US3193480A - Adiponitrile process - Google Patents

Adiponitrile process Download PDF

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Publication number
US3193480A
US3193480A US255586A US25558663A US3193480A US 3193480 A US3193480 A US 3193480A US 255586 A US255586 A US 255586A US 25558663 A US25558663 A US 25558663A US 3193480 A US3193480 A US 3193480A
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Prior art keywords
acid
catholyte
acrylonitrile
anolyte
salts
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US255586A
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Manuel M Baizer
Charles R Campbell
Robert H Fariss
Johnson Robert
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Monsanto Co
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Monsanto Co
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Priority to US255586A priority Critical patent/US3193480A/en
Priority to DE1468306A priority patent/DE1468306B2/de
Priority to LU45327A priority patent/LU45327A1/xx
Priority to NO151810A priority patent/NO119678B/no
Priority to FR1415524A priority patent/FR1415524A/fr
Priority to CH115764A priority patent/CH459168A/de
Priority to GB4261/64A priority patent/GB1030051A/en
Priority to NL6400836A priority patent/NL6400836A/xx
Priority to BE643247A priority patent/BE643247A/xx
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Publication of US3193480A publication Critical patent/US3193480A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • C25B3/01—Products
    • C25B3/09—Nitrogen containing compounds
    • 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 a process of electrolytically hydrodimerizing acrylonitrile to acliponitrile in a salt catholyte of a divided cell employing acid anolyte.
  • the figure of the drawing is an illustration of an acrylonitrile electrolysis system in which the anolyte and catholyte are separately circulated through the electrolysis cell which is illustrated in cross-section.
  • a salt solution is used for the electrolysis because of the. tendency of acrylonitrile to polymerize when electrolyzed under acid conditions. It is generally desirable to have the catholyte pH in the range of about 7 to about 9.5 or 10.
  • the alkalinity of the catholyte depends upon the rate at which ions or molecules move across the diaphragm relative to the rate phragm as a result of concentration differences.
  • an acid anolyte in the hydrodimcrization of acrylonitrile.
  • an aqueous solution containing a quaternary ammonium salt and acrylonitrile tends to have a high electrical resistance.
  • the overall resistance of the cell can be considerably lessened, therefore, if a mineral acid rather than a quaternary ammonium salt solution is utilized as anolyte.
  • Mineral acids e.g.. sulfuric acid. have the additional advantage of being inexpensive and readily available.
  • Phosphoric acid and other mineral acids can be employed, as can organic sulfonic acids, e.g., benzene or toluene sulfonic acids.
  • Sulfuric acid is definitely preferred as its use minimizes corrosion problems and the oxygen produced at the anode in such acid does not cause any special difiiculties.
  • electrothe catholyte While hydrodimerization of acrylonitrile square decimeter, and it is further possible to use cells having a large eflective electrode area, whether in a single set of electrodes or in a series of electrodes. Thus in commercial practice it is probable that individual cells will draw at least 20 to 30 ampe'res, most likely more than amperes, and cells drawing more than 1000 amperes are contemplated.
  • Various power sources are suitable for use in the present invention. particularly any efficient sources of direct current, and, if desired, various known means of varying the applied potential to regulate the current density and the cathode potential can be employed, for example the means described in Metcalf et al., US. Patent No. 2,835,631, issued May 20, 1958, the disclosure of which is incorporated herein by reference. If desired altcrnat ing current can be superimposed on the direct current applied to the cell.
  • the acid employed as anolyte will have a normality such that enough hydrogen ions migrate to the catholyte to counteract the hydroxyl ions generated at the chosen current density.
  • Example Acrylonitrile was hyd'rodimerized in a divided cell with acid anolyte in a number of runs under comparable conditions except that the current density was varied and the anolytenormality was correspondingly adjusted to control catholyte pH, with results as follows:
  • the acid anolyte' normality have a value in the range of about 0.02 to 0.06 times the current density (in ampe'rcs/dmF), for example, about 0.03 times the current density, in order to maintain the catholyte pH relatively constant.
