US3682793A - Process for hydrodimerizing acrylonitrile - Google Patents

Process for hydrodimerizing acrylonitrile Download PDF

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Publication number
US3682793A
US3682793A US135958A US3682793DA US3682793A US 3682793 A US3682793 A US 3682793A US 135958 A US135958 A US 135958A US 3682793D A US3682793D A US 3682793DA US 3682793 A US3682793 A US 3682793A
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United States
Prior art keywords
acrylonitrile
electrolysis
exchange resin
electrolyte
resin
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Expired - Lifetime
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US135958A
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English (en)
Inventor
Maomi Seko
Akira Yomiyama
Shinsaku Ogawa
Tetsuya Miyake
Toshiro Isoya
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

  • the method according to the present invention can be applied to any of the electrolyte taking place in any known electrolytic processes and solutions obtained in the course of the separation and the recovery of adiponitrile from the electrolyte.
  • Electrode reaction-impairing materials as referred to herein include ammonia, cyanoethylated products thereof such as hydroxy propionitrile and bis-cyanoethyl ether, l-imino-2-cyanocyclopentane, decomposition products of the electrolytic supporting salt such as trialkyl amine, amines formed by reduction of nitriles, organic carboxylic acids formed by hydrolysis of nitriles, polymers of acrylontrile and degenerated products thereof, and polymers of adiponitrile and modified products thereof, which are accumulated in the system, as well as metals dissolved out and accumulated in the electrolyte.
  • the presence of these materials results in reduction in the yield of adiponitrile and formation of agglutinates on the surface of the cathode which further promote reduction in the yield of adiponitrile.
  • the method of the present invention is applied to any electrolytes, i.e., in emulsion, in aqueous layer which was obtained by settling emulsion into oily and aqueous layers, in homogeneous solution, in aqueous layer which was obtained by separating a homogeneous solution into two layers by the addition of water and acrylontrile to a homogeneous solution and solutions which were obtained by removing acrylonitrile from aforementioned liquids.
  • the treatment according to the invention may be carried out after removal not only of acrylonitrile but also of adiponitrile, propionitrile and the like from the electrolyte by such means as solvent extraction.
  • the hydrolysis of the nitrile occurring during the treatment can be effectively prevented by removing acrylonitrile, adiponitrile, propionitrile and the like from the electrolyte prior to the treatment thereof with ion exchange resin.
  • Concentration of the electrode reaction-impairing materials in the electrolyte is indicated by the amount of alkali required for titration of the electrolyte from pH 7 to pH 11.
  • High yield of adiponitrile over a long period of time is continuously achieved by carrying out the electrolysis while maintaining the concentration of the electrode reaction-impairing material below 20 milliequivalents per liter electrolyte, preferably below 15 milliequivalents per liter.
  • the cation exchange resin is an exchange resin widely used for general purposes of adsorption, purification and separation, which has a characteristic of receiving the cation in a liquid phase while releasing another cation by itself.
  • the cation exchange resin is broadly classified into the strongly acidic cation exchange resin and the weakly acidic cation exchange resin.
  • Representative of the former are methacrylate-divinylbenzene resin and phenolcarboxresin having sulfonic group.
  • Representative of the latter are methacrylate-divinylbenzene resin and phenolcarboxylate resin containing carboxylic group and phenolic group as the exchange group.
  • any of these resins can be used in the present invention in which the resin may be either in hydrogen form or in the cation form of the electrolytic supporting salt used, the latter is preferred.
  • Use of a weakly acidic resin can enhance selectivity of the electrode reaction-impairing materials toward the resin thereby to enable the highly eicient adsorption of said material on the resin.
  • Wea'kly acid cation exchange resin having the cation of the supporting salt as exchange group promotes exchange between the electrode reaction-impairing materials and the cation of the supporting salt and adsorption of the former on the resin thereby further improving efiiciency in the adsorption.
  • electrolytic supporting salts are alkali metal salts and electrolyte salts represented by the general formula:
  • R is alkyl containing from to 2 carbon atoms such as p-toluenesulfonate and besides other anions forming an electrolytic supporting salt known to be effective for electrolytic hydrodimerization of acrylonitrile such as halogen ion, nitrate ion and phosphate ion.
  • Carboxy1ate(s) is excluded from the category of anions cited above.
  • these supporting salts are most suitable quaternary ammonium salts, which lead to a high yield of adiponitrile.
  • pH of the electrolyte in electrolytic hydrodimerization of acrylonitrile is between 3 and 10.
  • pH 3 the hydrolysis of nitriles and dissolution of metals will occur
  • pH hydrolysis of nitriles and formation of bis-cyanoethyl ether will be associated.
  • Quantity of the liquid to be placed under purification is desired to be as much as possible so far as it is economically acceptable and in general the treatment is conducted with the amount in the range from 0.1 to ml./a. hr.
