EP0635587B1 - Electrode comprenant un noyau contenant du fer et un revêtement contenant du plomb - Google Patents

Electrode comprenant un noyau contenant du fer et un revêtement contenant du plomb Download PDF

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Publication number
EP0635587B1
EP0635587B1 EP94108425A EP94108425A EP0635587B1 EP 0635587 B1 EP0635587 B1 EP 0635587B1 EP 94108425 A EP94108425 A EP 94108425A EP 94108425 A EP94108425 A EP 94108425A EP 0635587 B1 EP0635587 B1 EP 0635587B1
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Prior art keywords
lead
electrode
coating
copper
weight
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EP0635587A1 (fr
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David Dr. Sopher
Andreas Dr. Gieseler
Hartmut Dr. Hibst
Klaus Dr. Harth
Peter Dr. Jaeger
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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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
    • 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

  • the present invention relates to an improved electrode, consisting essentially of an electrically conductive core Iron and an electrically conductive coating from essentially Lead.
  • the present invention also relates to methods of manufacture the electrode according to the invention, its use for reductive coupling of olefinic reactants and a improved process for the reductive coupling of olefinic Reaction partners.
  • ADN acrylonitrile to adiponitrile
  • US-A 3,193,481 describes US-A 3,193,482 and US-A 3,193,483 the electrochemical manufacture of ADN in a divided cell, with pure cathode Lead is used.
  • Organic Electrochemistry Edit. Baizer and Lund, Marcel Dekker, New York, 1984, 986, becomes analog Manufacture of ADN a lead cathode containing 7% by weight Antimony used.
  • DE-A 2,338,341 describes the use of pure lead cathodes in undivided electrochemical cells for the production of ADN.
  • the disadvantage of the electrodes mentioned above is that regardless of whether the cathodes are made of lead or another Material, such as cadmium, are built up the anodes and corrode cathodes during the reaction and thereby disturbing Produce degradation products that include for deposits on the electrodes being able to lead.
  • these deposits can the electrohydrodimerization of acrylonitrile to a decrease selectivity for adiponitrile and increased Lead to hydrogen formation. It is therefore important to avoid deposits, caused by electrode degradation, i.a. on the cathode surface, to prevent.
  • the object of the present invention was therefore an electrode with a cathode consisting of lead or lead alloys increased resistance to corrosion put.
  • adiponitrile more economical through electrohydrodimerization of acrylonitrile and be made more environmentally friendly.
  • an electrode consisting of an electrical conductive core of essentially iron and an electrical conductive, single layer coating of lead and 0.3 to 3.5 wt .-% copper and optionally other elements selected from the group silver, selenium, tellurium, bismuth and antimony, found.
  • the electrode according to the invention consists of an electrically conductive Core of essentially iron and an electrically conductive, single-layer coating of lead and 0.3 to 3.5% by weight Copper and optionally further elements selected from the Group of silver, selenium, tellurium, bismuth and antimony.
  • the design of the electrodes is also not critical, so that the specialist from the variety of common electrode types such as plane-parallel plates, pipes, nets and disks suitable electrode types can choose. It is preferred to choose plane-parallel ones Plates.
  • the electrically conductive coating consists of Lead and 0.3 to 3.5% by weight copper.
  • the coating can other elements such as silver, selenium, tellurium, bismuth and antimony in amounts up to 3.5% by weight, preferably from 0.5 to 2% by weight, particularly preferably from 0.8 to 1.5% by weight.
  • Prefers is a coating with the following according to the previous observations Composition: 96.5 to 99.5, preferably 98 to 99.5% by weight Lead, 0.3 to 3, preferably 0.5 to 2% by weight copper, 0 to 3, preferably 0 to 2% by weight of silver and / or bismuth and / or selenium and / or tellurium and / or antimony.
  • the electrically conductive coating can be made by the usual methods be applied. Application is particularly preferred by electroplating, i.e. electrolytically, and by physical Deposition process selected from the group consisting of Vapor deposition, sputtering ("sputtering", i.e. metal vapor deposition) or arc coating.
  • electroplating i.e. electrolytically, and by physical Deposition process selected from the group consisting of Vapor deposition, sputtering ("sputtering", i.e. metal vapor deposition) or arc coating.