  • current density in ampe'rcs/dmF
  • normalities of about 0.4 to 1.2 are suitable for current densities of to 40 ampe'rcs/dm. of cathode area.
  • the acid employed as 'anolyte will be fairly dilute, particularly when a strong mineral acid is employed.
  • Sulfuric acid is very suitable for use in the present invention, and such concentrations of sulfurie acid can suitably be employed, and'are practical and useful from the viewpoint of conductivity and low anodic corrosion, as well as pH control.
  • Other strong acids e.g.. those having relatively high ionization constants,
  • cart suitably be embrane comprised of. a sulfonated styrcne-divinyl benzene polymer supported upon a glass fiber base.
  • embrane comprised of. a sulfonated styrcne-divinyl benzene polymer supported upon a glass fiber base.
  • the lnear flow rate of the catholyte along the cathode surface was approximately 1.5 ft./sec.
  • the electrolysis takes place in electrolysis cell 1 in which a cathode plate 2 and a diaphragm 3 with the other Walls of the completely enclosed cell chamber form a cathode compartment and the said diaphragm 3 and an ode plate 4 form a separate anode compartment.
  • cathode 2 is connected to the negative terminal of a source of direct current.
  • anode 4 is connected to the positive source'of, such current, and the cathode and anode are clamped in juxtaposition but separated by insulating gasketing material.
  • acrylonitrile is fed through pump 5 and the sal't'solution through pump 6 to the catholyte recirculating pump 7 and then through an aperture in the cathode plate 2, through the cathode cornpartment and out another aperture in the cathode plate to the catholyte reservoir 8.
  • the catholyte reservoir is provided with means (not illustrated) such as a gravity overflow system to discharge part of the catholyte, and means are also available to heat the catholyte in the reservoir if necessary.
  • a pH meter 9 is hooked into the catholyte recirculationline 10, and a water-jacketed heat exchanger 11 is hooked across the recirculation pump to permit cooling of.the catholyte if necessary.
  • the anolyte is made up by feeding water and acid to the anolyte reservoir 12 from which it is fed through a water-jacketed heat exchanger 13 to the anolyte recirculating pump 14. thence through an aperture in the anode plate 4 and through the anode chamber to return to the anolyte reservoir 12.
  • the anolyte reservoir is equipped with a water-jacketed condenser 15 to permit oxygen or other gases to escape from the anolyte.
  • the cathode was lead and the anode,platinum on titanium; other electrode materials are suitable, forexample, mercury or various lead alloys as cathode, and lead or lead alloys as anode. It will be understood that the electrodes are in actual contact, i.e., solid-liquid contact, with the catholyte and anolyte and are not separated therefrom by an air gap or otherwise.
  • the catholyte employed in the runs was a by weight concentration of tetrarnethylamrnonium toluene The Fit)
  • electrolyte salts are already known and suitable electrolyte salts can be selected in the light of the present disclosure for use in the catholyte in the present invention. In general it will be desirable to avoid overly acidic or overly basicsalts in view of the pH considerations discussed herein, and ordinarily salts of strong bases will be employed, particularly salts of strong bases and strong acids.
  • the amine and quaternary ammonium salts are generally suitable, especially those of sult'nnic and alkyl sulfuric acid.
  • Such salts can he the saturated aliphatic amine salts or heterocylic amine salts. c.g.. the mono-, dior trialkylamine salts, or the mono-. dior trialkanolamine salts. or the piperidine, pyrrolidine or morpholine salts, e.g., the cthylamine, dimcthyamine or triisopropylamine salts of various acids. especially various sulfonic' acids.
  • aliphatic and hctcrocyclic quaternary ammonium salts are particularly preferred, especially preferred are aliphatic and hctcrocyclic quaternary ammonium salts.
