US3642592A - Production of adiponitrile - Google Patents

Production of adiponitrile Download PDF

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Publication number
US3642592A
US3642592A US807895A US3642592DA US3642592A US 3642592 A US3642592 A US 3642592A US 807895 A US807895 A US 807895A US 3642592D A US3642592D A US 3642592DA US 3642592 A US3642592 A US 3642592A
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Prior art keywords
anode
electrolysis
acrylonitrile
percent
adiponitrile
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US807895A
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English (en)
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Fritz Beck
Harald Guthke
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
    • 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

Definitions

  • ABSTRACT Process for the production of adiponitrile by direct electrochemical hydrodimerization of acrylonitrile using a medium containing acrylonitrile, an electrolyte salt, water and, if desired, a solvent at a temperature of from 10 to 60 C. at a pH of from 1 to 10.
  • electrolysis is carried out in a cell having a liquid cathode which is contacted by a solid anode which is not wetted by the liquid cathode or into which the solid anode is immersed to a depth of up to 20 mm.
  • Adiponitrile is an important intermediate for synthetic fiber manufacture. I
  • An electrolysis mixture which contains 30 to vantageously from 50 to 65 is generally used.
  • Water is used as a proton donor, usually in a concentration of from 3 to 40 percent; larger or smaller water contents, for example down to 1 percent or up to 94 percent, may however be used. It is advantageous to use mixtures which form a homogeneous liquid phase. It is possible to use both solutions of acrylonitrile in water and solutions of water in acrylonitrile. 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 or of water in the mixture. Such solvents may either be inert or may to some extent undergo change during the reaction and may also themselves act as proton donors.
  • solvents lower aliphatic alcohols such as methanol, ethanol and isopropanol; acetonitrile; ethers which are partly or wholly miscible with water such as tetrahydrofuran, dioxane and glycol monomethyl ether; or open or cyclic amides of lower carboxylic acids which may be substituted by alkyl or dialkyl on the nitrogen atom, for example forma'mide, monomethylformamide, dimethylformamide, dimethylacetamide, diethylacetamide and N-methylpyrrolidone.
  • lower aliphatic alcohols such as methanol, ethanol and isopropanol
  • acetonitrile ethers which are partly or wholly miscible with water such as tetrahydrofuran, dioxane and glycol monomethyl ether
  • open or cyclic amides of lower carboxylic acids which may be substituted by alkyl or dialkyl on the nitrogen atom, for example forma'mide,
  • 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 90 percent, adpercent, by weight of acrylonitrile 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 the 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, sulfate, fluorides, tetrafluoroborates, fluorosulfonates toluenesulfonates 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, bis-tetraethylammonium sulfate, bis-tetrabutylammonium sulfate, tetramethylammonium methyl sulfate and tetramethylammonium fluorosulfate.
  • Mixtures of salts may also be used, sometimes with advantage.
  • Mercury is particularly suitable as cathode material because of its highway hydrogen and because it is liquid.
  • Gallium is also suitable at temperatures above 30 C.
  • the anode should not dissolve in the reaction mixture, particularly in the case of anodic polarization, and the anode material should not be'wettable by the liquid cathode.
  • These requirements are generally fulfilled by graphite or oxide anodes. Electrographites of all types are therefore suitable preferably compacted grades which have less of a tendency to disperse in the electrolytes, and also lead dioxide (either as solid shapes or better as a coating on electrode carbon), nickel or. titanium, and also magnetite electrodes which have been prepared by sintering or centrifugal casting methods.
  • Metallic e.g., platinum or gold anodes are suitable provided an anodic covering layer has been produced by appropriate pretreatment, for example by prolonged anodic prepolarization.
  • Alloys of tungsten with from 10 to 20 percent of nickel are also favorable, especially after anodic prepolarization in dilute acids, preferably phosphonic acid.
  • the shape of the anode is preferably cylindrical with rounded edges on the front face to be immersed. Other shapes, for example hemispheres, truncated cones or concave logarithmic or spherical caps may also be used.
  • the anodes may also have a rectangular or square cross section or be segments of a circle.
  • FIG. 1 a prototype of an electrolytic cell for carrying out the process according to this invention is shown diagrammatically.
  • the cell casing 1 (made from polyolefin or from steel coated with polyolefin for example) has the flat and elongated shape conventionally employed in chlorine/caustic cells using the amalgam method. Its width depends on the diameter of the anode 2 and its length on the number of anodes.
  • the anodes 2 have a cylindrical shape; the edges of the lower face are rounded.
  • a bus 3 is connected to a source of electricity.
  • Circular depressions 4 are provided in the bottom of the cell and these have a somewhat larger diameter than the anodes and are partly filled with the liquid cathodes.
  • the cathodes 2 dip into the liquid cathode to a depth of from 0 to 10 mm.
  • the reaction mixture 8 is pumped from below through nozzle 9 so that a thin coherent film of liquid is ensured between the anodes and cathodes.
  • the reaction mixture leaves the cell through an overflow l0 and is returned to the cell by a pump 1] through a heat exchanger 12 and the nozzles 9.
  • Temperature and pH are measured by a thermometer l3 and electrodes 14; the pH is controlled by adding a suitable base through line 15. Offgas formed during the electrolysis escapes through a cooled offgas pipe 17 which passes through a gastight cover 16.