  • an electroplating bath with an iron or Sheet steel as the cathode and a lead as the anode, being the two electrodes are advantageously arranged parallel to one another are (see “Modern Electroplating”).
  • the electrolyte solution usually contains what is to be separated Lead and, if desired, other elements in the form of their water-soluble Salts.
  • An aqueous silicic hydrofluoric acid, an aqueous fluoroborate or a C 1 -C 4 alkanesulfonic acid solution such as methane, ethane, propane or butanesulfonic acid solution, preferably methanesulfonic acid solution, is preferably used as the electrolyte solution.
  • the electrolyte solution is generally present essentially from lead fluoroborate.
  • the electrolytic solution still contains common auxiliaries such as fluoroboric acid, Boric acid and common organic additives such as a peptone, resorcinol or hydroquinone to achieve fine-grained, smooth precipitates.
  • lead fluoroborate is used in concentrations in the range from 5 to 500 g / l, preferably from 20 to 400 g / l, and copper in the form of its fluoroborate salt, oxide, hydride or Carbonates in concentrations ranging from 0.1 to 10, preferably from 0.5 to 10 g / l.
  • Fluoroboric acid is generally used in the range from 10 to 150, preferably from 15 to 90 g / l a.
  • Boric acid is usually used in the range from 5 to 50, preferably from 10 to 30 g / l.
  • Uses common organic additives one generally in amounts in the range of 0.1 to 5 g / l.
  • the other elements possible in addition to lead and copper such as silver, selenium, tellurium, bismuth and / or antimony expedient in the form of their fluoroborate salts, oxides, hydroxides or Carbonates in concentrations ranging from 0.1 to 10, preferably from 0.5 to 10 g / l.
  • lead is usually used in the form of its salt of methanesulfonic acid in amounts in the range from 10 to 200, preferably from 10 to 60 g / l and copper in the form of the corresponding C 1 -C 4 -alkanesulfonic acid salt, oxide, hydroxide or carbonate in amounts in the range from 0.1 to 20, preferably from 0.5 to 10 g / l.
  • the electrolyte solution also contains customary auxiliaries such as the corresponding C 1 -C 4 -alkanesulfonic acid, usually methanesulfonic acid, in an amount in the range from 20 to 150, preferably from 30 to 80 g / l, and surfactants, for example such based on alkylphenol ethoxylates such as Lutensol® AP 10 (BASF AG), in amounts in the range from 1 to 20, preferably from 5 to 15 g / l.
  • auxiliaries such as the corresponding C 1 -C 4 -alkanesulfonic acid, usually methanesulfonic acid, in an amount in the range from 20 to 150, preferably from 30 to 80 g / l
  • surfactants for example such based on alkylphenol ethoxylates such as Lutensol® AP 10 (BASF AG), in amounts in the range from 1 to 20, preferably from 5 to 15 g / l.
  • the electrode coating can contain the elements already listed above, such as silver, selenium, tellurium, bismuth and / or antimony, which are expediently in the form of their corresponding C 1 -C 4 -alkanesulfonic acid salts, oxides, hydroxides or carbonates in amounts in the range from 0.1 to 20, preferably from 0.5 to 10 g / l, to the electrolyte solution.
  • elements already listed above such as silver, selenium, tellurium, bismuth and / or antimony, which are expediently in the form of their corresponding C 1 -C 4 -alkanesulfonic acid salts, oxides, hydroxides or carbonates in amounts in the range from 0.1 to 20, preferably from 0.5 to 10 g / l, to the electrolyte solution.
  • a DC voltage of 0.5 to 20, preferably 1 to 10 volts is generally applied to the electrodes.
  • the current density during the electroplating is generally in the range from 1 to 200, preferably from 5 to 40 mA / cm 2 .
  • the duration of the electroplating depends on the chosen reaction parameters and the desired layer thickness of the coating from and is usually in the range of 0.5 to 10 hours. In general you choose the layer thickness in the range of 1 to 500, preferably from 20 to 200 ⁇ m.
  • the temperature during the electroplating is preferably chosen in the range from 10 to 70 ° C., the reaction is preferably carried out Room temperature through.
  • the selected pressure range is generally not critical, preferred one works at atmospheric pressure.
  • the pH value essentially depends on the electrolytes used and additives and is usually in the range from 0 to 2nd
  • pulse current techniques Pulsed current techniques
  • Another preferred embodiment is galvanic Deposition in a through an ion exchange membrane such as Cation or anion exchange membrane, preferably an anion exchange membrane, divided cell.
