US2033537A - Process of preparing nitriles - Google Patents

Process of preparing nitriles Download PDF

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Publication number
US2033537A
US2033537A US11348A US1134835A US2033537A US 2033537 A US2033537 A US 2033537A US 11348 A US11348 A US 11348A US 1134835 A US1134835 A US 1134835A US 2033537 A US2033537 A US 2033537A
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Prior art keywords
nitriles
fatty acid
higher fatty
nitrile
molecular weight
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US11348A
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English (en)
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Anderson W Ralston
William O Pool
Harwood James
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Armour and Co
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Armour and Co
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Priority to US11348A priority Critical patent/US2033537A/en
Priority to GB2961/36A priority patent/GB467044A/en
Priority to FR802129D priority patent/FR802129A/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles

Definitions

  • the present invention therefore simplifies methods of making lower molecular weight nitriles from higher fatty acid nitriles in that the process can be broadly divided into two steps, 30 the first of which consists in making the higher fatty acid nitriles by well-known ways, and then the pyrolysis of these nitriles while in fairly pure form. Better yields of desired products can be obtained and the reaction can be controlled nicely. 5
  • the present invention is therefore concerned with processes of cracking higher fatty acid nitriles.
  • any of the higher fatty acid nitriles namely those having at least six carbon atoms, 40 but we generally start with the nitriles of higher fatty acids having from ten to eighteen carbon I atoms.
  • Stearoand palmito nitrile can be easily and inexpensively prepared from the abundant stearic and palmitic acids and these nitriles can 45 be pyrolytically treated to give nitriles of very much lower weight and of much greater utility.
  • These lower nitriles can be'readily hydrolyzed to carboxylic acids, they can be reduced to amines by hydrogenation, and they thus are substances of wide usefulness as starting materials in organic synthesis. In themselves, they are good insecticides and doubtless many other uses will be found for them.
  • our invention consists in vaporizing a higher fatty acid nitrile, passing the vapors, at substantially atmospheric pressure, through a cracking zone, and condensing reaction products. Any unreacted nitrile can be recycled to the reaction or cracking zone and the lower boiling nitriles can be fractionated into nitriles of rather narrow boiling range. Concurrently with the formation of the lower nitriles considerable quantities of hydrocarbons are formed and these, too, can be fractionated into hydrocarbons of narrow boiling range.
  • the nitrile vapors in the reaction zone are brought into contact with a contact material such as pumice, silica gel, or simply battles to obtain better heat transference to and through the reaction zone.
  • the reaction chamber can contain a dehydrating catalyst such as aluminum oxide or others described in the Ralston Patent 1,991,955. These are metal oxide catalysts such as the oxides of thorium, osmium, and iron.
  • a reaction chamber 2 is provided with heating coils 4 and advantageously contains contact material 3 such as pumice, silica gel, bailies, or dehydrating catalysts as described above.
  • An inlet for nitriles is provided at I and products flowing from the reaction chamber issue by way of 5 and flow to receiver 5' advantageously provided with a heating coil I.
  • the receiver has an outlet 8 and a nitrile recycle line 9 for returning any unreacted nitrile to the reaction zone.
  • the receiver is also provided with an outlet l leading to a cooling coil or condenser I l which is in turn connected to a second receiver I! provided with an outlet II and an outlet l5.
  • Outlet I communicates with a water-cooled condenser l6 discharging into a third receiver H by way of line i8. Any non-condensible material collected in H can be drawn oil. through outlet I! and final products collected in I! can be withdrawn therefrom through line 20.
  • the series of receivers 6, I 2 and I1 together with condensers II and Hi constitutes a sort of fractionating device for roughly separating products of the reaction.
  • the catalyst in chamber 2 when a catalyst is used, is generally aluminum oxide but other metallic oxides such as those of thorium, titanium and zirconium can be used. These catalysts are well known dehydrating catalysts and they function very well in our process.
  • the catalyst can be supported on an inert material such as pumice in ways well known, and we do not, therefore, describe any particular way of preparing the catalyst. Since these catalysts are customarily classified as desteam hydrating catalysts, we so define them in the appended claims. We do not, however, need to use a contact material or catalyst. The reaction products are substantially the same both with and without a catalyst but use of the catalyst tends to increase the reaction rate somewhat and thus permits us to operate at somewhat lower temperatures. Although we ordinarily use a catalyst we are not obliged to do so.
  • This material can be prepared from steaiic acid in ways well known and it has a boiling point of about 360 C. at atmospheric pressure.
  • the chamber is best maintained at a temperature of about 550 C.
  • the product recovered in receiver 6 is a light greenish colored liquid of rather pleasing odor and amounts to about 90% of the quantity of stearonitrile fed to the catalyst.
