US4698144A (en) * 1986-05-15 1987-10-06 The Dow Chemical Company Apparatus for balancing electrolytic cell gas with circulating electrolyte
US4753718A (en) * 1986-11-20 1988-06-28 Fmc Corporation Hydrogen peroxide electrolytic cell

Also Published As

Publication number Publication date
BE648212A (enrdf_load_stackoverflow) 1964-11-23
GB1054119A (enrdf_load_stackoverflow)
DE1211617B (de) 1966-03-03

Similar Documents

Publication Publication Date Title
US4673473A (en) Means and method for reducing carbon dioxide to a product
US3113049A (en) Direct production of electrical energy from liquid fuels
US3262868A (en) Electrochemical conversion of electrolyte solutions
US4422911A (en) Method of recovering hydrogen-reduced metals, ions and the like at porous catalytic barriers and apparatus therefor
US5527436A (en) Akylene oxide production
GB1049756A (en) Electrochemical process for the production of olefin oxide
US3318735A (en) Fuel cell employing internal primary oxidant regeneration
US3607420A (en) Process of operating fuel-cell half cell with cupric-cuprous redox couple
US3214362A (en) Electrolysis of aqueous electrolyte solutions and apparatus therefor
US3379626A (en) Process and apparatus for oxidizing olefins
US3147203A (en) Process for the production of carbonyl compounds
US4726887A (en) Process for preparing olefin oxides in an electrochemical cell
US4795538A (en) Electrochemical process for recovering metallic rhodium from aqueous solutions of spent catalysts
EP0362157B1 (en) Process for converting ionic valence number and apparatus employed therefor
EP0242784A1 (en) Method in the production of a polyalcohol
Langer et al. Electrogenerative and voltameiotic processes
US4634506A (en) Process for preparing olefin oxides
US3245890A (en) Process for simultaneous production of carbonyl compounds and electrical energy
EP0250103B1 (en) Processfor recovering noble metal
EP0890566A1 (en) Oxidation process for the production of a chlorobenzaldehyde
US3214357A (en) Electrolytic redox process for chemical production
JPH07316865A (ja) 電解処理方法と電解反応槽
JPH08206661A (ja) 硝酸塩の電気化学的回収方法及び装置
US3546082A (en) Oxidation process
US3234116A (en) Method of operating a fuel cell to produce ketones and electric current