US3664936A - Electrolytic hydrodimerization of acrylonitrile - Google Patents

Electrolytic hydrodimerization of acrylonitrile Download PDF

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Publication number
US3664936A
US3664936A US35727A US3664936DA US3664936A US 3664936 A US3664936 A US 3664936A US 35727 A US35727 A US 35727A US 3664936D A US3664936D A US 3664936DA US 3664936 A US3664936 A US 3664936A
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United States
Prior art keywords
catholyte
exchange resin
acrylonitrile
cation exchange
adiponitrile
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Expired - Lifetime
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US35727A
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English (en)
Inventor
Maomi Seko
Akira Yomiyama
Yasunobu Takahashi
Shigetoshi Seta
Koji Nakagawa
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Chemical Industry Co Ltd
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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

  • This invention relates to a method of electrolytically dimerizing acrylonitrile which comprises conducting the electrolysis while purifying the catholyte by recovering the conductive supporting salt in the waste catholyte by means of a cation exchange resin and reusing the same. More particularly, it relates to a process for conducting the electrolysis while successively purifying the catholyte by recovering the conductive supporting salt which is taken out of the system in association with the deposits due to the successive removal from the system of the deposits formed during prolonged electrolysis of acrylonitrile and accumulated in the catholyte.
  • Other objects and efiects will be understood by the descriptions hereinbelow.
  • conductive supporting salt means an electrolyte that will not discharge at the cathode when acrylonitrile is hydrodimerized at the cathode.
  • Deposits accumulated in the catholyte means by-products formed during prolonged electrolysis of acrylonitrile or those generated by further deterioration of the same.
  • amides and carboxylates formed by hydrolysis of acrylonitrile and adiponitrile for example, amides such as acrylamide, w-cyanovaleramide and adipamide and carboxylates such as acrylic acid, w-carboxyvaleramide and adipic acid; and other by-products including lactones such as methylbutyrolactone, ethylbutyrolactone, or dimethylbutyrolactone, oxycarboxylates formed by hydrolysis of these lactones, and amides and carboxylates liberated from additives which, when used, will form or liberate the amides and carboxylates during electrolysis by deterioration, and also including polymers of acrylonitrile and deteriorated products thereof.
  • amides and carboxylates formed by hydrolysis of acrylonitrile and adiponitrile
  • these means can hardly permit maintenance of the yield of adiponitrile in terms of the consumed acrylonitrile over 90 percent during a long period of the electrolysis over 400 hours.
  • the electrolysis over 400 hours is conducted with a catholyte freshly prepared prior to the electrolysis from entirely freshly prepared acrylonitrile, conductive supporting salt and other additives and the results thereof are described.
  • the catholyte will not be freshly prepared following a batch of a long-term electrolysis but the adhered matter on the surface of the cathode will be removed followed by reassembling of the electrolytic cell and the next batch of electrolysis will be initiated.
  • a portion of the catholyte is continuously or intermittently removed from a catholyte tank during electrolysis of a catholyte containing acrylonitrile and a conductive supporting salt. Said portion is then treated with a cation exchange resin and the cations of the supporting salt are adsorbed thereon. Then, the cation exchange resin on which the cations of the supporting salt are adsorbed is treated with an aqueous solution of an acid having the same anions as that of the supporting salt. Preferably, the passage of the solution of the acid is preceded by washing of the resin with water.
  • the cations recovered from the cation exchange resin and the anions contained in the acid form the supporting salt which is used for the preparation of a fresh catholyte.
  • acrylonitrile or adiponitrile or the two Prior to the cation exchange resin treatment of the catholyte, if desired, acrylonitrile or adiponitrile or the two may be removed by such means as extraction, decantation or evaporation and recovered in a separate step. Recovery of acrylonitrile and/or adiponitrile may also be effected by applying the aforementioned means to the discharged solution following the resin treatment. It is also possible to recycle the acrylonitrile or adiponitrile thus removed and recovered directly into the mother catholyte.
  • the possibility that the deposits such as the aforementioned carboxylates may be recycled together with acrylonitrile or adiponitrile should be given into consideration.
  • the amount of the catholyte to be treated with a cation exchange resin should be increased or the treatment and circulation made more frequently.
  • the catholyte of an aqueous electrolyte may be employed either a solution or an emulsion containing acrylonitrile and a conductive supporting salt.
  • the method of this invention is effective independent of the type of conducting supporting salt and the concentration of acrylonitrile in the catholyte.
