US3305585A - Process for producing unsymmetrical dialkylhydrazines by catalytic hydrogenation of dialkylnitrosamines - Google Patents

Process for producing unsymmetrical dialkylhydrazines by catalytic hydrogenation of dialkylnitrosamines Download PDF

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Publication number
US3305585A
US3305585A US323558A US32355863A US3305585A US 3305585 A US3305585 A US 3305585A US 323558 A US323558 A US 323558A US 32355863 A US32355863 A US 32355863A US 3305585 A US3305585 A US 3305585A
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catalyst
weight
reaction medium
alloys
alloy
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Expired - Lifetime
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US323558A
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English (en)
Inventor
Besson Paul
Nallet Albert
Luiset Gilbert
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Societe dElectro Chimie dElectro Metallurgie et des Acieries Electriques Dugine SA SECEMAU
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Individual
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Priority claimed from FR915651A external-priority patent/FR1364573A/fr
Priority claimed from FR916495A external-priority patent/FR83406E/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C241/02—Preparation of hydrazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/10—Hydrazines
    • C07C243/12—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms
    • C07C243/14—Hydrazines having nitrogen atoms of hydrazine groups bound to acyclic carbon atoms of a saturated carbon skeleton

Definitions

  • This invention relates to catalytic hydrogenation of dialkylnitrosamines to produce unsymmetrical dialkylhydrazines and more particularly to hydrogenation of dialkylnitrosamines in the liquid phase and in the presence of Raney nickel which has been obtained from alloys of Ni-Al subjected to treatment by a caustic solution.
  • One of the known methods for preparation of unsymmetrical dialkylhydrazines comprises carrying out the hydrogenation of the corresponding dialkylnitrosamines according to the reaction:
  • R and R represent hydrocarbonaceous radicals.
  • the starting reaction medium comprises either pure dialkylnitrosamine or an aqueous solution of dialkylnitrosamine having a weight content which varies over a large range and is usually between 20 and 40%.
  • the reaction medium is made ionic by addition thereto of a hydroxide of an alkaline metal and of an alkaline earth metal and of a soluble salt of an alkaline metal, of an alkaline earth metal and of a heavy metal.
  • the foregoing compounds are added to the reaction medium in amounts such that the medium contains between substantially about 0.001 to 5 moles per dm. of same, and preferably substantially about 0.1 mole per dm. after dissolving.
  • the reaction medium becomes alkaline by addition of the hydroxide of an alkaline metal such as potassium, sodium or lithium hydroxide and of an alkaline earth metal.
  • an alkaline metal such as potassium, sodium or lithium hydroxide
  • the Raney nickel is obtained by caustic attack of an Ni-Al alloy passing through a No. 26 AFNOR sieve. It is subjected to a first attack with a solution of caustic soda (250 g. per liter) in such quantity that the weight of pure caustic soda dissolved is substantially equal to the weight of the Ni-Al alloy. During this attack, the temperature was maintained at substantially about C.
  • the catalyst After decanting, the catalyst is subjected to a second caustic soda attack under identical conditions. Upon completion of this second attack, the caustic soda solution is eliminated and the catalyst is swilled abundantly.
  • the Raney nickel so obtained is finally subjected to an electrochemical dehydrogenation, according to the French Patent No. 1,303,070, of July 25, 1961, and to the application for a first addition certificate of July 4, 1962: Process for Activating a Catalyst, wherein the catalyst is disposed close to a corrosion resistant anode in an alkaline electrolyte following which an electric current inferior to 500 milliamperes/cm. is passed thereth-rough.
  • the dehydrogenation treatment may also be carried out according to the French Patent No. 1,301,338 of July 4, 1961,
  • Ni 47.5 C 0.5 Fe 3 A1 49 This alloy which is passed through a No. 26 AFNOR sieve is subjected to a first attack with a caustic soda solution of 250 g./ 1., in such quantity that the weight of dissolved sodium hydroxide is substantially equal to the weight of alloy employed. During this attack, the temperature is held at substantially about 100 C.
  • the catalyst After decanting, the catalyst is subjected to a second caustic soda solution attack under identical conditions. Upon completion of the attack, the caustic soda solution is eliminated and the catalyst is swilled at least ten times. Then this catalyst is ready for use without further treatment.
  • the Raney nickel so obtained is not employed at once, or if after having been employed a while its use is temporarily stopped for any reason whatsoever, it is dipped into an aqueous solution of an alkaline metal hydroxide, whose alkaline hydroxide content is between 50 and 500 g./l., and preferably in the vicinity of 250 g./l.
