US3556961A - Electrolytic hydrodimerisation - Google Patents

Electrolytic hydrodimerisation Download PDF

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Publication number
US3556961A
US3556961A US649846A US3556961DA US3556961A US 3556961 A US3556961 A US 3556961A US 649846 A US649846 A US 649846A US 3556961D A US3556961D A US 3556961DA US 3556961 A US3556961 A US 3556961A
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solution
acrylonitrile
water
cell
tetra
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Jean Bizot
Guy Bourat
Daniel Michelet
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Rhone Poulenc SA
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Rhone Poulenc SA
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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

  • the electrolytic reduction potential of acrylonitrile is of the order of 2 v. relative to a calomel electrode [see W. L. Bird, Anal. Chem. XXIV 586 (1952)] and that for electrolytic reduction it is essential that the electrolyte should not be reduced before the compound which one wishes to reduce.
  • electrolytes based on quaternary ammonium salts it is possible to achieve sufliciently negative potentials [Bird, Anal. Chem. 24, 586 (1952); Strackelberg, Z. fiir elektrochem. 53,118 (1949)].
  • the present invention provides a process for the hydroice dimerisation of an ethylenically unsaturated monomer of the general formula:
  • R R and R which may be the same or different, each represents a hydrogen atom or a hydrocarbon radical, e.g. of l to 6 carbon atoms, and Z represents a ketone, ester, nitrile, amide or aldehyde group, which comprises electrolysing a mixture of (a) the monomer, (b) water, the ratio of monomer/water being from 15/85 to /25 by weight, and 10 to 30%, preferably from 15 to 25%, based on the total weight of the mixture of (c) a buffer containing at least one quaternary ammonium salt of an oxygen-containing inorganic acid having a pK in water of from 5 to 11, preferably from 7 to 10, the components of the buffer being in such a ratio that the pH of their aqueous solution is from 6 to 10.
  • the preferred ethylenically unsaturated monomer is acrylonitrile.
  • the process is particularly advantageous in that the electrolysis can be carried out without a separating membrane, concentrated aqueous solutions are used, and adiponitrile is obtained in a high degree of purity from acrylonitrile.
  • the weight ratio of water/monomer in the homogeneous mixture is from 60/40 to 35/65.
  • the anions of the butters used in the process of this invention are for example anions of weak acids such as borates, carbonates or bicarbonates, and phosphates which are not destroyed at the anode. They have a buffering effect this term being understood as the property of an aqueous solution, which contains an acid-base couple in the Bronsted sense, of varying little in pH whilst considerable quantities of acid or base are added to it. The pH of the aqueous solution is thus stabilised within a range on either side of the value of the pK of the acid-base couple.
  • Acidbase couples suitable for use in the process of the present invention are those whose pK is between 5 and 11 and more particularly between 7 and 10, such as, for example, the monobasic phosphatedibasic phosphate, borate-boric acid or carbonate-bicarbonate couples, in amounts such that the pH of their aqueous solution is between 9 and 10.
  • the buffering effect is a maximum when the basic form and the acid form are present in equal concentrations. Nevertheless these proportions can be changed if a pH other than the pK of the couple is desired, without however one of the forms being too much in excess relative to the other.
  • the best results are obtained when the acid form represents a concentration which is 25 to 75% of the concentration of the salt. Salts derived from a weak acid having a pK of between 5 and 11 and therefore having a buffering effect relative to the pH in an aqueous solution, but which would be oxidised or otherwise degraded at the anode may be used in the process of the invention though they are of less interest since their use requires separation of the anode and cathode compartments.
  • the presence of the buffer makes it possible to inhibit the formation of the usual byproducts such as, for example, propionitrile, p-hydroxypropionitrile or bis (B-cyanoethyD-ether.
  • tertiary amine salts which can have a certain buffering effect has been proposed previously, but they are reduced at a potential close to that necessary for the hydrodimerisation and this makes them of little value in most cases.
  • the cations which are suitable for the process of the present invention must impart a strong hydrotropic effect to the electrolyte.
  • the tetra(n-butyl) ammonium cation is particularly suitable. Solutions of acrylonitrile in water containing 75 of acrylonitrile by weight and less than 30% of salt, relative to the total of the three components,
  • tetrabutyl ammonium salt such as the carbonate