  • the product has a boiling range of from 50 to about 360 C. and analysis shows that it contains various lower molecular weight nitriles both saturated and unsaturated and also quantities of hydrocarbons. By fractional distillation we can separate the mixture into its constituents and we find that it contains valeronitrile, capronitrile, caprylonitrile, caprinitrile, and others.
  • the reaction chamber we fill the reaction chamber with granular aluminum oxide and pass stearonitrile vapors therethrough. If the temperature be kept at 550 C. the rate of flow can be increased to about 150 parts per hour with a shorter time of contact. If the rate of flow be kept at 100 parts per hour as in the preceding example, the temperature can be reduced to about 425475 C.
  • the stearonitrile in receiver 6 is advantageously recycled to the reaction zone by way of line 9.
  • a typical boiling point analysis of the products obtained is as follows: From 1000 parts of steamnitrile fed to the reaction zone, we obtain a total condensate of about 750 parts. The remainder is non-condensible gas leaving the gas outlet l9. Fractionation of the 750 parts gives the following cuts:
  • Fraction 1 is mostly saturated and unsaturated nitriles containing 5 and 6 carbon atoms with low boiling saturated and unsaturated hydrocarbons.
  • Fraction 2 is mostly saturated and unsaturated nitriles containing 6 and 7 carbon atoms with saturated and unsaturated hydrocarbons.
  • Fraction 3 is mostly saturated and unsaturated nitriles containing 7, 8, 9, 10, 11, 12 carbon atoms with high boiling saturated and unsaturated hydrocarbons.
  • the residue is saturated and unsaturated nitriles containing 12, 13, 14, 15, 16, 17 carbon atoms with saturated and unsaturated hydrocarbons and unchanged stearonitrile.
  • a temperature of about 550 C This seems to be the most desirable temperature for heating nitriles having from 14 to 18 carbon atoms, but we can operate at temperatures somewhat lower and somewhat higher. Thus, for instance we can operate at temperatures as high as 900 (3., although considerably lower yields of I that the particular temperature used for a particular nitrile will vary from that used for another nitrile and therefore we do not wish to limit our speciiically in this respect.
  • temperatures we have accordingly defined the temperature as a cracking temperature.
  • higher fatty acid nitrile is intended to cover nitriles having 6 or more carbon atoms.
  • the pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone .maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of 'the said higher fatty acid nitrile are formed.
  • the pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed, and separately condensing unreacted higher fatty acid nitrile and lower molecular weight nitriles.
  • the pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed, separately condensing higher fatty acid nitrile and lower molecular weight nitriles and returning the condensed higher fatty acid nitrile to the cracking zone.
  • the catalytic pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone containing a solid dehydrating catalyst maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed.
  • the catalytic pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone containing a solid dehydrating catalyst maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed and then condensing reaction products.
  • the catalytic pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone containing a solid dehydrating catalyst maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed and separately condensing unreacted higher fatty acid nitrile and lower molecular weight nitriles.
  • the catalytic pyrolysis of higher fatty acid nitriles which comprises introducing into a cracking zone containing a solid dehydrating catalyst maintained at a cracking temperature a vaporized mixture consisting substantially wholly of at least one vaporized higher fatty acid nitrile having at least six carbon atoms whereby nitriles having a molecular weight lower than that of the said higher fatty acid nitrile are formed, separately condensing unreacted higher fatty acid nitrile and lower molecular weight nitriles and returning the condensed higher fatty acid nitrile to the cracking zone.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US11348A 1935-03-15 1935-03-15 Process of preparing nitriles Expired - Lifetime US2033537A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US11348A US2033537A (en) 1935-03-15 1935-03-15 Process of preparing nitriles
GB2961/36A GB467044A (en) 1935-03-15 1936-01-31 Process of preparing nitriles
FR802129D FR802129A (fr) 1935-03-15 1936-02-19 Procédé de préparation de nitriles à poids moléculaire relativement faible à partir des nitriles d'acides gras supérieurs et produits en résultant

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FR (1) FR802129A (fr)
GB (1) GB467044A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2433182A (en) * 1944-05-13 1947-12-23 Phillips Petroleum Co Process for production of unsaturated nitriles
US2448275A (en) * 1945-06-29 1948-08-31 Armour & Co Nitrile-producing method
US2468436A (en) * 1944-10-24 1949-04-26 Emery Industries Inc Method of producing carboxylic aliphatic nitriles
US2496661A (en) * 1947-11-28 1950-02-07 Socony Vacuum Oil Co Inc Production of nitriles

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2433182A (en) * 1944-05-13 1947-12-23 Phillips Petroleum Co Process for production of unsaturated nitriles
US2468436A (en) * 1944-10-24 1949-04-26 Emery Industries Inc Method of producing carboxylic aliphatic nitriles
US2448275A (en) * 1945-06-29 1948-08-31 Armour & Co Nitrile-producing method
US2496661A (en) * 1947-11-28 1950-02-07 Socony Vacuum Oil Co Inc Production of nitriles

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Publication number Publication date
FR802129A (fr) 1936-08-28
GB467044A (en) 1937-06-10

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