US3616320A - Production of adiponitrile - Google Patents

Production of adiponitrile Download PDF

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Publication number
US3616320A
US3616320A US807896A US3616320DA US3616320A US 3616320 A US3616320 A US 3616320A US 807896 A US807896 A US 807896A US 3616320D A US3616320D A US 3616320DA US 3616320 A US3616320 A US 3616320A
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percent
acrylonitrile
electrodes
adiponitrile
electrolysis
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US807896A
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Fritz Beck
Hans Leitner
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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

  • the present invention relates to a process for the production of adiponitrile by electrochemical hydrodimerization of acrylonitrile.
  • reaction mixtures which contain high concentrations of salts such as sodium perchlorate or potassium thiocyanate and high concentrations of aprotic solvents such as dimethylformamide or dimethylsulfoxide. Our own experiments have shown that these solvents are however appreciably degraded anodically at the high concentrations used.
  • lt is an object of the present invention to provide a process for the electrochemical hydrodimerization of acrylonitrile which gives adiponitrile in very high yields and excellent purity. Another object of the invention is to provide a process offering high space-time yields even at low current densities.
  • adiponitrile by direct electrochemical hydrodimerization ofacrylonitrile in a medium which contains acrylonitrile, an electrolyte salt, water and, if desired, a solvent at a temperature of from to 60 C. and a pH value of from l to 10 using liquid-impermeable electrodes which comprises moving the medium through one or more pairs of electrodes which are 0.05 to 2 mm. apart and may be separated by liquid-permeable insulators.
  • the low current densities which may be used in the new process result in very favorably cell potentials even at low concentrations of electrolyte salt, for example at concentrations of about 1 percent by weight.
  • An electrolysis mixture is generally used which contains from ID to 90 percent by weight, advantageously from l5 to 65 percent by weight, of acrylonitrile.
  • a mixture having a content of from 20 to 35 percent by weight of acrylonitrile may be used with particular advantage.
  • Water is used as a proton donor, usually in a concentration of from 3 to 40 percent by weight; higher or lower water contents may however be used, for example down to 1 percent or up to 94 percent by weight. It is advantageous to use mixtures which from a homogeneous liquid phase. Both acrylonitrile solutions in water and solutions of water in acrylonitrile may be used. Although the reaction may be carried out without a solvent or diluent, it may be advantageous to use polar solvents in order to set up specific concentrations of acrylonitrile and water in the mixture. Such solvents may either be inert may to some extent undergo change during the reaction and they may also themselves act as proton donors.
  • solvents lower aliphatic alcohols such as methanol, ethanol, butanol and preferably isopropanol; acetonitrile; ethers which are wholly or partly miscible with water such as tetrahydrofuran, dioxane and glycol monomethyl ether; or open or cyclic amides or lower carboxylic acids which may be substituted by alkyl or dialkyl on the nitrogen atom, for example formamide, monomethylforrnamide, dimethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, or also the end product adiponitrile.
  • solvents or diluents When solvents or diluents are used they are generally used in concentration of from 5 to 40 percent by weight.
  • a substance which is more easily oxidized anodically than the electrolyte salt, acrylonitrile or adiponitrile is advantageous to add to the electrolysis mixture a small amount of a substance which is more easily oxidized anodically than the electrolyte salt, acrylonitrile or adiponitrile.
  • Anodic oxidation of the starting material or reaction product which occurs as a secondary reaction and results in loss of yield is suppressed by such an addition.
  • suitable substances are lower alcohols, particularly methanol, and lower aldehydes.
  • the substance which is more easily oxidized is advantageously added to the reaction mixture in an amount of from 5 to 30 percent by weight. If the whole of the oxygen normally formed in the reaction was to be used up for oxidation of methanol, about g. of methanol per kg. of adiponitrile would be required.