  • the catholyte may contain, in addition to acrylonitrile and a conductive supporting salt, adiponitrile or other by-products formed during the electrolysis and additives necessary for effectively conducting the electrolysis such as an emulsifier or polymerization inhibitor.
  • Either a strongly or a weakly acidic cation exchange resin may be used in the method of this invention and the fom'ler is especially effective in exchange and regeneration.
  • the Na-form Prior to the use of cation exchange resin the Na-form is converted to the H-form by conventional means and it is necessary prior to the practical use to make exchange with acid and washing with water sufficient to leave no Na ion remain.
  • the conductive supporting salts are usually employed alkali metal salts and electrolyte salts represented by the general formula wherein R,, R R and R respectively are alkyl containing 14 carbon atoms, preferably alkyl consisting of 2-3 carbon atoms and X is sulfate radical or arylsulfonate radical of the general formula such as paratoluenesulfonate radical in which R, as usually used, is alkyl containing -4 carbon atoms.
  • Anions forming conductive supporting salts known to be effective in electrolytic hydrodimerization of acrylonitrile other than the above such as halogens, nitrate radical and phosphate radical may be used except for the anions containing carboxylate radical.
  • the tetraalkyl ammonium ion consisting of the Rs mentioned above is recovered from the catholyte and recycled.
  • Recovery of the conductive supporting salt by means of a cation exchange resin can be achieved nearly in 100 percent yield by properly selecting the conditions of recovery.
  • the recovery may be cut in a recovering rate below 100 percent, for example, in a yield of 4080 percent in view of the problem of balancing and supplementing with fresh conductive supporting salt.
  • the electrolytic cell for electrolytic hydrodimerization of acrylonitrile to produce adiponitrile which consists of two chambers, a cathode chamber 1-1 and an anode chamber 1-2 divided by a cation exchange diaphragm l-3. Circulation is made of an anolyte between the anode chamber l-2 and an anolyte tank 2, and of a catholyte between the cathode chamber l-l and a cathode tank 3.
  • the catholyte is a solution or an emulsion or a suspension containing acrylonitrile, adiponitrile and a conductive supporting salt and other additives.
  • the catholyte in the catholyte tank 3 is consecutively in portions passed to an acrylonitrile stripper 4 and the acrylonitrile recovered is recycled to the catholyte tank 3.
  • Water condensed and separated from acrylonitrile is discharged through a discharge end 6.
  • the catholyte from which acrylonitrile and water have been removed in the acrylonitrile stripper 4 is allowed to stand in a decanter 7 for the separation.
  • the oil layer mainly comprising adiponitrile is passed through a discharge end 8 to the step of purifying adiponitrile (not shown).
  • the aqueous layer is recovered into the catholyte tank from the bottom of the decanter 7. Then, a portion of said aqueous layer is continuously or intermittently drawn out and, after cooled in a heat exchanger 9, is stored in a decanter 10.
  • the oil layer separated on cooling the solution is passed to the catholyte tank 3, or a supplement pipe 5, or the discharge end 8.
  • the aqueous layer is passed to a water addition tank 12, in which it is diluted with pure water to an appropriate dilution and then passed to a cation exchange resin column 13.
  • the cation in the solution is adsorbed.
  • the effluent is taken out of the system through a discharge end 14.
  • Pure water is then charged through an inlet 11 into the cation exchange resin column 13 thereby forcing out the catholyte in the column and then thoroughly washing the cation exchange resin inside the column.
  • the waste liquor is discarded through the discharge end 14 outside the system.
  • an aqueous solution of an acid containing the same anion as of the conductive supporting salt, prepared in an aqueous acid solution tank 15, is introduced into the cation exchange resin column 13 to regenerate the cation while forcing out the pure water remaining in the column.
  • the conductive supporting salt thus regenerated is stored in a tank 16 and thereafter continuously introduced into the catholyte tank.
  • the pipe 5, described in more detail, is a supplement pipe for supplementing acrylonitrile being decreased in the system by the transformation into adiponitrile.
  • EXAMPLE l An experimental apparatus similar to that shown by the flowsheet on the drawing was used, which includes an electrolytic cell in which a cathode of lead alloy containing 6% antimony 10 cm. by 10 cm. in conductive area and an anode of lead alloy containing 0.7% silver and 6% antimony with the same conductuve area were divided by a cation exchange diaphragm 1 mm. in thickness, thus forming the cathode and anode chambers each being 10 cm. by 10 cm. by 1 mm. in size. 2N aqueous sulfuric acid was used as the anolyte and flowed at a rate of 200 cm./sec.
  • the catholyte was used an emulsion consisting of an aqueous phase containing 2% acrylonitrile, 9% adiponitrile, 79.95% water, 8.0% tetraethylammonium sulfate and 0.05% emulsifier polyvinyl alcohol and an oil phase containing 17% acrylonitrile, 75% adiponitrile, 5% water and 3% electrolytic organic by-products mainly comprising propionitrile, and having a pH of 7. It was passed and circulated through the electrolytic cell at a flow rate of 200 cm./sec. Electrolysis was conducted at a temperature of the liquor of 50 C. with an electric current of 10 A.