  • an ion exchange membrane such as Cation or anion exchange membrane, preferably an anion exchange membrane, divided cell. This procedure has the advantage that unwanted deposits are used further Elements, especially copper, on the anode are suppressed can.
  • any suitable one can be used as a galvanizing cell
  • the process parameters are in general with the identical above.
  • anion exchange membranes can be used as the anion exchange membrane such as Selemion® AMV (Asahi Glass), Neosepta® ACH 45T AM1, -AM2, -AM3 (Tokoyama Soda) or Aciplex® A 101, -102 Use (Asahi Chemical).
  • the production can of the electrodes according to the invention also by physical deposition processes such as vapor deposition, sputtering ("sputtering") or carry out an arc coating.
  • physical deposition processes such as vapor deposition, sputtering ("sputtering") or carry out an arc coating.
  • Cathode sputtering allows the layer thickness of the electrode coating in the range between 5 Angstroms and 100 ⁇ m. Furthermore, cathode sputtering allows simple and reproducible production of a multi-component layer, according to the previous knowledge, no limitation regarding the number of elements applied can be observed.
  • the microstructure of the electrode coating can be influenced by means of sputtering by varying the process gas pressure and / or by applying a negative bias (bias).
  • bias a process gas pressure in the range of 4 * 10 -3 to 8 * 10 -3 mbar leads to a very dense, fine-crystalline layer with high corrosion stability.
  • the coating material is generally applied in solid form as a so-called target to the cathode of a plasma system, then under reduced pressure, for example from 1 * 10 -4 to 1 mbar, preferably 5 * 10 -4 to 5 * 10 -2 mbar , atomized in a process gas atmosphere by applying a plasma and deposited on the substrate to be coated (anode) (see RFBhunshah et al., "Deposition Technologies for Films and Coatings", Noyes Publications, 1982).
  • at least one noble gas such as helium, neon or argon, preferably argon, is selected as the process gas.
  • the plasma usually consists of charged (ions and electrons) and neutral (partly radical) components of the process gas, which interact with each other via shock and radiation processes stand.
  • Various methodological methods can be used to produce the electrode coating Variants of cathode sputtering such as magnetron sputtering, DC and RF sputtering or bias sputtering and their combinations be applied.
  • Magnetron sputtering is in the Rule the target to be atomized in an external magnetic field, which concentrates the plasma in the area of the target and thus increasing the atomization rate.
  • DC or RF sputtering is generally used to excite the sputtering plasma by a direct voltage (DC) or by an alternating voltage (RF), for example with a frequency in the range of 10 kHz to 100 MHz, preferably 13.6 MHz.
  • Bias sputtering is usually the substrate to be coated with a in the Usually negative bias (bias) proves which in general during the coating for an intensive bombardment of the substrate leads with ions.
  • Suitable targets are, for example homogeneous alloy targets in a known manner can be produced by melting or powder metallurgical processes are, and inhomogeneous mosaic targets that are usually caused by Assembling smaller sections of different chemical Composition or by placing or sticking small ones disc-shaped pieces of material can be produced on homogeneous targets are.
  • homogeneous alloy targets in a known manner can be produced by melting or powder metallurgical processes are, and inhomogeneous mosaic targets that are usually caused by Assembling smaller sections of different chemical Composition or by placing or sticking small ones disc-shaped pieces of material can be produced on homogeneous targets are.
  • the desired layer thickness and the chemical composition and the microstructure of the electrode coating are essentially through the process gas pressure, the atomization performance, the sputtering mode, to influence the substrate temperature and the coating time.
  • the atomizing power is the power for excitation of the plasma is used, and is usually in the range from 50 W to 10 kW.
  • the substrate temperature is generally chosen in the range from Room temperature to 350, preferably from 150 to 250 ° C.
  • the coating time essentially depends on the desired Layer thickness. Typical coating rates for sputtering are usually in the range of 0.1 to 100 nm / s.
  • Another preferred embodiment is the production of the electrode coating by vapor deposition (see L. Holland, Vacuum Deposition of Thin Films, Chapman and Hay Ltd., 1970).
  • the coating material is expediently introduced in a manner known per se into a suitable evaporation source, such as electrically heated evaporator boats or electron beam evaporators.