  • Amount of the resin to be used is from 0.0002 to 1 ml./ a. hr. in terms of the resin of lH-form.
  • the materials contained in the electrolyte that is passed through a cation exchange resin are selectively adsorbed on said resin, whereas most of the cation of the supporting salt can be recovered as the effluent flowed out. Therefore, separation of the electrode reaction-impairing materials and the cation of the supporting salt can be achieved by conducting the electrolysis while returning treated effliient to the catholyte tank.
  • Eicient separation is achieved by the following treatment:
  • Regeneration of the cation exchange resin which has cation of the electrolytic supporting salt and the electrode reaction-impairing materials as adsorbed on it with an acid is carried out in an ion-exchange chromatographic manner, by which the former cation is eluted earlier and the latter material later thereby both being separated.
  • the separation may also be effected by means of a multi-stage ion exchange using two or more ion exchange columns arranged in a cascade system, each column containing ion exchange resin of cation form of the supporting salt.
  • the catholyte effluent is first passed through the first column containing the ion exchange resin. Then an acid is passed through said column to desorb said materials to give an outiiow enriched with said materials. Then this outflow is passed through the second column, which is subsequently regenerated with an acid giving an outflow more enriched with said materials.
  • the outflow discharged from each column is then passed through next column and grows more and more concentrated with said materials, and less and less concentrated with cations of said supporting salts, linally giving an outflow which has carried off as much said impairing materials as possible.
  • the last one containing a large amount of said inipairing material being discarded.
  • the electrolytic supporting salt may also be recovered by extracting the electrode reaction-impairing materials from said outflow with an organic solvent to eliminate the same out of the system.
  • the salt may also be recovered by dialysis thereby removing the electrode reaction-impairing materials.
  • the electrolyte used for electrolytic hydrodimerizatiou of acrylonitrile may be either in solution or in emulsion containing acrylonitrile and an electrolytic supporting salt and the method of this invention can be applied independently of said supporting salt and concentration of acrylonitrile in the electrolyte.
  • the electrolyte may contain by-products other than acrylonitrile, and/ or an emulsilier, polymerization inhibitor and other additives necessary for effectively conducting the electrolysis.
  • the cathode is preferably employed one with a high hydrogen overvoltage and usually lead, mercury, zinc, carbon or cadmium, or alloys thereof. It is preferable to use as an anode any with a high corrosion resistance such as lead, lead oxide alloy, lead peroxide, platinum, carbon or titanium or alloys thereof.
  • the diaphragm may be of any of those materials as a porcelain plate, a parchment paper, a cation exchange membrane and an amphoteric membrane. It is also possible to conduct the electrolysis in an undivided cell.
  • any anolyte maybe employed, those which do not hamper the corrosion-resistance of anode nor adversely affect the hydrodimerization reaction and are cheap are preferably selected.
  • Particularly preferable is, therefore, sulfuric acid.
  • the electrolytic cell is designed in such a way as being capable of carrying out the electrolysis while stirring or circulating the electrolyte.
  • the electrolysis temperature is preferably below 70 C.
  • the current density is preferably so high that no evolution of hydrogen gas occurs, and generally below 50 a./ 100 cm?. Adjustment of pH changing as the electrolysis progresses to a desired value can be conducted by addition of an appripriate acid which is not conflicting with the supporting sa t.
  • the electrolyzer 1 in which electrolytic hydrodimerization of acrylonitrile is carried out for the production of adiponitrile, consists of two chambers, the cathode chamber 3 and the anode chamber 4 partitioned by a cation exchange diaphragm 2.
  • the anode chamber 4 Through the anode chamber 4 is circulated an anolyte sent from the anolyte tank 5, whereas through the cathode cell 3 is circulated a catholyte passed from the catholyte chamber 6.
  • the catholyte is a solution or an emulsion containing acrylonitrile, adiponitrile, an electrolytic supporting salt and other additives.
  • the catholyte in the catholyte tank 6 is in portions sent to the acrylonitrile stripper 7, where the acrylonitrile is recovered and returned to the catholyte tank 6 and the water condensed and separated from the acrylonitrile is led to the outlet 8.
  • the catholyte in the acrylonitrile stripper 7 from which acrylonitrile and water have been removed is settled for separation in the decanter 9, from which the oily layer mainly composed of adiponitrile is passed through the outlet 10 to the adiponitrile purification step (not shown).
  • the aqueous layer is recovered through the bottom of the decanter 9 into the catholyte tank 6.
  • a portion of said aqueous solution is cooled in the cooler 11 and continuously or intermittently drawn out.
  • the treated solution is stored in the decanter 12.
  • the aqueous layer is passed to the cation exchange resin column 13 in the form of cation of the electrolytic supporting salt.
