US3402112A - Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell - Google Patents

Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell Download PDF

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Publication number
US3402112A
US3402112A US474934A US47493465A US3402112A US 3402112 A US3402112 A US 3402112A US 474934 A US474934 A US 474934A US 47493465 A US47493465 A US 47493465A US 3402112 A US3402112 A US 3402112A
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US
United States
Prior art keywords
anolyte
anode
acrylonitrile
molecular weight
amine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US474934A
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English (en)
Inventor
David W Brubaker
Donald E Danly
Jr Jim N Maloney
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
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Monsanto Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Monsanto Co filed Critical Monsanto Co
Priority to US474934A priority Critical patent/US3402112A/en
Priority to GB31072/66A priority patent/GB1150303A/en
Priority to LU51543D priority patent/LU51543A1/xx
Priority to IL26151A priority patent/IL26151A/en
Priority to NL6610248A priority patent/NL6610248A/xx
Priority to FR70473A priority patent/FR1487571A/fr
Priority to AT707466A priority patent/AT264493B/de
Priority to CH1078366A priority patent/CH456565A/fr
Priority to DE19661593054 priority patent/DE1593054A1/de
Priority to BE684628D priority patent/BE684628A/xx
Application granted granted Critical
Publication of US3402112A publication Critical patent/US3402112A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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 invention relates to a method for reducing anode corrosion in an electrolytic cell employed to electrohydrodimerize acrylonitrile to adiponitrile.
  • an electrolytic cell employed to electrohydrodimerize acrylonitrile to adiponitrile.
  • a process has been developed whereby acrylonitrile can be electrohydrodimerizedto adiponitrile in a dually-compartmented cell.
  • the compartments are a cathode and an anode compartment and are separated by a cation permselective membrane.
  • An anolyte composed of an aqueous solution of sulfuric acid is continuously circulated through the anode compartment.
  • Sufficient electrical potential is established between the anode and cathode to produce unidirectional electrical current. Under the influence of such current acrylonitrile is electro'hydrodimerized at the cathode to produce adiponitrile which is then recovered.
  • the anode of the cell generally employed to accomplish acrylonitrile electrohydrodimerization is made from lead, lead'rsilver alloy, lead-antimony alloy, platinum, stainless steel, and other like materials.
  • the most commonly employed anode material is a lead-silver alloy.
  • certain deleterious ions invade the anode compartment. Among these are included nitrate, perchlorate, and chlorate ions.
  • nitric acid is an oxidizing agent. These acids were found to be extremely corrosive of the anodes used in the electrolytic cell.
  • the most concentrated deleterious ion is nitrate which forms nitric acid and is itself formed by the oxidation of acrylonitrile which has invaded the anode compartment and been oxidized at the anode.
  • the above general object is accomplished by intimately contacting the sulfuric acid anolyte with a water insoluble organic solution of a high molecular weight amine. Thereafter, the water insoluble organic solution of a high molecular weight amine is separated from the anolyte.
  • the amines here employed must be highly selective for nitric, perchlorate, and chlorate ions, must be substantially water insoluble, be low in cost, be highly miscible with low cost solvents, be capable of regeneration with common reagents, and be free from emulsion forming tendencies.
  • These criteria are met by primary, secondary, and tertiary amines having a molecular weight from about 250 to about 500.
  • these amines are unifunctional, i.e., they contain only one ionizable group per molecule. Such amines can be used singly or as a mixture. Mixtures of amines are much more easily obtainable on a commercial basis.
  • Amberlite LA-l is a mixture of N dodecenyl-N-trialkylmethylamines having a molecular weight from about 351-393, a neutral equivalency of 380410, a freezing point below C., a pour point below 20 C. and a steady state solubility in IN sulfuric acid in parts per million of 15 and an acid binding capacity of 2.5-2.7 milliequivalents per gram.
  • Amberlite LA2 is a mixture of N-lauryl-N-trialkylamine having a molecular weight from about 35 3-395, a neutral equivalency of 350-380, a freezing point below 10 C., an acid binding capacity of 2.6-2.8 milliequivalents per gram, and a steady state solubility in IN H 50 in parts per million of 0.
  • high molecular weight primary amines examples include 1-(3-ethylpentyl)-4-ethyloctylamine, l heptyloctylamine, and l-nndecyllaurylamine.
  • Other secondary amines of high molecular weight besides those described before include bis-(1-isobutyl-3,5-dimethylhexyl) amine, di-n-decylamine, dilaurylamine, N-(l-undecyllauryl) laurylamine, N-benzyl-(l-nonyldecyl) amine, and N benzyl-l-undecyllaurylamine.