  • the coating material is then evaporated under reduced pressure, usually in the range from 10 -7 to 10 -3 mbar, the desired coating being formed on the electrode introduced in the vacuum system.
  • the evaporation material can be used in the production of multi-component layers either in the appropriate composition a common source or simultaneously from different sources be evaporated.
  • Typical coating rates during evaporation are in general in the range from 10 nm / s to 10 ⁇ m / s.
  • that to be coated can be Substrate before or during the vapor deposition process an RF plasma or using a conventional ion gun Bombarded to the microstructure and the adhesion of the ions To improve layers. You can also see the microstructure and also affect the adhesion of the layers by heating the substrate.
  • the electrodes according to the invention can be used for reductive coupling of olefinic reactants.
  • olefinic reactants usually the olefinic reactants by electrohydrodimerization according to conventional reaction methods brought by being in an electrolytic cell with an anode and exposed to an electrode according to the invention as a cathode of electrolysis will.
  • R 1 R 2 C CR 3 X in which R 1 , R 2 and R 3 are the same or different hydrogen or C 1 -C 4 alkyl, such as methyl, ethyl, n-propyl , i-Propyl, n-butyl, i-butyl, sec-butyl or tert-butyl, and X is -CN, -CONR 1 R 2 or -COOR 1 .
  • Examples include olefinic nitriles such as acrylonitrile, methacrylonitrile, crotononitrile, 2-Methylenbutyronitril, 2-pentenenitrile, 2-Methylenvalerian Textrenitril or 2-Methylenhexanklarenitril, olefinic carboxylates such as acrylate, methyl or Ethylacryl Acidester olefinic carboxamides such as acrylamide, methacrylamide, N, N-dimethyl - or N, N-diethylacrylamide, particularly preferably acrylonitrile.
  • one provides with the help of the electrodes according to the invention adiponitrile Electrohydrodimerization from acrylonitrile.
  • the following information therefore refer to this procedure.
  • the type of electrolysis cell is based on previous observations uncritical, so that the specialist from the spectrum of commercially available Can choose electrolytic cells.
  • a preferred embodiment the undivided cell represents the electrolytic cell represents, especially plate stack cells or capillary gap cells to be favoured.
  • Such cells are, for example, in J. Electrochem. Soc. 131 (1984) 435c and J. Appl. Electrochemical. 2 (1972) 59 described in detail.
  • Known anodes can be used as the anode, preferably with undivided ones
  • Cells are usually made of materials with less Oxygen overvoltage, for example carbon steel, steel, Platinum, nickel, magnetite, lead, lead alloys or lead dioxide, a (see Hydrocarbon Processing (1981) 161).
  • the electrodes according to the invention are used as cathodes with a composition of the following type according to the previous ones Observations can preferably use: 96.5 to 100, preferably 98 to 99.5% by weight of lead, 0.3 to 3, preferably 0.5 up to 2% by weight copper, 0 to 3, preferably 0 to 2% by weight silver and / or bismuth and / or selenium and / or tellurium and / or antimony.
  • the electrolyte solution usually contains a conductive salt, in particular in the manufacture of adiponitrile, otherwise in usually propionitrile becomes the main product and with an increased one Hydrogen formation is to be expected.
  • a conductive salt in particular in the manufacture of adiponitrile, otherwise in usually propionitrile becomes the main product and with an increased one Hydrogen formation is to be expected.
  • the conducting salt in an amount in the range of 1 to 100 mmol / kg aqueous electrolyte solution, preferably from 5 to 50 mmol / kg.
  • Suitable conductive salts are: quaternary Ammonium compounds such as tetrabutylammonium salts, ethyltributylammonium salts, quaternary phosphonium salts and bisquaternaries Ammonium and phosphonium salts such as hexamethylene bis (dibutylethylammonium hydroxide) (see Hydrocarbon Processing 161 (1981); J. Electrochem. Soc. 131 (1984) 435c).
  • quaternary Ammonium compounds such as tetrabutylammonium salts, ethyltributylammonium salts, quaternary phosphonium salts and bisquaternaries Ammonium and phosphonium salts such as hexamethylene bis (dibutylethylammonium hydroxide) (see Hydrocarbon Processing 161 (1981); J. Electrochem. Soc. 131 (1984) 435c).
  • the electrolyte solution usually contains one Buffers such as hydrogen phosphate, hydrogen carbonate, preferably in the form their sodium salts, particularly preferably disodium hydrogen phosphate, in an amount ranging from 10 to 150, preferably from 30 to 100 g / kg aqueous electrolyte solution.
  • Buffers such as hydrogen phosphate, hydrogen carbonate, preferably in the form their sodium salts, particularly preferably disodium hydrogen phosphate, in an amount ranging from 10 to 150, preferably from 30 to 100 g / kg aqueous electrolyte solution.
