US3427234A - Electrochemical hydrodimerization of aliphatic alpha,beta-mono-olefinically unsaturated nitriles - Google Patents

Electrochemical hydrodimerization of aliphatic alpha,beta-mono-olefinically unsaturated nitriles Download PDF

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US3427234A
US3427234A US542255A US3427234DA US3427234A US 3427234 A US3427234 A US 3427234A US 542255 A US542255 A US 542255A US 3427234D A US3427234D A US 3427234DA US 3427234 A US3427234 A US 3427234A
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anode
cathode
polyelectrolyte
covered
catholyte
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Harald Guthke
Karl Wintersberger
Fritz Beck
Josef Georg Floss
Wolfgang Habermann
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BASF SE
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BASF SE
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    • 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
    • C25B3/29—Coupling reactions
    • C25B3/295—Coupling reactions hydrodimerisation

Definitions

  • anode is coated with a solid polyelectrolyte on the side facing the cathode (FIGURE l), or the cathode is coated on the side facing the anode (FIGURE 2) or both anode and cathode are coated on the sides facing each other (FIGURE 3).
  • both anode and cathode are covered with a solid polyelectrolyte, the latter may even extend from one electrode to the other, completely filling the space between them (FIGURE 4).
  • polyelectrolyte comprises both inorganic and organic materials having ion-exchange properties.
  • the new process has further advantages in addition to those already mentioned.
  • the conducting salt and the solvent in the catholyte may be dispensed with;
  • the salt and/or the yacid in the anolyte may be dispensed with;
  • both the conducting salt and the acid may be dispensed with.
  • the lower voltage drop in the electrolytic cell leads to better utilization of energy because heat loss is smaller.
  • the anode material should where possible be material having the lowest possible oxygen overvolta-ge, for examples less than l volt at l amps/ sq. dm.
  • the anode may consist for example of platium metals, graphite, lead, lead dioxide, nickel, nickel coated with nickel sulphide, nickel coated with nickel arsenide, or magnetite. Sintered graphite or Sintered nickel material may also be used.
  • anode is covered on the side facing the cathode with a solid polyelectrolyte
  • the same anode material may be used as in the case of an uncovered anode, and then provision should be made by the design of the anode, for example in the form of netting or grids, or in the form of porous material, which may if desired be provided with grooves and/ or channels, or in the form of a vibrating electrode, so that diffusion of the liquid anolyte can take place through the anode to the solid polyelectrolyte and the oxygen disengaged can escape.
  • the anode itself may however partly consist of solid polyelectrolyte.
  • the cathode material may consist for example of mercury, silver amalgam, lead, lead amalgam and lead alloys, particularly those with silver or mercury.
  • the same cathode material (except the coherent layer of liquid mercury) may be used as in the case of the uncovered cathode.
  • the design for example in the form of netting, grids, or heaped granulates, or by the use of sintered materials, that conveyance and convection of the liquid catholyte can ta-ke place through the cathode to the solid polyelectrolyte, while the electric current flows substantially direct from the cathode through the polyelectrolyte and not through the remaining cathode space containing the solution of catholyte containing the monomeric olenically unsaturated nitrile.
  • Cathodes consisting of silver amalgam or lead amalgam, but particularly those of supercially amalgamated silver, may be used with advantage.
  • the layers of polyelectrolyte used for the coating in general have thicknesses of 0.3 to 2 mm. and particularly of 0.5 to l mm.
  • the cathode and anode are as a rule spaced apart by 0.5 to 5 mm., particularly l to 3 mm. In special cases, however, the spacing may amount to up to 20 mm.
  • the covered electrodes must be such that diffusion of the catholytes or anolytes towards the cover consisting of the solid polyelectrolyte and serving as diaphragm is possible to a certain extent and that the oxygen disengaged can diffuse back.
  • the design of the electrolytic bath and the arrangement of the electrodes depends on the conditions of the electrolysis and may have different forms. For example, the arrangements which have been prepared as follows have proved to be suitable.
  • a layer about 0.5 to 2 mm. in thickness of an organic or inorganic ion exchanger for example a diaphragm, is applied to a porous hollow cylinder of metal or graphite whose surface is provided with vertical grooves or concentric annular grooves which are connected with the interior of the cylinder by inclined or horizontal chan- ⁇ nels, and then a porous sintered article or a netting or a plurality of nettings are rmly pressed onto the layer of ion exchanger.
  • the porous metal Sintered article or the netting is made the cathode and the porous hollow cylinder the anode.
  • the anolyte is placed in the interior of the hollow cylinder and passes through the porous wall and the channels to the polyelectrolyte.