  • the euent is stored in the tank 14 and continuously or intermittently returned to the catholyte tank 6. pH of the catholyte in the tank 6 is adjusted, as occasion demands, using an acid or an alkali corresponding to the type of hydroxide of the supporting salt.
  • the cation exchange resin which, upon contact with the catholyte, adsorbs the undesirable electrode reactionimpairing materials as mentioned above, is subjected to regeneration, i.e., desorption of the cations with an aqueous sulfuric acid in the tank 16, followed by Iwashing with water introduced from the nozzle 17.
  • An aqueous hydroxide solution of the electrolytic supporting salt introduced from the nozzle 18 is passed to convert the form of the resin to the form of cation of the supporting salt.
  • an aqueous solution of the supporting salt may be employed.
  • Pipe 1S is provided for introducing an aqueous solution of hydroxide of the electrolytic supporting salt or an appropriate acid to adjust pH of the catholyte.
  • EXAMPLE 1 An electrolyzer provided with an anode chamber and a cathode cell both being in a size l cm. in 'width x 10 cm. in length and 1 mm. in thickness and a partitioning cation exchange diaphragm 1 mm. in thickness placed between a cathode of lead alloy containing 6% antimony with an effective area of cathode surface cm. in width x 10 cm. in length and an anode of lead alloy containing 0.3% silver and 6% antimony with the same area was used as an experimental equipment shown in the accompanied drawing flow sheet. Through the anode charnber was circulated 2 N sulfuric acid at a ow rate of 200 cm./ sec.
  • a catholyte which was an emulsion of pH 7 containing in 8:2 volume ratio an aqueous phase consisting of 2% acrylonitrile, 79.75% Water, 10% tetraethyl ammonium sulfate, 0.05% emulsiier and by-products mainly composed of 0.2% 2-cyanoethyladiponitrile and an oily layer consisting of 70% adiponitrile, 20% acrylonitrile, 5% water, 2% trimer and 3% electrolytic by-products mainly composed of propionitrile at the same iiow rate. Electrolysis was conducted at a liquid temperature of 50 C. and an electric current of 20 a.
  • the catholyte was 3000 ml. in total amount and was treated using the equipment as shown in the accompanied drawing flow sheet, wherein electrolytic reaction was carried out while passing the catholyte at a tiow rate of 10 mL/hr. through an ion exchange resin column of 30 cm. in length x 2.5 cm.2 in sectional area iilled with 50 ml. of a cation exchange resin Amberlite IRC-84 of tetraethylammonium form. Alkali titration of the aqueous phase of the electrolyte from pH 7 to pH 11 was constantly held at 4 milliequivalents/l. The results of the electrolysis are shown in Table 1.
  • Example 2 Yield on the basis of acrylonitrile consumed Operation time (hr.) Adipcnitrile Propionitrile Example 2 TABLE 3 Yield on the basis of acrylonitrile consumed Operation time (hr.) Adiponitrlle Propiontrlle Example 3 An electrolysis was made under the same conditions as in Example 1 except that the catholyte tank 6 was connected to the ion exchange column 13 without passing Yield on the basis of acrylonltrile consumed Operation time (hr.) Adiponitrile Propionitrilo Example 4 An electrolysis was made using the same electrolyzer as in Example 1, the catholyte used being a homogeneous solution composed of 35% tetramethylammonium p-toluenesulfonate, acrylonitrile, 15% adiponitrile and 35% water, with an electric current of 20 A.
  • Example 5 50 TABLE 7 Yield on the basis of aorylonitrile consumed Operation W- 65 time (hr.) Adiponitn'le Propionitrile Exam le 6 An electrolysis was made under the same conditions as in Example 1 except that 80 ml. of a strongly acid cation exchange resin of sulfonate type Amberlite 200 in tetraethylammonium form were used in place of the weakly acid cation exchange resin. Alkali titration of the 75 aqueous layer of the electrolyte from pHl 7 to 1l was held at 4 milliequivalents/l.
  • the second fraction after- Wards contained the electrode reaction-impairing materials.
  • the separation of tetraethylammonium and the electrode reaction-impairing materials was feasible by the chromatography.
  • the first fraction in an amount of 15 l. was distillated, concentrated and subjected to electrolysis using an electrolyte of the same composition as in Example 1. pH of the electrolyte was 4. Results are shown in Table 10. Alkali titration of the aqueous phase of the electrolyte at the start of electrolysis from pH 7 to 11 was below 4.0 milliequivalents/l.
  • Electrode reaction-impairing materials 356 meq.
  • the outow was further passed through the third column packed with 0.6 l. of the resin, which was then regenerated in the same way as above to give the following out-flow.
  • Example 8 The same outflow as from the first column in Example 9, 7.5 l., was concentrated by distillation to a concentration of tetraethylammonium sulfate of about 50%.
  • One liter of the resulting liquor was subjected to continuous extraction using 1 l. of 1,2-dichloroethane for 24 hours to extract the electrode reaction-impairing materials into the 1,2-dichloroethane layer.
  • From the purified aqueous solution was removed 1,2-dichloroethane by distillation followed by electrolysis under the same conditions as in Example l. Results are shown in Table 12. Titration of the aqueous phase of the electrolyte at the start of electrolysis from pH 7 to 11 was 4 milliequivalents/l.
  • concentration of said electrode reaction-imparting materials in said electrolyte or in said aqueous phase is below 15 milliequivalents/l. in terms of the amount of alkali required for titration from pH 7 to 11.
  • Col. 3I line 6 "methacrylate-divinylbenzene resin and phenolcarb'ox" should read vpolystyrene-dvnylbenzene resin and phenol.'-