  • the electrolyte solution preferably contains an anode corrosion inhibitor like the borates known for this purpose (see Hydrocarbon Processing (1981) 161), preferably disodium diborate and orthoboric acid, in an amount in the range of 5 to 50, preferred from 10 to 30 g / kg aqueous electrolyte solution.
  • anode corrosion inhibitor like the borates known for this purpose (see Hydrocarbon Processing (1981) 161), preferably disodium diborate and orthoboric acid, in an amount in the range of 5 to 50, preferred from 10 to 30 g / kg aqueous electrolyte solution.
  • the electrolyte solution preferably contains a complexing agent, to prevent the precipitation of iron and lead ions.
  • a complexing agent examples include ethylenediaminetetraacetate (“EDTA”), triethanolamine (“TEOA”), nitrilotriacetate, preferred EDTA in an amount ranging from 0 to 50, preferably 2 to 10 g / kg aqueous electrolyte solution, and / or TEOA in an amount in the range of 0 to 10, preferably 0.5 to 3 g / kg more aqueous Electrolyte solution.
  • Acrylonitrile is generally used in an amount in the range from 10 to 50, preferably from 20 to 30 wt .-%, based on the organic phase, a.
  • the reaction temperature is generally chosen in the range from 30 to 80, preferably from 50 to 60 ° C.
  • the pH essentially depends on the composition of the Electrolyte solution and is generally in the range of 6 to 10, preferably 7.5 to 9.
  • reaction pressure is not critical. It is usually chosen in the range from normal pressure to 10 bar.
  • the current density is generally chosen in the range from 1 to 40, preferably from 5 to 30 A / dm 2 .
  • the flow rate with continuous operation is usually in the range of 0.5 to 2 m / sec, preferably 0.8 to 1.5 m / sec.
  • the advantage of the electrode according to the invention is that Use as a cathode in the electrohydrodimerization of acrylonitrile to adiponitrile the corrosion of the cathodes is significantly less than when using solid lead or lead alloy electrodes, resulting in longer downtimes and less Amount of heavy metals.
  • the indicated corrosion rates of the electrodes were by means of atomic absorption spectroscopy (determination of the concentration on lead ions (cathode) released by corrosion and Iron ions (anode)) and by determining the weight loss of the electrodes after the end of the reaction.
  • the specified selectivities were determined using a gas chromatograph determined.
  • a round steel disc (diameter 20 mm) was used as the cathode used, which degreased as usual before the galvanic coating and was stained.
  • a lead strip also served as the anode the same dimensions as the cathode.
  • the electrodes were mounted parallel to each other in a tank. The reaction mixture in the bathroom was moved by mechanical stirring, the bath temperature was 25 ° C.
  • the coating bath (1 l) had the following composition: free fluoroboric acid 20 g / l Boric acid 30 g / l Lead fluoroborate 90 g / l Peptone 0.5 g / l water to 1 l
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally contained 2.6 g / l copper fluoroborate.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally contained 0.7 g / l copper fluoroborate.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally contained 1.6 g / l copper fluoroborate.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally contained 5.6 g / l copper fluoroborate.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally 1.25 g / l copper fluoroborate and Contained 0.5 g / l bismuth nitrate.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally 1.5 g / l copper fluoroborate and Contained 0.65 g / l tellurium dioxide.
  • the layer thickness was 50 ⁇ m.
  • Example 2 The procedure was as in Example 1, with the difference that the coating bath additionally 2.7 g / l copper fluoroborate and Contained 0.15 g / l selenium dioxide.
  • the layer thickness was 50 ⁇ m.
  • the cathode consisted of a pencil strip of the same dimensions.
  • the coating bath (10 1) had the following composition: free methanesulfonic acid 32 g / l Lead methanesulfonate 70 g / l Copper methanesulfonate 5.2 g / l Lutensol® AP 10 10 g / l
  • the layer thickness was 60 ⁇ m.
  • the coating contained 1% by weight copper.
  • a round steel electrode with a diameter of 20 mm was placed in a cathode sputtering system. Parallel to the steel substrate, a round mosaic target (diameter 150 mm) consisting of lead with copper discs (diameter 2 mm) was used at a distance of 60 mm. The area occupancy rate is shown in Table 1. The system was evacuated to a pressure of 10 -6 mbar using a two-stage pump system.
  • the substrate was heated to a temperature of 200 ° C. Then argon was admitted to a pressure of 9 x 10 -3 mbar.