  • the individual cathode/anode units in a cell may be connected in parallel according to FIG. 1. Owing to the low electrolytic conductivity of the electrolysis mixture (which reaches only about 1 percent of the conductivity in chlorinecaustic cells) it is also possible however to connect the pairs of electrodes in a trough in series without corrosion occurring at the electrodes. The provision of vertical partitions between the pairs of electrodes and having a height not extending completely to the surface of the electrolysis mixture is advantageous in this case.
  • anodes prepolarized at a potential of about volts for from 10 to 30 minutes while withdrawn, i.e., at a distance ofa few mm from the liquid cathode, prior to electrolysis. Stabilization of the system during electrolysis is thus achieved.
  • the anode During electrolysis the anode has a depth of immersion of from 0 to mm. in the liquid cathode, i.e., it either rests on it or dips into it a little.
  • the current strength at constant potential increases with increasing depth of immersion, but only at the rate at which the contact area between anode and cathode increases.
  • central nozzle for example in the case of larger anode faces, two rakeshaped nozzles which cross over each other, in the case of pyramidal anode faces, appropriately crossed comb-shaped nozzles, and in the case of rectangular anodes a slot nozzle extending over the whole width at the lower end of the anode.
  • Cylindrical anodes may for example be rotated about their vertical axes.
  • a particularly favorable arrangement is a rotating circular disc or roller having a horizontal axis which may dip in the cathode to a depth of up to half its diameter. The portion which is not immersed is constantly wetted by fresh solution so that it is not necessary in this case to bathe the anodes.
  • electrolysis can be carried out without further measures. Exchange ofsubstance between the zone of contact and the surrounding reaction medium evidently is ensured by capillary forces. It is however advantageous in order to withdraw heat and ensure steady-state operation to pump the electrolyte upwardly through the liquid cathode against the anode. lt has proved to be particularly advantageous to use for this purpose a perforated ring nozzle (see reference 9 in FIGS. 1 and 2) which is located coaxially with the anode beneath the center of the face of the same. The nozzle may for example be secured to the anode so that uniform distribution is achieved; the feed line obviously has to be elastic in this case.
  • the electrolyte may however also be passed through a coaxial bore in the anode to the lower face of the anode.
  • a coaxial bore in the anode By bathing the zone of contact with fresh electrolyte, an improvement in the currentpotential relationship is achieved as may be seen from Table l.
  • the experimental conditions are the same as in Example 1 with the exception of the anode material. The test is carried out with a cylindrical anode having a cross-sectional area of 1 cm.
  • TEAES Z by weight oftctraethylammonium ethyl sulfate.
  • the electrolysis can be carried out with the arrangement according to this invention, even in the case of low concentrations of salt, at moderate potential with current densities of from 20 to amp./dm. i.e., in the range of current densities conventionally used in the electrolysis of alkali metal chlorides.
  • the favorable pH range is from 7 to 10
  • the pH may be lowered down to l.
  • the lower pH value has a very favorable effect on the consumption of quaternary ammonium hydroxide for regulating the pH.
  • the specific consumption of base for maintaining a constant pH of from 7 to 8 is from 0.5 to 1.0 millimole per ampere hour, while at a pH of from 3 to 4 it is only 0.05 to 0.1 millimole per ampere hour.
  • the electrolysis is carried out at a temperature of from l0 to 60 C., preferably from 25 to 40 C.
  • Conversion of the acrylonitrile is from 10 to 70 percent. Electrolysis may be carried out continuously by allowing the reaction mixture to circulate, for example according to FIG. 1 or 2, and after the desired conversion has been achieved keeping it constant by metering in freshreaction mixture while at the same time withdrawing reacted mixture from the cell.
  • AN adiponitrile 5 succionitrile and other byproducts in the high boiling fraction
  • a glass cell 1 contains a cylindrical anode 2 0 1 Plus. of graphite covered with a layer of lead dioxide having a thickness of 50 microns. Current is passed in through a copper lead 3. The diameter of the anode is 44 mm. and it has a front y EXAMPLE 2 face having anarea of 15 cm..
  • Electrolysis is carried out in the apparatusdescribed in Exmersedto a depth of 2 mm. into mercury 5 covering the botample. 1 under the conditions specified therein with the tom 4 of the cell.
  • Electrolyeffected through a platinum pin 6 which is fused into a glass sis is discontinued after a theoretical current conversion of 20 tube and welded to a copper lead 7.
  • the reaction mixture is percent. pumped upwardly through a perforated ring nozzle 9 made of 30 Yields obtained at various pH values, together with the polyethylene and leaves the cell by an overflow 10.
  • the reacmean cell potential and the specific consumption of base are tion medium is recycled through a cooler 12 by a pump 11. compared in Table 4.
  • Tne temperature is measured by means of a thermometer i3 7 m EXAMPLEB v and the pH is measured by means of an electrode 14.
  • the pH Electrol sis is carried out in the a aratus described in Exkeplt 2 -1 g 2M a dmppmg ample l uiider the conditions of Ex iiiple 2 (r-'67amp./dm. unne ending g z z f fi gf t mug a nnevcooler 17 ex pH 4,20 percent conversion) but with the followtngconcenf salt: At the beginning of the electrolysis 1,000 g.
  • the composition of the electrolyte is 54% of acrylonitrile, 28% of isopropanol, 16% of water, 1.5% of TEAES and 0.5% of TEAMS.
  • the specific base consumption is 0.06 millimole per ampere hour.
  • the cell potential is volts.
  • the electrolyte is pumped through a conventional glass nozzle situated 5 mm. beneath the center of the lower face of the anode.