  • quaternary ammonium salts of certain acids preferably in concentrations of less than 5 percent by weight, as electrolyte salts.
  • the salt may however be used in higher concentrations, for example up to 20 percent by weight.
  • the cations of the salts have a very negative discharge potential.
  • Those anions are particularly suitable which are only difficulty oxidizable or not at all, for example monoalkyl sulfates, sulfates, fluorides, tetrafluoroborates, fluorosulfonates, toluene sulfonates and benzene sulfonates.
  • tetramethylammonium and tetraethylammonium salts particularly of ethyl sulfate and p-toluene sulfonate.
  • Other salts which have proved to be suitable are for example triethylmethylammonium methyl sulfate, bistetraethylammonium sulfate, bis-tetrabutylammonium sulfate, tetramethylammonium methyl sulfate and tetramethylammonium fluorosulfate. Mixtures of salts may also be used, sometimes with advantage.
  • anodes Materials which do not pass into solution anodically under electrolysis conditions, for example platinum in the form of platinized titanium or in the form of platinum foil which has been struck by means of a conducting adhesive to graphite are suitable as anodes.
  • a completely smooth and level anode surface can be prepared on lead dioxide by polishing with carborundum powder.
  • Other suitable anodes consist of magnetite, graphite or gold.
  • the cathode surface generally consists of lead, amalgamated lead, copper, electrolytically amalgamated copper, silver, amalgamated silver and preferably of graphite or plastics-bonded graphite.
  • the process according to the invention may be carried out advantageously when the anodes consist of lead dioxide and the cathodes of graphite.
  • the electrode arrangement to be used according to the invention is surprisingly insensitive to short circuits, in that the potential does not collapse upon slight contact of the electrodes.
  • each electrode pair to be used the electrodes are 0.05 to 2 mm. apart, preferably from 0.1 to 0.5 mm. Such a small gap may be provided most simply by using plate electrodes having the smoothest possible surface. Electrodes having other shapes may however be used, for example pairs of concentric cylindrical electrodes. It is not expedient to use gaps smaller than 0.05 mm. because the risk of contact is appreciable with smaller gaps and the residence time of the electrolytes in the capillary gap is too long.
  • the reaction mixture is advantageously moved through in the form of a capillary flow between the anode and cathode. It is also possible however to pass the reaction mixture at such a rate between the electrodes that conveyance takes place in the form of a turbulent flow.
  • the yield of adiponitrile is generally more or less independent of the pH at values between 1 and 10.
  • the addition of acids or bases during electrolysis for controlling the pH is therefore usually unnecessary.
  • carbon dioxide or boron trifluoride is added during electrolysis to the reaction mixture, a certain increase in yield is however obtained.
  • These gaseous substances are advantageously added in an amount of from 0.5 to 10 ml. per minute per ampere.
  • Temperatures generally of from 10 to 60 preferably from 20 to 50 C., particularly from 25 to 40 C., are used for the electrolysis.
  • Conversion of the acrylonitrile used is from l to 80 percent.
  • Electrolysis can be carried out batchwise or continuously. The continuous method may be carried out by allowing the reaction mixture to circulate and after attainment of the desired conversion keeping this constant by metering in fresh reaction mixture with simultaneous withdrawal of reacted mixture from the cell.
  • FIGS. 1 and 1a of the drawings An apparatus for carrying out the process according to the invention is shown diagrammatically in FIGS. 1 and 1a of the drawings.
  • a plurality of flat plate bipolar electrodes 1 are connected in series.
  • the plates having a thickness of for example from to 20 mm. may be consist for example of graphite, and the anode side can be coated with lead dioxide.
  • the cathode side may be coated with lead or with copper in pure or amalgamated form.
  • the electrodes have a slightly trapezoidal shape so that they have liquidtight contact with the sidewalls of the tank 2.
  • the current leads 3 are connected to the end plates.