  • the substrate was subjected to a sputter etching treatment for 1 min by applying an RF voltage with a power of 500 W to the substrate holder. After completion of the sputter etching treatment, the Ar pressure was set to 5 x 10 -3 mbar.
  • An atomizing plasma was ignited by applying a DC voltage to the target (power 1000 W) and an RF voltage to the substrate holder (power 200 W) and a (Pb-Cu) layer with a thickness of 10 ⁇ m was deposited on the stainless steel substrate .
  • the Cu content of the electrodes produced in this way is shown in Table 1. Area coverage of the Cu chips [%] Cu content of the electrode coating [% by weight] a 0 0 b 0.43 0.3 c 0.86 0.8 d 1.7 1.2 e 3.4 2.4 f 4.2 3.0 G 18th 13.0
  • the electrolytic solution was pumped through the electrolytic cell. From there it came into a separation vessel, where the formed Adiponitrile as an organic phase. Then was the aqueous electrolyte is pumped back into the electrolytic cell.
  • the organic phase consisted of:
  • the two phases were pumped around equilibrated so that acrylonitrile is dissolved in the aqueous phase was (about 2 wt .-%).
  • the remaining components were distributed according to their distributional equilibrium between the two Phases.
  • the conductive salt and approx. 4 wt .-% water in the organic phase so that the acrylonitrile concentration was about 26% by volume in the organic phase.
  • the electrolysis was operated continuously for 90 hours. After The massive lead cathode showed a corrosion rate of 90 hours of 0.35 mm / year (0.2 mg / Ah). The selectivity for adiponitrile was 90.3%.
  • the electrolysis was operated continuously for 90 hours. After The corrosion rate of the lead coating was 90 h of 0.25 mm / year (0.14 mg / Ah), the selectivity for adiponitrile was 90.4%.
  • the electrolysis was operated continuously for 200 hours. After A corrosion rate of 0.05 mm / year resulted for 200 h (0.03 mg / Ah), the selectivity was 90.9%.
  • the electrolysis was operated continuously for 209 hours. After The corrosion rate of the lead / copper cathode was 209 h of 0.16 mm / year (0.09 mg / Ah), the selectivity was 91.4%.
  • the electrolysis was operated continuously for 96 hours. After The corrosion rate of the lead / copper cathode was 96 h of 0.07 mm / year (0.04 mg / Ah), the selectivity was 90.4%.
  • the electrolysis was operated continuously for 90 hours. After The corrosion rate of the lead / copper cathode was 90 h of 0.05 mm / year (0.03 mg / Ah), the selectivity was 88.8%.
  • the electrolysis was operated continuously for 96 hours. After The corrosion rate of the lead / copper cathode was 96 h of 0.08 mm / year (0.045 mg / Ah), the selectivity was 90.0%.
  • the electrolysis was operated continuously for 96 hours. After The corrosion rate of the lead / copper cathode was 96 h of 0.09 mm / year (0.05 mg / Ah), the selectivity was 90.9%.
  • the electrolysis was operated continuously for 96 hours. After The corrosion rate of the lead / copper cathode was 96 h of 0.05 mm / year (0.03 mg / Ah), the selectivity was 90.9%.
  • the aqueous phase was pumped through the electrolytic cell.
  • the adiponitrile formed separated as organic in a separating vessel Phase. Then the aqueous electrolyte was restored returned to the electrolytic cell.
  • the organic phase consisted of: 30 vol% acrylonitrile and 70 vol% adiponitrile.
  • the two phases were pumped around equilibrated so that acrylonitrile is dissolved in the aqueous phase was (about 2 wt .-%).
  • the remaining components were distributed according to their distributional equilibrium between the two Phases.
  • the conductive salt and approx. 4 wt .-% water in the organic phase so that the acrylonitrile concentration was about 24% by volume in the organic phase.
  • the alloy electrode After 650 h, the alloy electrode showed a corrosion rate of 0.05 mm / year (0.03 mg / Ah), the selectivity for adiponitrile was 91.4%.
  • the bathroom had the following composition: Catholyte free methanesulfonic acid 48 g / l Lead methanesulfonate 64 g / l Copper methanesulfonate 5 g / l Lutensol® AP 10 10 g / l Anolyte free methanesulfonic acid 42 g / l Lead methanesulfonate 95 g / l
  • Electroplating was carried out for 2 hours at a current density of 12.5 mA / cm 2 .
  • the layer thickness was 60 ⁇ m.
  • the alloy contained 0.8% by weight of copper.
  • the electrolysis was operated continuously for 132 hours. After The lead coating showed a corrosion rate of 132 h of 0.14 mm / year (0.08 mg / Ah), the selectivity for adiponitrile was 90.6%.
  • the electrolysis was operated continuously for 90 hours. After The corrosion rate of the lead / copper cathode was 90 h of 0.08 mm / year (0.045 mg / Ah), the selectivity for adiponitrile was 90.3%.