  • the catalyst is used in such proportions that the ratio by weight catalyst reaction medium is between 0.001 and 0.50, and preferably between 0.05 and 0.10.
  • the ratio by weight of catalyst dialkylinitrosamine is between 0.001 and 1.0, and preferably between 0.15 and 0.5.
  • the hydrogen pressure is between 5 atmospheres and below 50 atmospheres and usually amounts to 30 atmospheres.
  • the hydrogenation is carried out at a temperature between 20 C. and +50 C., and advantageously at about C.
  • the autoclave was equipped with a stirring system having a to-and-fro motion perpendicularly to its axis and obtained 2 20 stirrings a minute.
  • the temperature was raised to +10 C. and the pressure to 40 atmospheres by hydrogen injection. This operation was carried out at a temperature equal to +10 C. and the pressure varied between 30 and 40 atmospheres.
  • Dimethylnitrosamine 538 Water 1762 Sodium hydroxide l l Raney catalyst (identical to the one of Example 1)
  • the temperature was raised to +20 C. and the pres sure to 40 atmospheres by hydrogen injection. This operation was carried out at a temperature equal to +20 C. and the pressure varied between 30 and 40 atmospheres.
  • the catalyst kept its entire catalytic activity and it was possible to carry out other tests, the results of which were identical.
  • Raney catalyst prepared according to the second form of proceeding described above and used without any electrochemical treatment 200
  • the autoclave was equipped with a stirring system having a to-and-fro motion perpendicularly to its axis and obtained 220 stirrings per minute.
  • the temperature was raised to C. and the pressure to 40 atmospheres by hydrogen injection. This operation was carried out at a temperature equal to +10 C. and the hydrogen pressure varied between 30 and 40 atmospheres.
  • Dimethylnitrosamine 538 Water 1762 Sodium hydroxide 11 Raney catalyst (prepared according to the second method for preparation of the catalyst described above and used without any electrochemical treatment) 100
  • the temperature was raised to +10 C. and the pressure to 40 atmospheres by hydrogen injection.
  • This operation was carried out at a temperature equal to +10 C. and the hydrogen pressure varied between 30 and 40 atmospheres.
  • the temperature was raised to +20 C. and the pressure to 40 atmospheres by hydrogen injection. This operation was carried out at +20 C. and the pressure varied between 30 and 40 atmospheres.
  • the autoclave was equipped with a stirring system having a to-and-fro motion perpendicularly to its axis and obtained 280 stirrings a minute.
  • the temperature was raised to +10 C. and the pressure to 40 atmospheres by hydrogen injection. This operation was carried out at +10 C. and the pressure varied between 30 and 40 atmospheres.
  • the temperature was raised to +10 C. and the pressure to 40 atmospheres by hydrogen injection. This operation was carried out at +10 C. and the pressure varied between 30 and 40 atmospheres.
  • a pulverulent alloy nickel-aluminum having the following composition:
  • the Raney nickel obtained was used as a catalyst without any subsequent electrolytic dehydrogenation and under identical conditions to the ones set forth in Example 4, except that sodium hydroxide was not added to the reaction medium.
  • the catalyst was used again under the hereinabove conditions, but at a temperature equal to +30 C.
  • a process for production of unsymmetrical dimethylhydrazine comprising hydrogenating dimethylnitrosamine in the liquid phase in the presence of a Raney nickel catalyst whose composition is nickel4055%, aluminum3860%, cobalt-04% and iron-06% by weight, said catalyst being subjected to a first treatment with a solution of caustic soda in an amount such that the weight of caustic soda dissolved is substantially that of the weight of the catalyst; after decanting, said catalyst being subjected to a second treatment identical to said first treatment followed 'by elimination of said caustic soda solution; in carrying out said hydrogenating forming a reaction medium comprising a dimethylnitrosamine and a member selected from the group consisting of a hydroxide of an alkaline metal, of an alkaline earth metal, a salt of an alkaline metal and of an alkaline earth metal, said dimethylnitrosamine being at least 20% by weight of said reaction medium, said member being about 0.001 to 5 moles per dm.
  • said catalyst being present in said reaction medium in-a ratio by weight of catalyst dimethylnitrosamine of about 0.00l-1.0, said hydrogenating being carried out at a pressure between about 5 and less than-50 atmospheres, and at a temperature between substantially 20 C. and +50 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US323558A 1962-11-16 1963-11-14 Process for producing unsymmetrical dialkylhydrazines by catalytic hydrogenation of dialkylnitrosamines Expired - Lifetime US3305585A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR915651A FR1364573A (fr) 1962-11-16 1962-11-16 Procédé de fabrication de dialcoylhydrazines dissymétriques par hydrogénation catalytique des dialcoylnitrosamines
FR916495A FR83406E (fr) 1962-11-24 1962-11-24 Procédé de fabrication de dialcoylhydrazines dissymétriques par hydrogénation catalytique des dialcoylnitrosamines