  • the saturated aliphatic or heterocyclic quaternary ammonium cations in general have suitably high cathode discharge potentials for use in the present invention and readily form salts having suitably high. water solubility with anions suitable for use in the electrolytes employed in the present invention.
  • the saturated, aliphatic or heterocyclic quaternary ammonium salts of such acids are therefore in general well adapted to dissolving high amounts of olcfinic compounds in their aqueous solutions, i.e., hydrotropic salts, and to effecting reductive couplings of such olefinic compounds. It is understood, of course, that it is undesirable that the ammonium groups contain any reactive groups which might interfere to some extent with the reductive coupling reaction. In this connection it should be noted that aromatic unsaturation as such does not interfere as benzyl substituted ammonium cations can be'employed (as also can aryl sulfonate anions).
  • the aryl and alkaryl sulfonic acids are especially suitable, for example. salts of the following acids: lw'cnzenesulfonic acid, o-. mor p-toluencsulfonic acid, o-. m or p-cthylbenzenesulfonic acid.
  • pentamethylbenzenesulfonie acid o-dipropylbcnzenet-sultonic acid, alphaor beta-naphthalenesulfonie acid, o-, mor p-biphenylsulfonic acid, and alpha-methyl-beta-naphthalenesulfonic acid.
  • Alkali metal salts are useful with certain limitations, and the alkali metal salts of such sulfonic acids can be employed, i.e., the sodium, potassium, lithium, cesium, or rubidium salts such as sodium benzenesulfonate, potassium p-toluenesulfonate, lithium o biphenylsulfonate, rubidium beta naphthalenesulfonate, cesium p-ethylbenezenesulfonate, sodium o-xylene-3-su]fonate, or potassium pentamethylhenzenesulfonate.
  • the alkali metal salts of such sulfonic acids can be employed, i.e., the sodium, potassium, lithium, cesium, or rubidium salts such as sodium benzenesulfonate, potassium p-toluenesulfonate, lithium o biphenylsulfonate, rubidium beta naphthalene
  • the salts of such sulfonic acids may also be the saturated, aliphatic amine or heterocyclic amine salts, e.g., the monodior trialkylamine salts, or the mono-, di or trialkanolamine salts, or the piperidine, pyrrolidine, or morpholine salts, e.g., the ethylamine, dimethylamine or triisopropylamine salt of benzenesulfonic acid or of 0-, por m-toluenesulfonic acid; the isopropanolamine, dibutanolamine or triethanolamine salt of o-, por m-toluenesulfonic acid or of o-, p-, or m-biphenylsulfonic acid; the piperidine salt of alphaor beta-naphthalenesulfonic acid or of the cumenesulfonic acids, the pyrrolidine salt of o-, m-, or pa
  • the sulfonates of any of the ammonium cations disclosed generically or specifically herein can be employed in the present invention.
  • the aliphatic sulfonates are prepared by reaction of the correspondingly substituted ammonium hydroxide with the sulfonic acid or with an acyl halide thereof.
  • quaternary ammonium 'sulfonates are, e.g., tetraethylammoni- T urn 0- or m-toluenesulfonate or benzenesulfonate; tetraethyl-ammonium o-, mor p-cumenesulfonate or o-, m-, or I p-ethylbenzenesulfonate, tetraethylammonium benzenesulfonate, or o-, mor p-toluenesulfonate; N, N-di-methylpiperidinium o-, mor p-toluenesulfonate or o-, m or pbipyhenylsulfonate; tetrabutylammonium alphaor betanaphthalenesulfonate or o-, mor p-toluene
  • tetraalkylammonium salts of the aryl or alkarylsulfonic acids are generally preferred for use as the salt constituents of the electrolysis solution because the electrolyses in the tetraalkylammonium sulfonates are exclusively electrochemical processes.