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  • Electroplating And Plating Baths Therefor (AREA)
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Claims (7)

  1. Electrode constituée par un noyau électroconducteur constitué essentiellement de fer et par un revêtement monocouche électroconducteur constitué par du plomb et par du cuivre à concurrence de 0,3 à 3,5% en poids et éventuellement par d'autres éléments choisis parmi le groupe comprenant l'argent, le sélénium, le tellure, le bismuth et l'antimoine.
  2. Electrode selon la revendication 1, caractérisée en ce qu'on applique le revêtement électroconducteur par galvanisation ou par des procédés de déposition physique choisis parmi le groupe constitué par la métallisation au vide, la pulvérisation cathodique ("sputter") ou via une enduction par l'arc électrique, sur le noyau électroconducteur.
  3. Cellule électrochimique comprenant au moins une électrode selon les revendications 1 à 2, montée pour faire office de cathode.
  4. Procédé pour la fabrication d'une électrode selon les revendications 1 à 3, caractérisé en ce qu'on applique le revêtement électroconducteur par galvanisation ou par des procédés de déposition physique choisis parmi le groupe constitué par la métallisation au vide, la pulvérisation cathodique ("sputter") ou via une enduction par l'arc électrique, sur le noyau électroconducteur.
  5. Procédé pour le couplage par réduction de partenaires réactionnels oléfiniques par électrohydrodimérisation d'une manière connue en soi, caractérisé en ce qu'on expose les partenaires réactionnels à une électrolyse dans une cellule électrochimique selon la revendication 3.
  6. Procédé selon la revendication 5, caractérisé en ce qu'on met en oeuvre, à titre de partenaires réactionnels oléfiniques, des composés répondant à la formule générale R1R2C=CR3X dans laquelle R1, R2 et R3 sont identiques ou différents et représentent un atome d'hydrogène, un groupe alkyle en C1-C4 et X représente CN, CONR1R2 ou COOR1.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on met en oeuvre, à titre de partenaire réactionnel oléfinique, de l'acrylonitrile.
EP94108425A 1993-06-16 1994-06-01 Electrode comprenant un noyau contenant du fer et un revêtement contenant du plomb Expired - Lifetime EP0635587B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97122734A EP0931856A3 (fr) 1993-06-16 1994-06-01 Procédé de couplage réductif dans une cellule d'électrolyse ayant une cathode comprenant un support à base de fer et un revêtement à base de plomb