  • a few of the many tertiary amines are trilaurylamine, tri-n-octylamine, didodenyl-n-butylamine, butylidaurylamine, and tribenzylamine.
  • the amnies here employed can be in the free base form, or in the salt form. It is possible to use the salt form and exchange an anion for the deleterious anions. However, by far the most practical procedure is to use the amines in the free base form to thereby neutralize and remove the deleterious acids found in the anolyte.
  • the organic solvents employed herein to produce organic solutions of amines must meet two general requirements. First, the solvent must be substantially water insoluble and second the amine employed must be highly soluble in the solvent.
  • the generally useful organic solvents are included petroleum distillates, aromatic and aliphatic hydrocarbons, and high molecular weight alcohols. Specifically useful materials include benzene, xylene, and kerosene. It must be clearly understood, however, that there is a broad range of water insoluble materials whose usefulness should be apparent to one skilled in the art to which the present invention pertains.
  • the organic solvent plus amine soluble therein, which in contact with water forms an organic phase, must be only slightly soluble if not completely insoluble in acidic aqueous solutions, especially aqueous sulfuric acid solution.
  • An aqueous to organic phase ratio greater than about :1 is undesirable and should be avoided.
  • the instant process can be practiced on a batch basis or it can be practiced in a continuous fashion.
  • the main requirement is that whatever method be employed the aqueous and organic phases be thoroughly and intimately contacted.
  • Various methods of contacting include counter flow in packed columns, contact in a vessel mechanically agitated, or in centrifugal contact apparatus. Many contact methods should be apparent to those skilled in the art.
  • the high molecular weight amines here employed have become loaded with deleterious ions they can then be recharged by contact with a number of alkaline materials including anhydrous ammonia, aqueous ammonia, sodium hydroxide solution, and other materials. If, in the poorer procedure, an anion exchange procedure is used then the proper recharging anion must be provided. Once the material 'has been recharged it is generally preferred that the organic solution containing amine be water-washed prior to its reuse for deleterious ion removal.
  • Example Two volumes of a N organic solution of high molecular weight amine having the trademark Amberlite LA-2 (described hereinbefore) dissolved in xylene were contacted in a separatory funnel with 5 volumes of anolyte containing 500 milliequivalents per liter (2.5%) of sulfuric acid and 9.3 milliequivalents per liter of nitrate ion along with a small quantity of non-deleterious ions. After separating and analyzing the aqueous phase it was found that the nitrate level in the anolyte had been reduced to 2.9 millicquivalents per liter by this single stage extraction procedure. A loss of only 8% sulfuric acid was sustained.
  • test anode-panels of lead containing 1% silver were conatcted with the treated anolyte in a beaker test at a current density of 0.15 ampere per square centimeter of effective anode surface.
  • the corrosion rate was found to be 0.2 inch per year as compared with a corrosion rate of 2.5 inches per year when untreated anolyte containing deleterious ions was employed.
  • the contaminated organic solution of amine was regenerated with 0.27 volume of 0.46 N aqueous ammonia. Stoichiometrically this was of the amount required. Thereafter the regenerated amine solution was water washed three times using 0.1 volume of water per wash, thereby reducing the ammonium ion content to about 0.5 milliequivalent per liter.
  • Organic amine solution recovery for reuse was about 99%.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US474934A 1965-07-26 1965-07-26 Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell Expired - Lifetime US3402112A (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US474934A US3402112A (en) 1965-07-26 1965-07-26 Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell
GB31072/66A GB1150303A (en) 1965-07-26 1966-07-11 A Process for Reducing Anode Corrosion in an Acrylonitrile Hydrodimerization Cell.
LU51543D LU51543A1 (is") 1965-07-26 1966-07-12
IL26151A IL26151A (en) 1965-07-26 1966-07-14 A process for reducing the anode's digestion in a cell for the hydrodimerization of acrylonitrile
NL6610248A NL6610248A (is") 1965-07-26 1966-07-20
FR70473A FR1487571A (fr) 1965-07-26 1966-07-22 Procédé de réduction de la corrosion de l'anode dans les cellules d'hydrodimérisation de l'acrylonitrile
AT707466A AT264493B (de) 1965-07-26 1966-07-25 Verfahren zur elektrolytischen Hydrodimerisierung von Acrylnitril zu Adipinnitril
CH1078366A CH456565A (fr) 1965-07-26 1966-07-25 Procédé d'électrohydrodimérisation de l'acrylonitrile en adiponitrile
DE19661593054 DE1593054A1 (de) 1965-07-26 1966-07-26 Verfahren zur Herabsetzung der Anodenkorrosion in einer Elektrolysezelle
BE684628D BE684628A (is") 1965-07-26 1966-07-26