  • 'Ihe cathode is brought into contact with the catholyte by allowing the catholyte to flow in a thin ⁇ film over the cathode or by causing it to flow past the cathode in laminar or turbulent flow.
  • Tubular cells of this type may be arranged vertically, horizontally or obliquely and may have the form of straight, angled or coiled tubes. Any cooling required may be effected by external ushing of the cathode space with the cooling medium or by cooling the anolyte or ⁇ by installing cooling coils in the cell. Individual cells may be connected together in series or in parallel.
  • netting electrodes or porous electrodes which may contain polyelectrolyte, are rmly pressed onto both sides of an ion-exchange diaphragm and this arrangement is inserted in a frame which is installed in a trough where it separates the anode chamber from the cathode chamber.
  • an electrode which has such mechanical stability that it serves as support for the polyelectrolyte and counterelectrode.
  • This arrangement is also installed in a trough and separates the anode chamber from the cathode chamber.
  • the electrodes may be arranged vertically, horizontally or obliquely in the cells.
  • the catholyte and anolyte may as previously described ow over the electrodes in a thin lm or may flow past them in laminar or turbulent flow, for example it may be pumped continuously over the electrodes or may remain stationary in contact therewith and be moved on periodically.
  • a porous or netting anode is covered with a thin coherent layer of polyelectrolyte and this arrangement is used as a partition between the anode and cathode chambers in a trough.
  • an amalgamated lead electrode or another electrode havingr a high hydrogen overvoltage or a sheet of steel which is covered with mercury or over which mercury is ilowing is arranged parallel to the polyelectrolyte layer.
  • the catholyte is allowed to ilow in a laminar or turbulent manner between the cathode and the polyelectrolyte layer, while the anolyte is stationary or moved in the anode chamber.
  • Such a cell may be disposed vertically, horizontally or obliquely.
  • a porous or netting cathode may also be covered with polyelectrolyte and installed in a trough, as described above for the anode.
  • the anode is then located on the polyelectrolyte side at a distance of about 0.5 to 5 mm.
  • Porous, netting or compact anodes Y may be used.
  • one or both electrodes may consist of a nely grained or coarse bulk material of granulate or metal wool, the said material having if desired been enclosed in netting or pressed onto the polyelectrolyte.
  • the thickness of such electrodes may be about 1 to 50l mm.
  • the electrodes prefferably be segmental, i.e. subdivided.
  • the electrolyte layers which cover at least one of the two electrodes may be homogeneous, i.e. may consist of a uniform layer of polymer or copolymer containing charge-carrying groups, or may be heterogeneous, i.e. may ⁇ consist of particles of ion ⁇ exchanger distributed in a binder.
  • Additional supporting material for example a netting, grid, fabric, or fibers, for example of glass, polyethylene, polystyrene, polyperhaloethenes, polytril'luoroethylene or polytetratiuoroethylene, for the layer of ion exchanger may in general be dispensed with because of the special design of the electrolytic cell.
  • the ion exchanger, and also any binder used may be organic or inorganic.
  • Both cation exchangers and anion exchangers are suitable as ion exchangers.
  • Solid polyelectrolyte layers having amphoteric character may however also be used.
  • the polyelectrolyte layer should be mecahnically stable and should be chemically resistant in the electrolyte used; it should also have good electrolytic conductivity. Thus the concentration of the ionic groups should be at least 1 milliequvalent per gram and these should as far as possible be completely dissociated in the electrolyte used.
  • inorganic ion exchange materials are zirconium oxides, particularly hydrated zirconium oxides or those which have been obtained by precipitation of zirconium (IV) compounds, for example oxychlorides, with sodium triphosphate or sodium tungstate, but glauconite or zeolites, such as sodium permutite, apatite (Ca5(PO4)3(+)F(-)) or hydroxylapatite may also be used.
  • These inorganic ion exchange materials may if desired be held together ⁇ by an organic or inorganic binder, such as polystyrene, polybutadiene, polyisoprene or cement.
  • Condensed or polymerized high molecular weight organic compounds which contain ionic groups, basic or acid groups, are suitable as organic solid polyelectrolytes. They may contain for example acid groups, such as sulfonic acid groups, or also carboxylic acid groups, phosphonium groups, phosphine groups, arsenic acid groups or hydroxyl groups, ammonium groups or amino groups in a concentration of at least 2 milliequivalents per gram.
  • sutiable compounds are particularly styrene polymers, such as polystyrene, copolymers of dimethylstyrene and divinylbenzene, styrene and divinylbenzene, or also phenyl-formaldehyde resins, or polymers or copolymers of vinyl chloride which contain phosphonium groups, sulfonic acid groups or carboxylic acid groups as cation exchangers, or those containing amino groups or quaternary ammonium groups as anion exchangers.