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4319951A DE4319951A1 (de) 1993-06-16 1993-06-16 Elektrode, bestehend aus einem Eisen-haltigen Kern und einem Blei-haltigen Überzug
DE4319951 1993-06-16

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP97122734A Division EP0931856A3 (fr) 1993-06-16 1994-06-01 Procédé de couplage réductif dans une cellule d'électrolyse ayant une cathode comprenant un support à base de fer et un revêtement à base de plomb

Publications (2)

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EP0635587A1 EP0635587A1 (fr) 1995-01-25
EP0635587B1 true EP0635587B1 (fr) 1998-09-23

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EP94108425A Expired - Lifetime EP0635587B1 (fr) 1993-06-16 1994-06-01 Electrode comprenant un noyau contenant du fer et un revêtement contenant du plomb
EP97122734A Withdrawn EP0931856A3 (fr) 1993-06-16 1994-06-01 Procédé de couplage réductif dans une cellule d'électrolyse ayant une cathode comprenant un support à base de fer et un revêtement à base de plomb

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Country Status (7)

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US (1) US5593557A (fr)
EP (2) EP0635587B1 (fr)
JP (1) JPH07305189A (fr)
BR (1) BR9402435A (fr)
CA (1) CA2125829A1 (fr)
DE (2) DE4319951A1 (fr)
ES (1) ES2121120T3 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9502665D0 (en) * 1995-02-11 1995-03-29 Ici Plc Cathode for use in electrolytic cell
DE10039171A1 (de) 2000-08-10 2002-02-28 Consortium Elektrochem Ind Kathode für Elektrolysezellen
WO2009071478A1 (fr) * 2007-12-03 2009-06-11 Basf Se Procédé d'hydrodimérisation réductrice de composés organiques insaturés au moyen d'une électrode de diamant
US8840770B2 (en) * 2010-09-09 2014-09-23 International Business Machines Corporation Method and chemistry for selenium electrodeposition
US9005409B2 (en) 2011-04-14 2015-04-14 Tel Nexx, Inc. Electro chemical deposition and replenishment apparatus
US9017528B2 (en) 2011-04-14 2015-04-28 Tel Nexx, Inc. Electro chemical deposition and replenishment apparatus
WO2013026737A2 (fr) 2011-08-24 2013-02-28 Basf Se Procédé de préparation électrochimique d'esters d'acide γ-hydroxycarboxylique et de γ-lactones
WO2013180443A1 (fr) * 2012-05-29 2013-12-05 한국생산기술연구원 Barre omnibus en fer ayant une couche de cuivre, et procédé de fabrication de cette dernière
US9303329B2 (en) 2013-11-11 2016-04-05 Tel Nexx, Inc. Electrochemical deposition apparatus with remote catholyte fluid management
EP2985364A1 (fr) 2014-08-14 2016-02-17 Basf Se Procédé de préparation d'alcools par couplage réductive électrochimique
US11313045B2 (en) * 2019-03-30 2022-04-26 New York University Electrohydrodimerization of aliphatic olefins with electrochemical potential pulses

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193481A (en) * 1962-10-05 1965-07-06 Monsanto Co Electrolytic hydrodimerization alpha, beta-olefinic nitriles
US3193482A (en) * 1964-01-14 1965-07-06 Monsanto Co Electrolysis of alpha, beta mono-olefinic carboxylates
US3193483A (en) * 1964-01-14 1965-07-06 Monsanto Co Electrolysis of acrylamides
US3844911A (en) * 1972-07-27 1974-10-29 Phillips Petroleum Co Method for producing adiponitrile
JPS5127773B2 (fr) * 1972-09-11 1976-08-14
US3898140A (en) * 1973-08-06 1975-08-05 Monsanto Co Electrolytic hydrodimerization process improvement
US4038170A (en) * 1976-03-01 1977-07-26 Rhees Raymond C Anode containing lead dioxide deposit and process of production
US4306949A (en) * 1979-12-19 1981-12-22 Monsanto Company Electrohydrodimerization process
CA1232227A (fr) * 1982-02-18 1988-02-02 Christopher Vance Electrode enduite de plomb ou d'un alliage de plomb et methode de fabrication
JPS59193866U (ja) * 1983-06-13 1984-12-22 高安　清澄 不溶性鉛電極
JPS6396299A (ja) * 1986-10-13 1988-04-27 Yoshizawa Kiko Toubu Kk 鉛合金製不溶性陽極
JPS63111193A (ja) * 1986-10-30 1988-05-16 Asahi Chem Ind Co Ltd アジポニトリルの製法

Also Published As

Publication number Publication date
CA2125829A1 (fr) 1994-12-17
JPH07305189A (ja) 1995-11-21
EP0931856A2 (fr) 1999-07-28
US5593557A (en) 1997-01-14
ES2121120T3 (es) 1998-11-16
BR9402435A (pt) 1995-01-24
EP0635587A1 (fr) 1995-01-25
DE4319951A1 (de) 1994-12-22
EP0931856A3 (fr) 1999-08-18
DE59406960D1 (de) 1998-10-29

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