  • small strips 4 of insulating material for example plastic film, such as polyester film, may be arranged between the plates parallel to the flow.
  • the thickness of the strips depends on the desired gap and may be from 0.05 to 2 mm.
  • An offgas pipe 6 passes through cover 5 of the cell.
  • the reaction mixture supplied through feed line 7 is moved through the pairs of electrodes, leaves the cell through a discharge l5 and is circulated by means of a centrifugal pump 8, passing through a heat exchanger 9 and a flowmeter 10.
  • the cell is also fitted with an inlet 11 for fresh reaction solution and an outlet 12 for partly reacted mixture.
  • the pH is measured at 13 and the temperature at M.
  • the process makes possible the use of low concentrations of salt. Particularly at low concentrations of salt the discharge is very easy to process.
  • PN propionitrile
  • AN adiponitrile
  • CEE biscyanodiethyl ether
  • HPN fi-hydroxypropionitrile
  • SN succinonitrile
  • BP other byproducts
  • R residue
  • TEAES tetraethylammoniurn ethyl sulfate.
  • EXAMPLE 1 Electrolysis is carried out in an apparatus as shown diagrammatically in FIGS. 2 and 2a.
  • the cell is built up from circular graphite discs 1 having a diameter of [17 mm. and a thickness of 10 mm. which have a central bore having a diameter of 30 mm.
  • the area of the electrode is exactly 1 square decimeter.
  • the arrangement is located in a glass cell 2.
  • the tenninals are connected by leads 3 with a source of direct current.
  • An offgas pipe 6 passes through the cover 5.
  • the reaction solution is pumped through a feed line 7 by means of a circulating pump 8 into the cavity of the electrode system, flows through the capillary gaps and returns over a cooler 9 and a flow meter 10.
  • each graphite disc is covered with a layer of lead dioxide having a thickness of 190 microns which has been applied by electrolytic deposition from nitric acid lead nitrate solution at 65 C. and a current density of 2 aJdm. Both sides of each graphite disc are ground completely flat with line carborundum powder.
  • Electrolysis of the recirculating reaction mixture is carried out at 10 amperes, i.e. l0 ajdm
  • the temperature is kept at 30 C. by water cooling.
  • a potential of 23.4 volts is set up at the six pairs of bipolar electrodes, equivalent to an average individual potential of 3.9 volts.
  • After 1 hour and 23 minutes, i.e. 83.4 ampere hours, and a theoretical conversion of acrylonitrile of 30 percent the electrolysis is discontinued.
  • the reaction mixture is clear and colored quite pale yellow. The pH value if 3.5 during electrolysis.
  • the product worked up by distillation of the low-boiling components in a film evaporator followed by distillation of the high-boiling components at subatmospheric pressure. Analysis for sulfur and nitrogen are carried out in the residue and the content of oligomeric acrylonitrile is calculated therefrom; the PN is determined by gas chromatography in the low-boiling fraction and the AN, CEE, HPN, SN and BP in the high-boiling fraction.
  • EXAMPLE 3 The reaction is carried out in a cell as described in example I under the conditions therein specified but at different current densities.
  • the concentration of salt is 0.75 percent by weight.
  • the results obtained are collected in table 3 wherej is measured in amperes per square decimeter.
  • EXAMPLE 5 The reaction is carried out in the cell described in example 1 under the conditions specified therein but using other cathodes.
  • the metals used are applied direct to the graphite by electrolytic deposition in a layer thickness of 100 microns. Amalgamation takes place in the case of lead by treatment with a nitric acid solution of mercury(ll) nitrate and in the case of copper by electrolytic deposition from a sulfuric acid solution of mercury(ll) sulfate.
  • the concentration of salt is 0.75 percent by weight and the current density is 7 amperes per square decimeter.
  • the results are collected in table 5. ln the table:
  • EXAMPLE 6 The reaction is carried out in the cell described in example 1 under the conditions specified therein. but during electrolysis carbon dioxide is passed at a rate of 20 ml. per minute or boron trifluoride at a rate of 5 ml. per minute is passed into the reaction mixture at the lower end of the cooler in FIG. 2.
  • the concentration of salt is 0.75 percent by weight.
  • the yield of AN can thus be raised to 86.8 percent and 87.5 percent, respectively, at current efficiencies of 80 percent and 82 percent.