  • styrene polymers such as polystyrene, copolymers of dimethylstyrene and divinylbenzene, styrene and divinylbenzene, or also phenyl-formaldehyde resins, or polymers or copolymers of vinyl chloride which contain phosphonium groups, sulfonic acid groups or carboxylic acid groups as cation exchangers, or those containing amino groups
  • polystyrene copolymers with 75 to 95% of styrene and 5 to 25% of divinylbenzene, which have been sulfonated to such an extent that they contain 5 to 5.2. milliequivalents of hydrogen ions per gram, or polystyrene copolymers with 70 to 96% of styrene, 0 to of ethylstyrene, 4 to 16% of divinylbenzene containing 3 to 4 milliequivalents of amino groups per gram.
  • the ion exchanger layers may be prepared by pressing or by consolidation from a dispersion
  • the temperature in the catholyte is advantageously kept at 10 to 40 C., particularly 20 to 30 C., by cooling.l
  • a multiphase system consisting of ,-olefinically unsaturated nitrile, water and a conducting salt, if desired in the presence of an inert organic solvent, is used as the liquid phase in the cathode chamber.
  • the conducting salt one whose cations have a high ⁇ discharge potential, e.g. above 1.8 volt (vs. a calomel electrode).
  • suitable salts are those of tetraalkyl ammonium bases or tetraalkanol ammonium bases, and also those of alkylamines or alkanolamines.
  • salts of tetramethyl ammonium, tetraethyl ammonium, trimethylethyl ammonium, butylamine, hexylamine, ethanolamine, diethanolamine or triethanolamine have proved to be particularly suitable.
  • Particularly suitable anions for such salts are those 'which are derived from arylsulfonic acids or arylalkylsulfonic acids, for example from toluenesulfonic acids, benzenesulfonic acids, ethylbenzenesulfonic acids or salts of monoalkylsulfuric acids, for example ethylsulfuric acid.
  • suitable salts are tetraethyl ammonium p-toluenesulfonate or tetraethyl ammonium ethylbenzenesulfonate or tetraethyl ammonium ethyl sulfate.
  • a liquid anion exchanger for example amines having weakened basicity and having molecular weights of 250 to 500, such as trialkylmethylamines with alkyl groups having eighteen to twenty-four carbon atoms, N-dodecenyl-N-(trialkylmethyl)amines having eighteen to twenty-four carbon atoms in the alkyl groups or a liquid cation exchanger, for example monododecylphosphoric acid, monoheptadecylphosphoric acid or di-(Z-ethylhexyl)-phosphoric acid.
  • amines having weakened basicity and having molecular weights of 250 to 500 such as trialkylmethylamines with alkyl groups having eighteen to twenty-four carbon atoms, N-dodecenyl-N-(trialkylmethyl)amines having eighteen to twenty-four carbon atoms in the alkyl groups or a liquid cation exchanger, for example monododecylphospho
  • organic solvents examples include polar solvents such as acetonitrile, ⁇ dioxane, tetrahydrofurane, acetone, dialkylamides of lower carboxylic acids, such as dimethylformamide, and also N-alkyllactams, for example N- methylpyrrolidone, glycols, such as ethylene glycol, or lower alcohols, such as methanol or ethanol.
  • polar solvents such as acetonitrile, ⁇ dioxane, tetrahydrofurane, acetone, dialkylamides of lower carboxylic acids, such as dimethylformamide, and also N-alkyllactams, for example N- methylpyrrolidone, glycols, such as ethylene glycol, or lower alcohols, such as methanol or ethanol.
  • the monomeric olenic nitriles are usually employed in concentrations of l to 90%, particularly 40 to 65%, in the catholyte.
  • the conducting salt is usually used in amounts of to 40% by weight on the multiphase system used as the catholyte. When organic solvents are added, up to about 40%, particularly 5 to 25%, by weight is added.
  • the -water content in the multiphase system containing the conducting salt and used as the catholyte is preferably kept at more than by weight.
  • either multiphase systems such as are used in the case of an uncovered cathode, but in this case preferably with a higher concentration of monomeric oleiinic nitrile, particularly more than 90%, are used as the liquid phase in the cathode chamber; it is however possible to dispense with the conducting salt and/ or the organic solvent and, provided a cation exchanger is used in its H(+)ion form as polyelectrolyte, even with the water, so that pure monomeric unsaturated nitrile may be used as the liquid phase in the cathode chamber.
  • conducting salt concentrations of from 0.5 to 3.0% by weight are preferred.
  • the liquid phase in the anode chamber may be either aqueous conducting salt solutions as in the cathode chamber or aqueous solutions of salts, acids or bases, for example of phosphates, sulfates, phosphoric acid, sulfuric acid, benzenesulfonic acid or toluenesulfonic acid, or quaternary ammonium bases, and the conductivity-producing compounds should be correlated to the ion form of the ion exchanger. It is preferred to use electrolyte solution whose ions do not undergo any change during the electrolysis.
  • the liquid phase in the anode chamber should preferably contain such an amount of electrolyte that it has a conductance of at least 10'2S/cm. S21.cm.1).
  • Sulfuric acid for example, is very suitable, but other mineral acids, particularly those having a high ionization constant, erg. above 103 at 25 C. l
  • a pH value of 3 to 10, particularly 6 to 9, in the cathode chamber It is preferable to maintain a pH value of 3 to 10, particularly 6 to 9, in the cathode chamber.