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

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US (2) US3642592A (enExample)
AT (1) AT289750B (enExample)
BE (1) BE729856A (enExample)
CH (1) CH517708A (enExample)
DE (2) DE1693005C3 (enExample)
ES (1) ES364863A1 (enExample)
FR (1) FR2004052A1 (enExample)
GB (1) GB1258619A (enExample)
LU (1) LU58169A1 (enExample)
NL (1) NL6903828A (enExample)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12435033B2 (en) 2020-01-19 2025-10-07 Zhejiang Nhu Company Ltd Method and device for preparing adiponitrile

Families Citing this family (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
DE2502167C2 (de) * 1975-01-21 1982-09-23 Basf Ag, 6700 Ludwigshafen Elektrochemische Zelle mit bipolaren Elektroden
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
US4472252A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactants
US4636286A (en) * 1983-03-25 1987-01-13 Ppg Industries, Inc. Electro organic method
US4472251A (en) * 1983-03-25 1984-09-18 Ppg Industries, Inc. Electrolytic synthesis of organic compounds from gaseous reactant
US4462876A (en) * 1983-03-25 1984-07-31 Ppg Industries, Inc. Electro organic method and apparatus for carrying out same
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1146481B (de) * 1961-07-17 1963-04-04 Uhde Gmbh Friedrich Verfahren zur Elektrolyse von Alkalichlorid-loesungen nach dem Amalgamverfahren unter Verwendung von Graphitanoden
FR1404896A (fr) * 1964-08-12 1965-07-02 Procédé d'électrolyse des solutions et des sels fondus d'électrolytes
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
US3193479A (en) * 1962-08-13 1965-07-06 Monsanto Co Electrolytic coupling of an olefinic compound with a ketone
US3193477A (en) * 1962-04-20 1965-07-06 Monsanto Co Electrolytic hydrodimerization process and extraction procedure

Patent Citations (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
US3193477A (en) * 1962-04-20 1965-07-06 Monsanto Co Electrolytic hydrodimerization process and extraction procedure
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 (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12435033B2 (en) 2020-01-19 2025-10-07 Zhejiang Nhu Company Ltd Method and device for preparing adiponitrile

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ES364863A1 (es) 1971-01-01
US3616320A (en) 1971-10-26
GB1258619A (enExample) 1971-12-30
LU58169A1 (enExample) 1969-07-09
CH517708A (de) 1972-01-15
DE1804809A1 (de) 1970-06-04
DE1693005C3 (de) 1974-12-19
DE1693005B2 (enExample) 1974-05-02
BE729856A (enExample) 1969-09-15
DE1693005A1 (de) 1971-09-02
NL6903828A (enExample) 1969-09-18
FR2004052A1 (enExample) 1969-11-21
AT289750B (de) 1971-05-10

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