  • Salts or mixtures of salts which are particularly suitable for use in the process of the present invention are for example equimolecular mixtures of the tetra-(n-butyl) ammonium monobasic phosphate and the tetra(n-butyl) ammonium dibasic phosphate, Whose pH in aqueous solution is 7.4.
  • the pH in water can be fixed at a value of between 7.5 and 8.5.
  • mixtures of boric acid and tetra(nbutyl) ammonium borate (which makes it possible to stabilise the pH in water at about 9) and especially mixtures of tetra(n-butyl) ammonium or tetra(n-propyl) ammonium carbonates and bicarbonates can be used.
  • the proportions used are such that the resulting pH in water is preferably between 8.5 and 10.
  • the acrylonitrile content is normally from to 75% by weight based on the total weight of the solution and preferably from to 50% by weight.
  • a mixture which is particularly suitable for the hydrodimerisation of acrylonitrile contains 50% by weight of acrylonitrile, 25% by weight of water and 25 by weight of one of the above-mentioned mixtures of tetra-(n-butyl) ammonium salts.
  • the electrolysis is generally carried out in a cell with a single compartment, although cells having separate compartments may also be used.
  • electrical energy yields kWh. per kg. of adiponitrile produced
  • the cathodes which can be used are those which make it possible electrochemically to reduce compounds which are difi'icult to reduce without interference by the reduction of the water.
  • Mercury, graphite and lead which have previously been used, provide suitable cathodes, but it has been found that alloys of lead with mercury, and Darcet alloy, also give good results.
  • Suitable anodes are those which have a low oxygen overpotential in the electrolysis of water, such as, for example, lead anodes which may or may not be coated with oxide, nickel which may or may not be surfaceoxidised, platinum deposited onto graphite, gold, or stainless steel which has preferably been made passive. Insoluble anodes which have an oxygen overpotential less than that of gold are preferably used.
  • the potential which has to be applied between the anode and the cathode in order to carry out the process of the present invention is generally low.
  • the ohmic potential drop, and correspondingly the energy loss by the Joule effect, in the electrolyte can be reduced by bringing the electrodes closer together.
  • This distance is not limited but in order to have good circulation of liquid between the electrodes their distance apart may advantageously be from 1 to 15 millimetres and preferably from 1 to 3 millimetres.
  • the potentials to be applied are chosen so as to have a suitable cathode potential, and potentials of 3 to 8 volts are generally very suitable for a single-compartment cell.
  • the electrolytic bath is moderately stirred and the electrolysis is preferably stopped when about half the product has been converted for a discontinuous process.
  • the apparatus comprises a single-compartment cell equipped with a reflux condenser, a mercury cathode of cm. surface area and a lead anode in the form of a perforated plate of area 60 cm. arranged parallel to the surface of the mercury and 10 mm. therefrom.
  • the mercury and the electrolytic solution are stirred.
  • a butter solution is prepared by bubbling carbon dioxide into an aqueous solution containing 40% by weight of tetra (n-butyl) ammonium hydroxide until the pH of the solution is 9.
  • the solution then contains about 500 g./l. of a mixture of tetra-(n-butyD ammonium carbonate and bicarbonate. 5 3 g. of this solution are mixed with 53 g. of acrylonitrile and 27 g. of water and the combined solution is introduced into the cell.
  • the potential at the terminals is adjusted to 6 v. and the temperature to 40 C. 42,500 coulombs are passed across the cell with moderate stirring of the mercury and the electrolytic solution.
  • the cell is then emptied, rinsed with methanol, and 149 g. of a practically colourless solution are thus obtained.
  • EXAMPLE 2 An electroyte obtained by mixing equal amounts of acrylonitrile and an aqueous solution containing 500 g./l. of a mixture of tetra(n-butyl) ammonium carbonate and bicarbonate and having a pH of 9 (prepared as described in Example 1) is introduced into a closed cell under reflux at ambient temperature, the cell having a single compartment provided with a mercury cathode and an anode consisting of a spiral of pure nickel wire previously oxidised with air in a flame.
  • the process is carried out at ambient temperature. 2,900 coulombs are passed whilst keeping the potential of the mercury at about 2 v. relative to the calomel electrode. 9.5 g. of a very pale yellow solution containing 15.8% of adiponitrile and 0.1% of propionitrile are collected. Neither bis-(,S-cyanoethyl) ether nor fl-hydroxypropionitrile are detected by gas-liquid chromatography. The electrical yield is thus 82%.
  • EXAMPLE 3 A closed electrolysis cell under reflux is provided with a mercury cathode, a platinum anode and a commercial cation exchange membrane based on sulphonated polyethylene for separating the compartments. The process is carried out at ambient temperature.