  • the cation exchange resin As the cation exchange resin was employed the sulfonate-type one.
  • the conductive supporting salt was recovered by passing 200 cc. of the aqueous layer from the decanter 7, which amount corresponds to percent of the total amount of the catholyte which was 2,000 cc., per 24 hours to the cation exchange column 13 containing 300 cc. of the cation exchange resin.
  • the exchange capacity of the resin was 0.4 equivalents/l.
  • the sulfuric acid for regeneration fed from the aqueous acid solution tank 15 was 130 cc. of 3N sulfuric acid.
  • 100 cc. of the washing water left, in the cation exchange resin column 13 was forced out with the same volume of aqueous sulfuric acid and was wasted off, while 200 cc. of the solution forced out with cc. of the remaining aqueous sulfuric acid and another water additionally introduced was drawn into the tank 16 and recycled to the catholyte tank 3.
  • the yield of recovery of the conductive supporting salt was approximately 50 percent and the balance due was supplemented by fresh conductive supporting salt.
  • polyvinyl alcohol the emulsifying effect of which is gradually lost during the progress of electrolysis, should be supplementarily and successively added in order to maintain the emulsion.
  • more polyvinyl alcohol should be supplementarily added because the catholyte was successively drawn out of the system.
  • Experiment in this example was made while adding to the tank 3 polyvinyl alcohol at a rate of 3.4 mg./hour.
  • Electrolysis was initiated with an entirely freshly prepared catholyte under the conditions described above and continuously operated for 300 hours. The surface of the electrode was then cleaned and thereafter continuous operation was conducted with the same catholyte for additional 300 hours. Totally five runs of the electrolysis was made over 1,500 hours with the results shown in Table 1 below. A certain amount of polymers was adhered on the surface of electrode after each run, but the amount was far smaller than that in the case where the method according to this invention was not applied to indicate very satisfactory results.
  • EXAMPLE 2 An electrolysis was carried out under entirely the same conditions as in Example 1 except that on the flowsheet the outlet pipe A of the catholyte tank 3 was connected directly with the pipe B of the heat exchanger thereby the catholyte being Only a little polymer was adhered on the surface of the electrode on completion of every run in a similar manner to in Example 1.
  • EXAMPLE 3 An electrolysis was carried out under the same conditions as in Example 1 except that a weakly acidic cation exchange resin of carboxylate type was used in place of the strongly acidic cation exchange resin of sulfonate type. The results were similar to those in Examples 1 and 2, as shown in Table 4. Only a little polymer was adhered on the surface of the electrode on completion of every run in a similar manner to in Examples l and 2.
  • EXAMPLE 4 An electrolysis was made using the same electrolytic cell as in Example 1 where a homogeneous solution containing 35% tetraethylammonium paratoluenesulfonate, 12% acrylonitrile and 10% adiponitrile, and having a pH of 7, was employed as the catholyte and an electric current of 40 A was applied at 50 C. During progress of the electrolysis was drawn out portionwise the solution in the catholyte tank, to which was added acrylonitrile and water. There were separated two layers, adiponitrile being thereby separated, and the aqueous phase was treated with a cation exchange resin in the same way as in Example 1.
  • the tetraethylammonium ion then adsorbed was regenerated with two equivalents of a 2N aqueous solution of paratoluenesulfonic acid, followed by concentration and recycling into the catholyte for reuse.
  • EXAMPLE 5 An electrolysis was carried out using the same electrolytic cell under the same conditions as in Example 4 except that the aqueous phase from the separation of adiponitrile after the addition of acrylonitrile and water was passed prior to the treatment with a cation exchange resin to the acrylonitrile stripper to remove the acrylonitrile. The results are shown in Table 7. Adhesion of the polymer on the surface of the electrode was similar to that in Example 4.
  • EXAMPLE 6 An electrolysis was carried out using the same electrolytic cell as in Example 1 where an emulsion having a pH of 7 and consisting of an aqueous phase containing 20% sodium hydrophosphate, 1% tetraethylammonium hydrophosphate, 1% acrylonitrile, 2% adiponitrile, 17% polyvinyl alcohol and the balance of water and an oil phase containing 17% acrylonitrile, 75% adiponitrile, 5% water and 3% by-products of the electrolysis such as propionitrile'was employed as the catholyte, which was passed and circulated through the electrolytic cell at a flow rate of 200 cm./sec. at a liquid temperature of 40 C. under application of an electric current of 10 A. Ion exchange was conducted in the same way as in Example 1 using a cation exchange resin of sulfonate type.
  • said conductive supporting salt is a quarternary ammonium salt.
  • catholyte is an emulsion containing an aqueous phase as continuous phase.
  • catholyte is a homogeneous aqueous solution.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US35727A 1969-05-08 1970-05-08 Electrolytic hydrodimerization of acrylonitrile Expired - Lifetime US3664936A (en)