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US474934A US3402112A (en) 1965-07-26 1965-07-26 Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell

Publications (1)

Publication Number Publication Date
US3402112A true US3402112A (en) 1968-09-17

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US474934A Expired - Lifetime US3402112A (en) 1965-07-26 1965-07-26 Process for reducing anode corrosion in an acrylonitrile hydrodimerization cell

Country Status (10)

Country Link
US (1) US3402112A (is")
AT (1) AT264493B (is")
BE (1) BE684628A (is")
CH (1) CH456565A (is")
DE (1) DE1593054A1 (is")
FR (1) FR1487571A (is")
GB (1) GB1150303A (is")
IL (1) IL26151A (is")
LU (1) LU51543A1 (is")
NL (1) NL6610248A (is")

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505186A (en) * 1966-05-03 1970-04-07 Crylor Process for obtaining polymers based on acrylonitrile
US3619388A (en) * 1969-02-05 1971-11-09 Asahi Chemical Ind Process for electrolyzing nitriles
US3664936A (en) * 1969-05-08 1972-05-23 Asahi Chemical Ind Electrolytic hydrodimerization of acrylonitrile
US3897318A (en) * 1973-08-06 1975-07-29 Monsanto Co Single-compartment electrolytic hydrodimerization process
CN105543888A (zh) * 2015-12-29 2016-05-04 重庆紫光国际化工有限责任公司 丙烯腈电解制备己二腈的电解液及方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1149325A (en) * 1978-02-10 1983-07-05 John M. Mellor Liquid-phase electrochemical reaction with particulate trapping agent present

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1065112A (en) * 1912-04-06 1913-06-17 Thomas James Clarke Label-holder.
US2460259A (en) * 1946-01-22 1949-01-25 W H And L D Betz Method of protecting systems for transporting media corrosive to metal
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process
US3335162A (en) * 1965-05-10 1967-08-08 Monsanto Co Polymeric impurity removal from an aqueous quaternary ammonium salt solution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1065112A (en) * 1912-04-06 1913-06-17 Thomas James Clarke Label-holder.
US2460259A (en) * 1946-01-22 1949-01-25 W H And L D Betz Method of protecting systems for transporting media corrosive to metal
US3193480A (en) * 1963-02-01 1965-07-06 Monsanto Co Adiponitrile process
US3335162A (en) * 1965-05-10 1967-08-08 Monsanto Co Polymeric impurity removal from an aqueous quaternary ammonium salt solution

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505186A (en) * 1966-05-03 1970-04-07 Crylor Process for obtaining polymers based on acrylonitrile
US3619388A (en) * 1969-02-05 1971-11-09 Asahi Chemical Ind Process for electrolyzing nitriles
US3664936A (en) * 1969-05-08 1972-05-23 Asahi Chemical Ind Electrolytic hydrodimerization of acrylonitrile
US3897318A (en) * 1973-08-06 1975-07-29 Monsanto Co Single-compartment electrolytic hydrodimerization process
CN105543888A (zh) * 2015-12-29 2016-05-04 重庆紫光国际化工有限责任公司 丙烯腈电解制备己二腈的电解液及方法

Also Published As

Publication number Publication date
FR1487571A (fr) 1967-07-07
GB1150303A (en) 1969-04-30
DE1593054A1 (de) 1970-07-30
AT264493B (de) 1968-09-10
CH456565A (fr) 1968-07-31
BE684628A (is") 1967-01-26
NL6610248A (is") 1967-01-27
LU51543A1 (is") 1967-01-12
IL26151A (en) 1970-02-19

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