  • Working in the acid range in the anode chamber is preferred when using a cation exchanger, and in the alkaline range when using an anion exchanger.
  • Buffer substances may be added to set up a definite pH value.
  • a solution of a buffering system in monomers may be used.
  • Weakly basic or weakly acidic substances whose cations are only discharged at high deposition potential are particularly suitable as buffering substances, examples being primary tetraalkyl ammonium phosphates, tetraaklyl ammonium acetates, acid alkyl ammonium sulfonates, acid alkyl ammonium sulfates, alkylaryl ammonium hydroxides, if desired in combination with weak acids.
  • a bulfer substance for example when using a cation exchanger, by a mixture of a mineral acid and glycocoll or when using an anion exchanger, by a mixture of caustic alkali solution and glycocoll.
  • the essential advantage of the process according to the invention is that the conducting salt or the acid or base may be dispensed with in the catholyte when using a covered anode or in the anolyte when using a covered cathode.
  • anode is covered with a solid lpolyelectrolyte as shown diagrammatically in FIGURE 1, pure water or an electrolyte may be used on the side 1 remote from the cathode.
  • a known multiphase system of a-unsaturated nitriles and conducting salts may be used on the side 2 facing the cathode but covered with polyelectrolyte.
  • the solvent may however be dispensed with, especially when solubilizing conducting salts are used.
  • the cathode is covered with solid polyelectrolyte
  • either the usual multiphase system containing conducting salt maybe used with the na-unsaturated nitrile on the side 3 remote from the anode, or the conducting salt and if desired the solvent may be dispensed with. All that is necessary then on the side 4 facing the anode is the presence of a suitable liquid electrolyte. It is preferred to use aqueous phosphoric acid, sulfuric acid or solutions of phosphates or sulfates.
  • a particular advantage of using this arrangement results when the conducting salt is dispensed with because then the dimerization product produced in the cathode chamber, for example adipodinitrile, may be worked up in a particularly simple way. All that is needed is for the dimerization product obtained to be separated from the monomers by simple distillation.
  • both the anode and the cathode are covered with solid polyelectrolyte, the advantages of both arrangements, as described above, are obtained, i. e. it is possible to use pure water on the side 1 of the anode remote from the cathode and pure na-unsaturated nitrile on the side 3 of the cathode remote from the anode, while in the space 5 between the two electrodes only a liquid electrolyte is required.
  • a somewhat higher cell voltage for example of 7 to 9 volts, is required as a rule than when using the other arrangements according to the invention.
  • Example l The anode consists of a porous graphite tube surrounded by a dense layer of a copolymer of styrene and divinylbenzene into which sulfonate groups have been introduced.
  • the counterelectrode is an amalga-mated silver netting which is arranged as a tube around the anode. Pure water is filled into the graphite tube.
  • the catholyte used is a mixture of 40% by weight of acrylonitrile, 34% by weight of water and 26% by weight of tetraethyl ammonium p-toluenesulfonate.
  • the anode is completely separated from the cathode by the layer of ion exchanger.
  • Example 2 The anode consists of a porous graphite tube. An amalgamated silver netting having 900 meshes per sq. crn. is arranged concentrically around this electrode. A layer 1 mm. in thickness of polystyrene into which sulfonic acid groups have been introduced is situated on the inside of this netting. A mixture of 40% by weight of acrylonitrile, 36% by Weight of water and 34% -by weight of tetraethyl ammonium p-toluenesulfonate is situated on the cathode side.
  • a 2.5% aqueous phosphoric acid is situated on the anode side.
  • a yield of adipodinitrile of 80.8% (on the reacted acrylonitrile) and a current yield of 65% are obtained at a current density of 3 amps/sq. dm.
  • the pH value remains practically constant at 2 in the anode chamber and at 5 to 7 in the cathode chamber.
  • the fact that the current yield is 65 means that adipodinitrile produced at an applied voltage of 4.5 v./kg. requires an energy of only 3.5 kwh.
  • Example 3 The electrolytic cell used has an anode of a porous graphite tube 45 mm. in height, 4 mm. in wall thickness and having a diameter of 38 mm.
  • a layer of ion exchanger (consisting of highly crosslinked polystyrene into which quaternary ammonium groups have been introduced) is applied to the outer surface of the graphite tube.
  • the ion exchanger is in the hydroxyl form.
  • the thickness of the layer is 0.8 mm.
  • An amalgamated silver netting is applied to this ion exchanger layer.
  • the netting has 64 meshes per sq. cm. and the thickness of the Wire is 0.5 mm.
  • Pure distilled water is filled into the hollow graphite cylinder (anode chamber), and the outer space is lilled with pure acrylonitrile.
  • a 75 to 80% yield of adipodinitrile (on reacted acrylonitrile) is obtained at a conversion of 25
  • the current yield is at least 73% so that a maximum of 3.2 kwh. is required for 1 kg. of adipodinitrle.