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DE (1) DE2022654C3 (enrdf_load_stackoverflow)
FR (1) FR2047505A5 (enrdf_load_stackoverflow)
GB (1) GB1311354A (enrdf_load_stackoverflow)
NL (1) NL7006700A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4318783A (en) * 1978-11-30 1982-03-09 Bayer Aktiengesellschaft Process for the preparation of optionally substituted benzaldehyde dialkyl acetals

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH638548A5 (de) * 1978-07-21 1983-09-30 Ciba Geigy Ag Kationische oxazinfarbstoffe.

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3335162A (en) * 1965-05-10 1967-08-08 Monsanto Co Polymeric impurity removal from an aqueous quaternary ammonium salt solution
US3402112A (en) * 1965-07-26 1968-09-17 Monsanto Co Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell
US3484348A (en) * 1964-04-27 1969-12-16 Monsanto Co Quaternary ammonium salt recovery
US3493597A (en) * 1967-05-25 1970-02-03 Monsanto Co Purification of aqueous quaternary ammonium salt solutions
US3497429A (en) * 1965-12-03 1970-02-24 Asahi Chemical Ind Electrolytic method of manufacturing hydrodimer of acrylonitrile
US3595764A (en) * 1966-06-14 1971-07-27 Asahi Chemical Ind Adiponitrile production by the electrolytic hydrodimerization of acrylonitrile

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484348A (en) * 1964-04-27 1969-12-16 Monsanto Co Quaternary ammonium salt recovery
US3335162A (en) * 1965-05-10 1967-08-08 Monsanto Co Polymeric impurity removal from an aqueous quaternary ammonium salt solution
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
US3595764A (en) * 1966-06-14 1971-07-27 Asahi Chemical Ind Adiponitrile production by the electrolytic hydrodimerization of acrylonitrile
US3493597A (en) * 1967-05-25 1970-02-03 Monsanto Co Purification of aqueous quaternary ammonium salt solutions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4318783A (en) * 1978-11-30 1982-03-09 Bayer Aktiengesellschaft Process for the preparation of optionally substituted benzaldehyde dialkyl acetals

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GB1311354A (en) 1973-03-28
FR2047505A5 (enrdf_load_stackoverflow) 1971-03-12
DE2022654C3 (de) 1975-03-06
NL7006700A (enrdf_load_stackoverflow) 1970-11-10
DE2022654B2 (enrdf_load_stackoverflow) 1974-07-18
DE2022654A1 (de) 1970-11-19

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