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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)
US807896A 1968-03-16 1969-03-17 Production of adiponitrile Expired - Lifetime US3616320A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1693005A DE1693005C3 (de) 1968-03-16 1968-03-16 Verfahren zur Herstellung von Adipinsäuredinitril
DE19681804809 DE1804809A1 (de) 1968-03-16 1968-10-24 Verfahren zur Herstellung von Adipinsaeuredinitril

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US3616320A true US3616320A (en) 1971-10-26

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US807896A Expired - Lifetime US3616320A (en) 1968-03-16 1969-03-17 Production of adiponitrile
US807895A Expired - Lifetime US3642592A (en) 1968-03-16 1969-03-17 Production of adiponitrile

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US (2) US3616320A (enrdf_load_stackoverflow)
AT (1) AT289750B (enrdf_load_stackoverflow)
BE (1) BE729856A (enrdf_load_stackoverflow)
CH (1) CH517708A (enrdf_load_stackoverflow)
DE (2) DE1693005C3 (enrdf_load_stackoverflow)
ES (1) ES364863A1 (enrdf_load_stackoverflow)
FR (1) FR2004052A1 (enrdf_load_stackoverflow)
GB (1) GB1258619A (enrdf_load_stackoverflow)
LU (1) LU58169A1 (enrdf_load_stackoverflow)
NL (1) NL6903828A (enrdf_load_stackoverflow)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755100A (en) * 1972-06-09 1973-08-28 Nalco Chemical Co Method for producing acrylamide from acrylonitrile
FR2298615A1 (fr) * 1975-01-21 1976-08-20 Basf Ag Cellule electrochimique a electrodes bipolaires
US4087336A (en) * 1976-12-27 1978-05-02 Monsanto Company Electrolytic reductive coupling of hydroxybenzaldehydes
US4155818A (en) * 1978-07-17 1979-05-22 Monsanto Company Semi-continuous electro-hydrodimerization of acrylonitrile to adiponitrile with replating of cathode
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
US4636286A (en) * 1983-03-25 1987-01-13 Ppg Industries, Inc. Electro organic method
CN113774413A (zh) * 2021-09-30 2021-12-10 大连理工大学 一种在单相溶液中安全高效电解丙烯腈制备己二腈的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
DE1146481B (de) * 1961-07-17 1963-04-04 Uhde Gmbh Friedrich Verfahren zur Elektrolyse von Alkalichlorid-loesungen nach dem Amalgamverfahren unter Verwendung von Graphitanoden
BE631302A (enrdf_load_stackoverflow) * 1962-04-20
US3193479A (en) * 1962-08-13 1965-07-06 Monsanto Co Electrolytic coupling of an olefinic compound with a ketone
FR1404896A (fr) * 1964-08-12 1965-07-02 Procédé d'électrolyse des solutions et des sels fondus d'électrolytes

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755100A (en) * 1972-06-09 1973-08-28 Nalco Chemical Co Method for producing acrylamide from acrylonitrile
FR2298615A1 (fr) * 1975-01-21 1976-08-20 Basf Ag Cellule electrochimique a electrodes bipolaires
US4087336A (en) * 1976-12-27 1978-05-02 Monsanto Company Electrolytic reductive coupling of hydroxybenzaldehydes
US4155818A (en) * 1978-07-17 1979-05-22 Monsanto Company Semi-continuous electro-hydrodimerization of acrylonitrile to adiponitrile with replating of cathode
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
US4636286A (en) * 1983-03-25 1987-01-13 Ppg Industries, Inc. Electro organic method
CN113774413A (zh) * 2021-09-30 2021-12-10 大连理工大学 一种在单相溶液中安全高效电解丙烯腈制备己二腈的方法

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Publication number Publication date
FR2004052A1 (enrdf_load_stackoverflow) 1969-11-21
DE1693005B2 (enrdf_load_stackoverflow) 1974-05-02
US3642592A (en) 1972-02-15
BE729856A (enrdf_load_stackoverflow) 1969-09-15
GB1258619A (enrdf_load_stackoverflow) 1971-12-30
ES364863A1 (es) 1971-01-01
DE1693005C3 (de) 1974-12-19
CH517708A (de) 1972-01-15
NL6903828A (enrdf_load_stackoverflow) 1969-09-18
AT289750B (de) 1971-05-10
LU58169A1 (enrdf_load_stackoverflow) 1969-07-09
DE1693005A1 (de) 1971-09-02
DE1804809A1 (de) 1970-06-04

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