  • ammonium and amine sulfonates useful as electrolytes in the present invention are the alkyl, aralkyl, and heterocyclic amine and ammonium sulfonates, in which ordinarily the individual substituents on the nitrogen atom contain no more than atoms, and usually the amine or ammonium radical contains from 3 to carbon atoms. It will be understood, of course, that diand poly-amines and diand poly-ammonium radicals are operable and included by the terms amine and ammonium.
  • the sulfonate radical can be from aryl, alkyl,
  • cations are suitable for use in the present invention, e.g., tetraalkyl-phosphonium and trialkylsult'onium cations, particularly from sulfonate salts formed from sulfonic acids as described above. Similar- 1y, other anions can be selected from alkylsulonates and anions of other acids. Further guides to the choice and use of the electrolyte salt are found in the aforementioned Ser. No. 228,740.
  • a permselective membrane as the cell divider, particularly a membrane which is permselective as to particles carrying a positive electric charge and which therefore permits the passage of cations, while preventing the passage of undesirable amounts of anions.
  • a permselective membrane as the cell divider, particularly a membrane which is permselective as to particles carrying a positive electric charge and which therefore permits the passage of cations, while preventing the passage of undesirable amounts of anions.
  • Continuous, non-porous permselective cationic membranes comprising insoluble cation-exchange resin are suitable.
  • the cation-exchange resins which are preferred for use in such membranes are those of the sulfonic and carboxylic types, many of which are available commercially, such as sulfonated phenolaldehyde resin products, sulfonated cross-linked polymers of styrene, and carboxylic resins such as typified by those included in U.S. Patents Nos. 2,340,110 and 2,340,111, or any of the resins disclosed as suitable for such membranes in Juda et al., Reissue Patent 24,865.
  • a cationic membrane comprised of a sulfonated styrene-divinyl benzene polymer supported upon a glass fiber or fabric material can be employed.
  • the cation permselective membranes employed comprise a solid polymeric matrix with at least 1 milliequivalent per dry gram of membrane of dissociable ionic groups, e.g., acid groups such as carboxylate group's, fixed into said matrix, said membrane being reinforced by an embedded non-corrodible material.
  • a suitable polymer of the indicated type is the sulfonated styrene-divinyl benzene copolymer described under the name Dowex 50 in the Journal of the American Chemical Society, volume 69, page 2830, (1947).
  • the membranes can be particles of ion exchange material formed together by the same or a different type of resin or by water-insoluble jelly-like material such as petrolatum, amorphous wax, hydrocarbon jels, etc. It is preferred that the membrane be substantially non-porous in order that it may be sufiiciently permselective and will not permit too rapid movement of ions. It will be understood that the membranes must be reasonably resistant to attack by both anolyte and catholyte solutions under conditions of operation and also that good mechanical strength is necessary for the embodiment in which there is highly turbulent liquid flow over the membrane surface.
  • the method of electrolyzing acrylonitrile to obtain The membranes employed can be substantially and recover adiponitrilc which comprises passing electric current through a catholyte in contact with a cathode, the
  • catholyte consisting essentially of water, acrylonitrile and an electrolyte salt which has a discharge potential more negative than that of acrylonitrile and being separated by a diaphragm from the anolyte which is an aqueous acid solution having an acid concentration of 0.05 to 20% by weight, and of strength matched to the current density to provide sumcient hydrogen ion to neutralize hydroxyl ionsgen erated at the cathode, and recovering adiponitrile from the catholyte.
  • the method of electrolyzing acrylonitrile to obtain and recover adiponitril'e which comprises passing electric current through a catholyte in contact with a cathode, the catholyte being an aqueous electrolyte salt solution containing acrylonitrile, the electrolyte salt having a discharge potential more negative than that of acrylonitrile, and the catholyte'being separated by. an ion exchange membrane from the anolyte which is an aqueous'acid solution of acidity such that thepH of the catholyte is maintained in the range of 7 to 9.5, and recovering adiponitrile from the catholyte.