Publications (1)

Publication Number Publication Date
US3305585A true US3305585A (en) 1967-02-21

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US323558A Expired - Lifetime US3305585A (en) 1962-11-16 1963-11-14 Process for producing unsymmetrical dialkylhydrazines by catalytic hydrogenation of dialkylnitrosamines

Country Status (6)

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US (1) US3305585A (enExample)
CH (1) CH415671A (enExample)
DE (1) DE1251328B (enExample)
GB (1) GB1070907A (enExample)
LU (1) LU44774A1 (enExample)
NL (1) NL300533A (enExample)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172096A (en) * 1977-10-24 1979-10-23 Societe Europeenne De Propulsion Process for the preparation of asymmetric dimethylhydrazine in the presence of hydrazine
US4535154A (en) * 1981-07-13 1985-08-13 United States Of America Reductive destruction of nitrosamines, hydrazines, nitramines, azo- and azoxy-compounds
CN102701391A (zh) * 2012-05-08 2012-10-03 江苏腾龙生物药业有限公司 一种用于降解有机废水的镍铝催化剂的增效且循环使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB881339A (en) * 1959-05-27 1961-11-01 Olin Mathieson Preparation of hydrazines
US3102887A (en) * 1959-04-13 1963-09-03 Du Pont Preparation of unsymmetrically disubstituted hydrazines
US3154538A (en) * 1962-03-09 1964-10-27 Fmc Corp Process for hydrogenating nitrosamines
US3182086A (en) * 1955-07-20 1965-05-04 Hercules Powder Co Ltd Catalytic hydrogenation of nitrosamines to hydrazines

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3182086A (en) * 1955-07-20 1965-05-04 Hercules Powder Co Ltd Catalytic hydrogenation of nitrosamines to hydrazines
US3102887A (en) * 1959-04-13 1963-09-03 Du Pont Preparation of unsymmetrically disubstituted hydrazines
GB881339A (en) * 1959-05-27 1961-11-01 Olin Mathieson Preparation of hydrazines
US3154538A (en) * 1962-03-09 1964-10-27 Fmc Corp Process for hydrogenating nitrosamines

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4172096A (en) * 1977-10-24 1979-10-23 Societe Europeenne De Propulsion Process for the preparation of asymmetric dimethylhydrazine in the presence of hydrazine
US4535154A (en) * 1981-07-13 1985-08-13 United States Of America Reductive destruction of nitrosamines, hydrazines, nitramines, azo- and azoxy-compounds
CN102701391A (zh) * 2012-05-08 2012-10-03 江苏腾龙生物药业有限公司 一种用于降解有机废水的镍铝催化剂的增效且循环使用方法
CN102701391B (zh) * 2012-05-08 2013-12-18 江苏腾龙生物药业有限公司 一种用于降解有机废水的镍铝催化剂的增效且循环使用方法

Also Published As

Publication number Publication date
NL300533A (enExample)
LU44774A1 (enExample) 1964-01-08
GB1070907A (en) 1967-06-07
DE1251328B (de) 1967-10-05
CH415671A (fr) 1966-06-30

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