  • EXAMPLE 4 A closed electrolysis cell under reflux having a single compartment is provided with an anode consisting of a lead wire of diameter 5 mm. and length 3 cm. The
  • cathode is a similar wire of length 5 cm., which has been surface-amalgamated by immersing it in mercury for 1 minute, followed by careful wiping. The process is carried out at ambient temperature.
  • the electrolytic bath consists of 6 g. of an aqueous solution of a tetra-(n-butyl)ammonium carbonate-bicarbonate buffer (prepared as described in Example 1) to which 6 g. of acrlyonitrile and 5 g. of Water were added.
  • the electrolysis is stopped after 2,147 coulombs have been passed through the cell at 5 volts.
  • a closed cell with a condenser is made up from a battery of 12 identical lead sheets each 13.25 cm. in area, arranged vertically with a distance between the plates of 2 mm. They are connected to two conductors so that each anode is interposed between two cathodes and each cathode between two anodes.
  • the electrolyte is circulated by means of a pump and passes between the plates, and then into a cooling and degassing chamber kept at a temperature of 20 C.
  • the electrolytic solution introduced into the cell has the following composition:
  • Tetra-(n-butyl) ammonium carbonate-bicarbonate butfer solution (of identical composition to that described in Example 1) 120 Acrylonitrile 120 Water 60 100,000 coulombs are then passed through the cell. The potential applied between the two electrodes is between 4 and 6 v. during the electrolysis.
  • 'EXAMPLE 6 10.25 g. of acrylonitrile and g. of an aqeuous solution of a tetra(n-butyl) ammonium monobasic phosphatedibasic phosphate buffer obtained by neutralising a 40% by weight aqueous solution of tetra-(n-butyl) ammonium hydroxide to pH 8.3 with concentrated phosphoric acid are introduced into the cathode campartment of the separate compartment cell described in Example 3.
  • a tetra(n-butyl) ammonium monobasic phosphatedibasic phosphate buffer obtained by neutralising a 40% by weight aqueous solution of tetra-(n-butyl) ammonium hydroxide to pH 8.3 with concentrated phosphoric acid
  • the solution contains 1.57 g. of adiponitrile representing an electrical yield of 97.5%.
  • EXAMPLE '8 The same arrangement as in Example 2 is used but the nickel anode is replaced by a lead sheet.
  • the electrolytic bath consists of a mixture of 21.8 g". of acrylonitrile and 10 g. of a solution containing 450 g./l. of a mixture of tetra-(n-propyl) ammonium carbonate and bicarbonate.
  • the mixture of these salts is in such a ratio that the pH of their aqueous solution is 9.
  • the potential at the terminals of the cell is 5 v.; after 12,200 coulombs have been passed, the cell is emptied and rinsed with methanol.
  • the combined solution so obtained weighs 40 g.
  • Example 9 The procedure of Example 8 is followed, the electrolytic bath consisting of a mixture of 17.3 g. of acrylonitrile, 10.5 :g. of water and 11.4 g. of an aqueous solution containing 589 g./litre of a mixture of tetra-(n-hexyl) ammonium carbonate and bicarbonate. The mixture of these salts is in a ratio such that the pH of their aqueous solution is 9.4. The potential at the terminals of the cell is 8 v.; after 14,500 coulombs have been passed, the cell is emptied and rinsed with methanol. The combined solution so obtained weighs 44 g.
  • Example 10 The procedure of Example '8 is followed.
  • the electrolytic bath? consists of a mixture of 7.7 g. of acrylonitrile, 2.25 g. of water and 5 g. of a solution containing 680 g./litre of a mixture of tri(n-butyl)n-propyl ammonium carbonate and bicarbonate, the mixture of these salts being in a ratio such that the pH of their aqueous solution is 9.
  • the potential at the terminals of the cell is 7 v.; after 6,900 coulombs have been passed, the cell is emptied and rinsed with methanol. Analysis shows that the combined solution contains 3.04 g. of adiponitrile which has thus been obtained in an electrical yield of 78.7%.
  • propionitrile, fi-hydroxypropionitrile nor bis-(B-cyanoethyl) ether is detected by gas-liquid chromatography.
  • R R and IR which may be the same or difi'erent, each represents a hydrogen atom or a hydrocarbon radical and Z represents a ketone, ester, nitrile, amide or aldehyde group, by the electrolysis, between a cathode at which the said monomer is reduced at a potential lower than that required to reduce water and an anode having an oxygen over-potential less than that of gold, of a mixtureof (a) the said monomer, and (b) water, the ratio of monomer/Water being from 15/85 to 75/25 by weight, the improvement which comprises including in the said mixture, as buffer, 10 to 30%, based on the total weight of the mixture, of (c) a quaternary ammonium salt of an oxygen-containing inorganic acid having a pK in water of from 5 to 11, such as to provide such a pH of the said mixture of from 6 to 10, and effecting the electrolysis in a single compartment cell.
  • oxygen-containing inorganic acid is carbonic, boric or orthophosphoric acid.
  • cathode is of a lead/mercury alloy, Daroet alloy, graphite, or mercury.