  • the method oficlaim 1 in which the anolyte is an aqueous solution of an inorganic acid which is separated from the catholyte by a perm-selective cationic menibrane and the electrolysis is conducted on a continuous basis involving addition of acrylonit'rile to the catholyte and removal of adiponitrile from the catholyte during the elcctrolysis'without the necessity of adding materials to the catholyte to adjust the hydrogen ion concentration thereof.
  • the method of electrolyzing acrylonitrile which comprises passing electric current through an aqueous quaternary ammonium sulfonate solution containing acrylonitrile in contact with a lead metal cathode, the said anolyte is an solution being separated by an ion exchange membrane References Cited by the Examinerv UNITED STATES PATENTS 2,726,204 12/55 Park etal. 204- 72 2,921,005 '1/60 BOdatnet' 204-72 FOREIGN PATENTS 566,274 11/58 Canada.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Geophysics And Detection Of Objects (AREA)
US255586A 1960-12-12 1963-02-01 Adiponitrile process Expired - Lifetime US3193480A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US255586A US3193480A (en) 1963-02-01 1963-02-01 Adiponitrile process
DE1468306A DE1468306B2 (de) 1963-02-01 1964-01-29 Verfahren zur Herstellung von Adipinsäuredinitril durch elektrolytische Hydrodimerisaten von Acrylnitril
LU45327A LU45327A1 (no) 1963-02-01 1964-01-30
FR1415524A FR1415524A (fr) 1963-02-01 1964-01-31 Procédé d'hydrodimérisation de composés oléfiniques
NO151810A NO119678B (no) 1963-02-01 1964-01-31
CH115764A CH459168A (de) 1960-12-12 1964-01-31 Verfahren zur Elektrolyse von Acrylnitril für die Herstellung von Adipinsäurenitril
GB4261/64A GB1030051A (en) 1963-02-01 1964-01-31 Production of adiponitrile
NL6400836A NL6400836A (no) 1963-02-01 1964-01-31
BE643247A BE643247A (no) 1963-02-01 1964-01-31

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BE (1) BE643247A (no)
DE (1) DE1468306B2 (no)
FR (1) FR1415524A (no)
GB (1) GB1030051A (no)
LU (1) LU45327A1 (no)
NL (1) NL6400836A (no)
NO (1) NO119678B (no)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile
US3402112A (en) * 1965-07-26 1968-09-17 Monsanto Co Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell
US3427234A (en) * 1965-04-14 1969-02-11 Basf Ag Electrochemical hydrodimerization of aliphatic alpha,beta-mono-olefinically unsaturated nitriles
US3455986A (en) * 1964-11-24 1969-07-15 Ici Ltd Process for the reductive dimerization of alpha,beta-olefinic compounds
US3475305A (en) * 1966-05-31 1969-10-28 Toray Industries Process for manufacture of adiponitrile
US3481846A (en) * 1963-06-24 1969-12-02 Du Pont Electrolytic production of adiponitrile
US3489789A (en) * 1964-04-16 1970-01-13 Ici Australia Ltd Process for the reductive dimerization of alpha,beta-olefinicallyunsaturated nitriles or esters
US3492209A (en) * 1963-11-04 1970-01-27 Hooker Chemical Corp Hydrodimerization in a wicking type cell
US3497429A (en) * 1965-12-03 1970-02-24 Asahi Chemical Ind Electrolytic method of manufacturing hydrodimer of acrylonitrile
US3523068A (en) * 1966-12-19 1970-08-04 Monsanto Co Process for electrolytic preparation of quaternary ammonium compounds
US3619388A (en) * 1969-02-05 1971-11-09 Asahi Chemical Ind Process for electrolyzing nitriles
US3755101A (en) * 1970-11-19 1973-08-28 Rhone Poulenc Sa Process for the preparation of saligenol
US3898140A (en) * 1973-08-06 1975-08-05 Monsanto Co Electrolytic hydrodimerization process improvement