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US135958A 1970-04-25 1971-04-21 Process for hydrodimerizing acrylonitrile Expired - Lifetime US3682793A (en)

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JP45035107A JPS4941175B1 (enrdf_load_stackoverflow) 1970-04-25 1970-04-25

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US (1) US3682793A (enrdf_load_stackoverflow)
JP (1) JPS4941175B1 (enrdf_load_stackoverflow)
BR (1) BR7102483D0 (enrdf_load_stackoverflow)
DE (1) DE2119979C3 (enrdf_load_stackoverflow)
ES (1) ES390572A1 (enrdf_load_stackoverflow)
FR (1) FR2090659A5 (enrdf_load_stackoverflow)
GB (1) GB1316401A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377453A (en) * 1978-02-10 1983-03-22 National Research Development Corporation Electrochemical synthesis and product
US4432856A (en) * 1980-05-13 1984-02-21 The Japan Carlit Co., Ltd. Apparatus for manufacturing chlorine dioxide
US4566957A (en) * 1984-12-10 1986-01-28 United Technologies Corporation Use of gas depolarized anodes for the electrochemical production of adiponitrile
US4596638A (en) * 1985-04-26 1986-06-24 International Fuel Cells Corporation Method for the electrochemical production of adiponitrile using anodes having NiCo2 O4 catalyst
US5232561A (en) * 1989-12-15 1993-08-03 Tanaka Kikinzoku Kogyo K.K. Electrolytic method of preparing compounds with a gas permeable electrode

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377453A (en) * 1978-02-10 1983-03-22 National Research Development Corporation Electrochemical synthesis and product
US4432856A (en) * 1980-05-13 1984-02-21 The Japan Carlit Co., Ltd. Apparatus for manufacturing chlorine dioxide
US4566957A (en) * 1984-12-10 1986-01-28 United Technologies Corporation Use of gas depolarized anodes for the electrochemical production of adiponitrile
US4596638A (en) * 1985-04-26 1986-06-24 International Fuel Cells Corporation Method for the electrochemical production of adiponitrile using anodes having NiCo2 O4 catalyst
US5232561A (en) * 1989-12-15 1993-08-03 Tanaka Kikinzoku Kogyo K.K. Electrolytic method of preparing compounds with a gas permeable electrode

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DE2119979C3 (de) 1975-02-06
DE2119979B2 (de) 1974-06-12
ES390572A1 (es) 1973-06-01
FR2090659A5 (enrdf_load_stackoverflow) 1972-01-14
JPS4941175B1 (enrdf_load_stackoverflow) 1974-11-07
BR7102483D0 (pt) 1973-05-17
DE2119979A1 (enrdf_load_stackoverflow) 1971-11-18
GB1316401A (en) 1973-05-09

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