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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)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US649846A 1966-06-30 1967-06-29 Electrolytic hydrodimerisation Expired - Lifetime US3556961A (en)

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FR67733A FR1491516A (fr) 1966-06-30 1966-06-30 Procédé d'hydrodimérisation électrolytique

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BE (1) BE700699A (pt)
CH (1) CH469644A (pt)
DE (1) DE1618838B2 (pt)
ES (1) ES342495A1 (pt)
FR (1) FR1491516A (pt)
GB (1) GB1156955A (pt)
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NL (1) NL6709073A (pt)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674661A (en) * 1971-03-01 1972-07-04 Phillips Petroleum Co Electrochemical production of nickel (i) complexes
US3945896A (en) * 1974-08-28 1976-03-23 Monsanto Company Electrolytic carboxylation of acetonitrile and alpha-substituted acetonitriles
US4941954A (en) * 1989-05-08 1990-07-17 E. I. Du Pont De Nemours And Company Electrochemical preparation of branched unsaturated dinitriles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674661A (en) * 1971-03-01 1972-07-04 Phillips Petroleum Co Electrochemical production of nickel (i) complexes
US3945896A (en) * 1974-08-28 1976-03-23 Monsanto Company Electrolytic carboxylation of acetonitrile and alpha-substituted acetonitriles
US4941954A (en) * 1989-05-08 1990-07-17 E. I. Du Pont De Nemours And Company Electrochemical preparation of branched unsaturated dinitriles

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DE1618838B2 (de) 1973-05-10
LU53981A1 (pt) 1968-03-11
DE1618838C3 (pt) 1973-12-06
GB1156955A (en) 1969-07-02
CH469644A (fr) 1969-03-15
BE700699A (pt) 1967-12-29
NL6709073A (pt) 1968-01-02
FR1491516A (fr) 1967-08-11
DE1618838A1 (de) 1972-04-13
ES342495A1 (es) 1968-07-16

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