US4046651A (en) * 1975-07-28 1977-09-06 Monsanto Company Electrolytic hydrodimerization process improvement
US4490243A (en) * 1980-07-09 1984-12-25 Terukatsu Miyauchi Process for thermal cracking of heavy petroleum oils
US4941954A (en) * 1989-05-08 1990-07-17 E. I. Du Pont De Nemours And Company Electrochemical preparation of branched unsaturated dinitriles
WO2018172927A3 (en) * 2017-03-20 2018-11-15 Ecole Polytechnique Federale De Lausanne (Epfl) Solar production of nylon polymers and prescursors for nylon polymer production

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2726204A (en) * 1949-04-14 1955-12-06 Monsanto Chemicals Polymerization process
CA566274A (en) * 1958-11-18 Sun Oil Company Polymerization of ethylene
US2921005A (en) * 1952-10-17 1960-01-12 Rohm & Haas Electrolytic conversions with permselective membranes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA566274A (en) * 1958-11-18 Sun Oil Company Polymerization of ethylene
US2726204A (en) * 1949-04-14 1955-12-06 Monsanto Chemicals Polymerization process
US2921005A (en) * 1952-10-17 1960-01-12 Rohm & Haas Electrolytic conversions with permselective membranes

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3481846A (en) * 1963-06-24 1969-12-02 Du Pont Electrolytic production of adiponitrile
US3492209A (en) * 1963-11-04 1970-01-27 Hooker Chemical Corp Hydrodimerization in a wicking type cell
US3489789A (en) * 1964-04-16 1970-01-13 Ici Australia Ltd Process for the reductive dimerization of alpha,beta-olefinicallyunsaturated nitriles or esters
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile
US3455986A (en) * 1964-11-24 1969-07-15 Ici Ltd Process for the reductive dimerization of alpha,beta-olefinic compounds
US3427234A (en) * 1965-04-14 1969-02-11 Basf Ag Electrochemical hydrodimerization of aliphatic alpha,beta-mono-olefinically unsaturated nitriles
US3402112A (en) * 1965-07-26 1968-09-17 Monsanto Co Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell
US3497429A (en) * 1965-12-03 1970-02-24 Asahi Chemical Ind Electrolytic method of manufacturing hydrodimer of acrylonitrile
US3475305A (en) * 1966-05-31 1969-10-28 Toray Industries Process for manufacture of adiponitrile
US3523068A (en) * 1966-12-19 1970-08-04 Monsanto Co Process for electrolytic preparation of quaternary ammonium compounds
US3619388A (en) * 1969-02-05 1971-11-09 Asahi Chemical Ind Process for electrolyzing nitriles
US3755101A (en) * 1970-11-19 1973-08-28 Rhone Poulenc Sa Process for the preparation of saligenol
US3898140A (en) * 1973-08-06 1975-08-05 Monsanto Co Electrolytic hydrodimerization process improvement
US4046651A (en) * 1975-07-28 1977-09-06 Monsanto Company Electrolytic hydrodimerization process improvement
US4490243A (en) * 1980-07-09 1984-12-25 Terukatsu Miyauchi Process for thermal cracking of heavy petroleum oils
US4941954A (en) * 1989-05-08 1990-07-17 E. I. Du Pont De Nemours And Company Electrochemical preparation of branched unsaturated dinitriles
WO2018172927A3 (en) * 2017-03-20 2018-11-15 Ecole Polytechnique Federale De Lausanne (Epfl) Solar production of nylon polymers and prescursors for nylon polymer production

Also Published As

Publication number Publication date
DE1468306A1 (de) 1968-11-28
NO119678B (no) 1970-06-22
LU45327A1 (no) 1964-07-30
DE1468306B2 (de) 1975-08-21
FR1415524A (fr) 1965-10-29
NL6400836A (no) 1964-08-03
GB1030051A (en) 1966-05-18
BE643247A (no) 1964-07-31

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