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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US542255A 1965-04-14 1966-04-13 Electrochemical hydrodimerization of aliphatic alpha,beta-mono-olefinically unsaturated nitriles Expired - Lifetime US3427234A (en)

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661739A (en) * 1968-09-28 1972-05-09 Andrei Petrovich Tomilov Method of electrochemical hydrodimerization of olefinic compounds
US3871976A (en) * 1973-09-10 1975-03-18 Standard Oil Co Electrochemical adiponitrile process
US3887442A (en) * 1970-11-23 1975-06-03 Scm Corp Polymerization process
US3898140A (en) * 1973-08-06 1975-08-05 Monsanto Co Electrolytic hydrodimerization process improvement
US3925172A (en) * 1972-02-14 1975-12-09 American Cyanamid Co Electrochemical oxidation and reduction
US3966566A (en) * 1974-08-15 1976-06-29 Monsanto Company Electrolytic hydrodimerization process improvement
US4012295A (en) * 1972-07-21 1977-03-15 Keuffel & Esser Company Electrolytically induced polymerization utilizing bisulfite adduct free radical precursor
US4043879A (en) * 1972-07-21 1977-08-23 Keuffel & Esser Company Electrolytically induced polymerization utilizing bisulfite adduct free radical precursor
US4090931A (en) * 1975-07-07 1978-05-23 Tokuyama Soda Kabushiki Kaisha Anode-structure for electrolysis
US4101395A (en) * 1976-08-30 1978-07-18 Tokuyama Soda Kabushiki Kaisha Cathode-structure for electrolysis
US4235695A (en) * 1977-12-09 1980-11-25 Diamond Shamrock Technologies S.A. Novel electrodes and their use
US4462876A (en) * 1983-03-25 1984-07-31 Ppg Industries, Inc. Electro organic method and apparatus for carrying out same
US4472252A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactants
US4472251A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactant
US4521283A (en) * 1983-03-25 1985-06-04 Ppg Industries, Inc. Electro organic method and apparatus for carrying out same
US4596638A (en) * 1985-04-26 1986-06-24 International Fuel Cells Corporation Method for the electrochemical production of adiponitrile using anodes having NiCo2 O4 catalyst
US4636286A (en) * 1983-03-25 1987-01-13 Ppg Industries, Inc. Electro organic method

