US3681217A - Photo-chemical production of oximes - Google Patents

Photo-chemical production of oximes Download PDF

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Publication number
US3681217A
US3681217A US784895A US78489568A US3681217A US 3681217 A US3681217 A US 3681217A US 784895 A US784895 A US 784895A US 78489568 A US78489568 A US 78489568A US 3681217 A US3681217 A US 3681217A
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US
United States
Prior art keywords
halide
lamp
group
lamps
chromium
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
US784895A
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English (en)
Inventor
Georges Lucas
Claude Viallet
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.)
Societe Nationale des Petroles dAquitaine SA
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Societe Nationale des Petroles dAquitaine SA
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Publication of US3681217A publication Critical patent/US3681217A/en
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/12—Selection of substances for gas fillings; Specified operating pressure or temperature
    • H01J61/125—Selection of substances for gas fillings; Specified operating pressure or temperature having an halogenide as principal component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S204/00—Chemistry: electrical and wave energy
    • Y10S204/902—Production of desired compound by wave energy in presence of a chemically designated nonreactant chemical treating agent, excluding water, chloroform, carbon tetrachloride, methylene chloride or benzene
    • Y10S204/903—Inorganic chemical treating agent

Definitions

  • the maximum quantum yield of a particular photochemical reaction may be established as a function of the principal lines of the emission spectrum of a lamp, and the variation of this yield may be established as a function of the concentration and the nature of the reaction medium.
  • the lamps according to the invention have the advan tage of providing a radiation appropriate for the main reactions in an emission range from 3600 to 6000 A. while substantially reducing the radiation which generates secondary reactions.
  • these lamps such as the photochemical preparation of the cycloalkanone oximes and in particular of cyclododecanone oxime, greatly improved yields of the order of 3 to 4 moles kwh. of pure oxime are obtained.
  • the lamps according to the invention are high-pressure mercury vapour discharge lamps optionally containing one or more rare gases, and doped by the introduction into the enclosed space of the lamp of at least one halide of Group 6 of the Periodic System of the Elements, with which there may be associated a halide of Group 3 and/ or a halide of the lanthanide group, the total content of halides being variable from 0.002 mg. to 1 mg./ cc. and preferably from 0.02 to 0.5 mg./cc.
  • the lamps always comprise a halide of Group 6, such as a chromium halide. They may comprise a mixture of chromium and yttrium halides. Finally, there may be associated with all the aforesaid doping systems a halide of the lanthanide group such as a holmium halide.
  • the doping mixture comprises a halide of the metals of Group 6, for example chromium, a halide of the metals of Group 3, for example yttrium, indium and thallium, and a halide of lanthanide, for example holmium
  • the weight ratio of these halides may be of the order of:
  • the doping mixture may consist of:
  • the total concentration of the doping mixture and the relative concentrations of the various doping agents may vary to a large extent in accordance with the geometry of the lamp.
  • the geometry of the lamp is in turn chosen with a view to obtaining the maximum radiation power in the reaction system for producing the maximum yield.
  • These lamps have a radiated-energy yield in relation to the consumed energy which ensures an optimum yield in the photochemical reactions independently of the chemical process employed.
  • the halogen or halogens may be introduced into the lamp in a form in which they are not combined with'the elements belonging to the aforesaid groups, which are preferably chromium, yttrium, thallium, and holmium.
  • the introduced halogen must be present therein in a proportion at least equivalent to the number of gramme-molecules of the elements of Groups 6 and 3 and of the lanthanides contained in the lamp.
  • EXAMPLE 1 Into a reactor consisting of a cylindrical Pyrex glass receptacle having an internal diameter of 110 mm. and a height of 200 mm., as described in French Pat. 1,331,478, and provided with an undoped mercury vapour lamp of 25 w. enclosed in a Pyrex glass tube, through which a current of cooling Water is passed, are introduced 150 g of cyclododecane in solution in 1650 g. of carbon tetrachloride, and then 50 g. of 99% sulphuric acid. The mixture is stirred and the temperature is maintained between 15 and 20 C. There are introduced 4.3 g. of nitrosyl chloride in solution in carbon tetrachloride and the mercury vapour lamp is ignited.
  • the sulphuric acid solutions are combined and poured onto crushed ice.
  • the oxime precipitates and is filtered, washed with water and, after drying, crystallised from cyclohexane. There are thus obtained 35 g. of oxime in 7 hours, which is a yield of 200 g./kwh.
  • Example 2 The procedure of Example 1 is followed with a 25-watt lamp doped with chromium iodide. It is found that it is necessary to introduce 21 g. of nitrosyl chloride in 3 lots in order to decolourise the solution. There are obtained 56.84 g. of cyclododecanone oxime after 7 hours of irradiation, which is a yield of 325 g./kwh.
  • EXAMPLE 4 Into a reactor consisting of a cylindrical Pyrex glass receptacle having a diameter of 130 mm. and a height of 350 mm., and provided with a stirrer, a thermometer and tubes for the introduction and discharge of gas are introduced 600 g: of cyclododecane in solution in 3000 g. of carbon tetrachloride and 400 g. of 99% sulphuric acid.
  • the lamp employed is a 75-watt high-pressure mercury.
  • vapour lamp doped with the mixture of three iodides, i.e. yttrium, chromium and holmium iodide's. It is mounted vertically on the axis of the reactor and in a'Pyrex glass jacket cooled by a current of water. The stirrer is started and the lamp is ignited.
  • iodides i.e. yttrium, chromium and holmium iodide's.
  • the temperature is maintained at 15 C., and after irradiation for 6 hours the sulphuric acid layer is decanted and poured onto crushed ice and, after purification, there are recovered 278.4 g. of cylododecanone oxime, M.P. 132 C. The yield is 611.8 g./kwh.
  • the doping 25,937 medium contains holmium iodide. 3,141,839 6.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US784895A 1967-12-20 1968-12-18 Photo-chemical production of oximes Expired - Lifetime US3681217A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR133142A FR1571329A (enrdf_load_stackoverflow) 1967-12-20 1967-12-20

Publications (1)

Publication Number Publication Date
US3681217A true US3681217A (en) 1972-08-01

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Family Applications (1)

Application Number Title Priority Date Filing Date
US784895A Expired - Lifetime US3681217A (en) 1967-12-20 1968-12-18 Photo-chemical production of oximes

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US (1) US3681217A (enrdf_load_stackoverflow)
BG (1) BG15233A3 (enrdf_load_stackoverflow)
FR (1) FR1571329A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140158522A1 (en) * 2012-06-26 2014-06-12 Toray Industries, Inc. Method of producing cycloalkanone oxime
WO2021165627A1 (fr) 2020-02-20 2021-08-26 Arkema France Lampe pour réacteur photochimique à base de diodes électroluminescentes

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140158522A1 (en) * 2012-06-26 2014-06-12 Toray Industries, Inc. Method of producing cycloalkanone oxime
US9181177B2 (en) * 2012-06-26 2015-11-10 Toray Industries, Inc. Method of producing cycloalkanone oxime
WO2021165627A1 (fr) 2020-02-20 2021-08-26 Arkema France Lampe pour réacteur photochimique à base de diodes électroluminescentes
FR3107612A1 (fr) 2020-02-20 2021-08-27 Arkema France Lampe pour réacteur photochimique à base de diodes électroluminescentes
US11844154B2 (en) 2020-02-20 2023-12-12 Arkema France Lamp for photochemical reactor with light-emitting diodes

Also Published As

Publication number Publication date
BG15233A3 (bg) 1976-11-18
FR1571329A (enrdf_load_stackoverflow) 1969-06-20

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