Classifications

• • 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
• • 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
• • 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

• a high-pressure mercury vapour discharge lamp for carrying out photo-chemical reactions comprises an envelope defining an enclosed space, the enclosed space having therein a doping medium comprising at least one halide of a metal of Group 3a (such as yttrium), with which there may be associated a halide of a metal of Group 3b (such as thallium) and/ or a halide of a metal of the lanthanide group (such as holmium), the concentration of the doping medium being from 0.002 to 1 'mg./cc. and preferably from 0.02 to 0.5 mg./cc.
• a doping medium comprising at least one halide of a metal of Group 3a (such as yttrium), with which there may be associated a halide of a metal of Group 3b (such as thallium) and/ or a halide of a metal of the lanthanide group (such as holmium)
• concentration of the doping medium being from 0.002 to 1
• the lamps generally employed for photochemical reactions are mercury vapour discharge lamps.
• the maximum quantum yield of a particular photochemical reaction may be established'as a function of the main 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 advantage 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 always comprise a halide of the Group 3a such as an yttrium halide. They may comprise a mixture of halides of the Groups 3a and 3b such as mixtures of yttrium and indium halides or mixtures of yttrium and thallium halides. Finally, there may be associated with all the previously described doping agents a halide of the lanthanide group such as a holmium halide.
• yttrium halide/ indium halide 1/ 2 holmium halide/ yttrium halide: 1/2
• the concentration of the holmium halide employed is at most equal to that of the halide of the metal of the Groups 3a and 3b employed in a smaller quantity, and notably when it is between 0.01 and 0.15 mg./cc.
• the relative power of the radiation below 4000 A. is 1.2%, while it is 18% in an undoped mercury vapour lamp.
• 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 above-designated groups, which are preferably yttrium, indium, thallium and holmium.
• the introduced halogen must be present therein in a proportion at least equivalent to the number of grammemolecules of the elements of the Groups 3a and 3b 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 150 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.
• Example 2 The procedure of Example 1 is followed with a 25-watt lamp doped with yttrium iodide. It is found that it is necessary to introduce 20.1 g. of nitrosyl chloride in 3 lots in order to decolourise the solution. After irradiation for 7 hours, there are obtained 53.9 g. of oxime, which is a yield of 310.20 g. of oxime/kwh.
• Example 3 The procedure of Example 1 is followed with a lamp doped with a mixture of yttrium and indium iodides.
• Example 4 The procedure of Example 1 is followed with a lamp doped with a mixture of yttrium and thallium iodides.
• Example 6 The procedure of Example 3 is followed, using a lamp comprising holmium iodide in addition to yttrium and indium iodides.
• EXAMPLE 7 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 g. of sulphuric acid.
• the lamp employed is a 75-watt high-pressure mercury vapour lamp vertically mounted 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.
• a gaseous mixture of nitrosyl chloride and hydrogen chloride is then introduced at a rate of 30 litres per hour at the bottom of the liquid, the mole ratio of NOCl/HCI being 1/8.
• the temperature of the reaction mixture is maintained between 15 and 20 C.
• the irradiation is stopped and the sulphuric acid layer is decanted and poured on the crushed ice, and after neutralisation with dilute caustic soda there are obtained 90 g. of cyclodoecanone oxime, i.e. a yield of 200 g. of oxime per kwh.
• EXAMPLE 9 The operation is carried out in the same reactor as in Example 8 with a 75-watt lamp doped with indium and yttrium iodides. 400 g. of 99% sulphuric acid are added and the gaseous nitrosyl chloride/hydrogen chloride mixture is introduced at a rate of 75 litres per hour. After irradiation for 6 hours, 265.5 g. of cyclododecanone oxime are collected, which is a yield of 592.9 g./kwh.
• EXAMPLE 10 The procedure of Example 8 is followed with a 75-watt lamp doped with yttrium, indium and holmium iodides. 450 g. of 99% sulphuric acid are introduced and the rate of flow of the nitrosyl chloride/hydrogen chloride mixture is 90 litres per hour. After irradiation for 6 hours, there are obtained 324 g. of cyclododecanone oxime, which is a yield of 720 g./kwh.
• EXAMPLE 1 1 Into a reactor identical to that described in Example 9 and provided with the same lamp are introduced 3 litres of cyclohexane. 450 g. of sulphuric acid are added and the gaseous nitrosyl chloride/hydrogen chloride mixture is run in at a speed of 90 litres per hour. After irradiation for 6 hours, there are obtained 216 g. of cyclohexanone oxime, which is a yield of 480 g. kWh.
• Table I shows the comparisons of yields obtained with lamps according to the invention and undoped lamps, taking as reference the yield obtained in Example 8 (200 g. of oxime per kwh.).
• a process for carrying out a photochemical reaction especially a process for the production of oximes by exposing a solution of a cycloal'kane mixed with sulphuric acid to the radiation of a high pressure mercury vapor lamp and adding nitrosyl chloride to said solution
• the improvement comprising increasing the yield of the reaction by using a doped high pressure mercury vapor lamp emitting energy having a wavelength lying preponderantly in the range 4000 A. to 6000 A. with at least about 77% of the power of said emitted energy lying in the range 4500 A. to 5500' A.
• said doped lamp including a doping mixture comprising,
• a mixture of at least one Group 3a metal halide, at least one Group 3b metal halide and at least one lanthanide metal halide the total content of said halides being between about 0.002 mg. and about 1.0 mg. per cubic centimeter.
• halide of the metal of Group 3a is in a ratio by weight of 1/ 2 in relation to the concentration of the halide of the metal of Group 3b and the concentration of the halide of the metal of the lanthanide group is in a ratio by weight of 1/2 in relation to the concentration of the halide of the metal of Group 3a.

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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)
• Discharge Lamp (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

Applications Claiming Priority (2)

Publications (1)

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Cited By (2)

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• 1968
  • 1968-12-05 FR FR176718A patent/FR95327E/fr not_active Expired
  • 1968-12-17 DE DE19681815197 patent/DE1815197A1/de active Pending
  • 1968-12-17 LU LU57575D patent/LU57575A1/xx unknown
  • 1968-12-17 CH CH1876368A patent/CH493935A/fr not_active IP Right Cessation
  • 1968-12-17 BE BE725585D patent/BE725585A/xx unknown
  • 1968-12-18 GB GB60117/68A patent/GB1280990A/en not_active Expired
  • 1968-12-18 US US784896A patent/US3681218A/en not_active Expired - Lifetime
  • 1968-12-18 NL NL6818232A patent/NL6818232A/xx unknown

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