Citations (7)

* 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
US2815320A (en) * 1953-10-23 1957-12-03 Kollsman Paul Method of and apparatus for treating ionic fluids by dialysis
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3135674A (en) * 1960-06-06 1964-06-02 Electric Storage Battery Co Method and apparatus for the purification of water
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process
US3244612A (en) * 1961-11-29 1966-04-05 George W Murphy Demineralization electrodes and fabrication techniques therefor
US3245889A (en) * 1963-02-25 1966-04-12 Monsanto Co Electrolytic method for preparing low weight polymers of acrylonitrile

Patent Citations (7)

* 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
US2815320A (en) * 1953-10-23 1957-12-03 Kollsman Paul Method of and apparatus for treating ionic fluids by dialysis
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3135674A (en) * 1960-06-06 1964-06-02 Electric Storage Battery Co Method and apparatus for the purification of water
US3244612A (en) * 1961-11-29 1966-04-05 George W Murphy Demineralization electrodes and fabrication techniques therefor
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process
US3245889A (en) * 1963-02-25 1966-04-12 Monsanto Co Electrolytic method for preparing low weight polymers of acrylonitrile

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3661739A (en) * 1968-09-28 1972-05-09 Andrei Petrovich Tomilov Method of electrochemical hydrodimerization of olefinic compounds
US3887442A (en) * 1970-11-23 1975-06-03 Scm Corp Polymerization process
US3925172A (en) * 1972-02-14 1975-12-09 American Cyanamid Co Electrochemical oxidation and reduction
US4012295A (en) * 1972-07-21 1977-03-15 Keuffel & Esser Company Electrolytically induced polymerization utilizing bisulfite adduct free radical precursor
US4043879A (en) * 1972-07-21 1977-08-23 Keuffel & Esser Company Electrolytically induced polymerization utilizing bisulfite adduct free radical precursor
US3898140A (en) * 1973-08-06 1975-08-05 Monsanto Co Electrolytic hydrodimerization process improvement
US3871976A (en) * 1973-09-10 1975-03-18 Standard Oil Co Electrochemical adiponitrile process
US3966566A (en) * 1974-08-15 1976-06-29 Monsanto Company Electrolytic hydrodimerization process improvement
US4090931A (en) * 1975-07-07 1978-05-23 Tokuyama Soda Kabushiki Kaisha Anode-structure for electrolysis
US4101395A (en) * 1976-08-30 1978-07-18 Tokuyama Soda Kabushiki Kaisha Cathode-structure for electrolysis
US4235695A (en) * 1977-12-09 1980-11-25 Diamond Shamrock Technologies S.A. Novel electrodes and their use
US4462876A (en) * 1983-03-25 1984-07-31 Ppg Industries, Inc. Electro organic method and apparatus for carrying out same
US4472252A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactants
US4472251A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactant
US4521283A (en) * 1983-03-25 1985-06-04 Ppg Industries, Inc. Electro organic method and apparatus for carrying out same
US4636286A (en) * 1983-03-25 1987-01-13 Ppg Industries, Inc. Electro organic method
US4596638A (en) * 1985-04-26 1986-06-24 International Fuel Cells Corporation Method for the electrochemical production of adiponitrile using anodes having NiCo2 O4 catalyst

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GB1137544A (en) 1968-12-27
DE1518548A1 (de) 1969-05-14

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