US3131135A - Electrolysis of alkyl grignardcontaining electrolytes - Google Patents

Electrolysis of alkyl grignardcontaining electrolytes Download PDF

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Publication number
US3131135A
US3131135A US84209A US8420961A US3131135A US 3131135 A US3131135 A US 3131135A US 84209 A US84209 A US 84209A US 8420961 A US8420961 A US 8420961A US 3131135 A US3131135 A US 3131135A
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electrolyte
alkyl
electrolysis
alkyl halide
grignard
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US84209A
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English (en)
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John M Coopersmith
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Standard Oil Co
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Standard Oil Co
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Priority to NL273589D priority Critical patent/NL273589A/xx
Application filed by Standard Oil Co filed Critical Standard Oil Co
Priority to US84209A priority patent/US3131135A/en
Priority to DEST18771A priority patent/DE1153753B/de
Priority to FR885378A priority patent/FR1311057A/fr
Priority to GB2232/62A priority patent/GB998024A/en
Application granted granted Critical
Publication of US3131135A publication Critical patent/US3131135A/en
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    • 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
    • C25B15/00—Operating or servicing cells
    • 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
    • C25B3/01—Products
    • C25B3/13—Organo-metallic compounds

Definitions

  • This invention relates to electrolytic cells used in chemical conversion processes, and more particularly concerns a novel cooling system for such cells when employed in the electrolysis of alkyl Grignard-containing electrolytes.
  • organometallic compounds of such metals as zinc, aluminum, magnesium, cadmium, tin, lead, and others may be prepared by electrolyzing a Grignard reagent with an anode composed of the metal which is to form the organometallic compound.
  • Such processes by reason of their versatility, simplicity, and economy, are now becoming of increasing value. Nevertheless, certain construction and operating problems remain, and it is an object of the present invention to provide a unique solution to what has heretofore been the most troublesome of these.
  • a primary ob iect of the present invention to provide a cooling system for such cells wherein any leakage between coolant and electrolyte will be substantially completely innocuous, and which, at all events, will not be hazardous to surrounding personnel.
  • an electrolytic cell employing an alkyl Grignard electrolyte and a consumable metal anode is cooled by indirect heat exchange with a coolant stream composed of the alkyl halide which corresponds to the alkyl Grignard electrolyte. That is, for example, if ethyl magnesium chloride is electrolyzed with a lead anode to produce tetraethyl lead, the electrolyte is cooled with circulating ethyl chloride. Thus, should there by any leakage, the coolant and electrolyte will be non-reactive.
  • the alkyl halide is maintained in the liquid phase, and is itself cooled by external heat exchange with an extraneous coolant such as water, which is not, however, permitted to come in the vicinity of the electrolyte.
  • an extraneous coolant such as water
  • liquid alkyl halide is supplied to cooling coils disposed within the electrolyte, and is permitted to vaporize under controlled pressure.
  • heat produced during electrolysis is absorbed as latent heat of evaporation.
  • the resultant alkyl halide vapors are then recompressed, cooled and condensed, and the resultant liquid is then available for return to the coils.
  • this embodiment is, in effect, a vapor compression type refrigeration system, and offers the advantages of large heat capacity for a relatively small coil size.
  • FIGURE 1 schematically depicts an electrolytic cell cooled by recirculating liquid alkyl halide
  • FIGURE 2 schematically shows an elevation of a cell cooled by the vapor compression refrigeration system utilizing alkyl halide as refrigerant.
  • alkyl groups of from 1 to, say, 8 or more carbon atoms in an alkyl Grignard reagent e.g. methyl magnesium chloride or ethyl magnesium chloride
  • an alkyl Grignard reagent e.g. methyl magnesium chloride or ethyl magnesium chloride
  • the consumable anode metal for example lead
  • the corresponding metal alkyl e.g. tetramethyl or tetraethyl lead.
  • the alkyl Grignard electrolyte comprises the alkyl Grignard reagent together with an appropriate solvent.
  • Known Grignard solvents require the presence of an ether or tertiary amine, such as diethyl ether, dimethyl ether of ethylene glycol, dibutyl ether of diethylene glycol, hexylethyl ether of diethylene glycol, triethylamine, etc.
  • An additional ether, for example tetrahydrofuran is often found to be of advantage for increasing electrolyte conductivity, as is the presence of a normally liquid aromatic hydrocarbon such as benzene, toluene, xylenes, etc.
  • the electrolyte may contain excess alkyl halide to react with magnesium metal plating out at the anode and thereby reconvert it to additional Grignard reagent.
  • a typical alkyl Grignard electrolye prior to electrolysis may have an alkyl Grignard reagent concentration of about 1.5-3.5 Normal, an ether concentration of about 3080 weight percent, about 1040% tetrahydrofuran, about 20-50 weight percent benzene, and about 1-10 weight percent excess alkyl halide.
  • Conditions within a typical electrolytic cell depend largely upon cell design and considerations of thermodynamics and economics; consequently, they will vary widely depending upon the particular system.
  • a temperature within the range of about 20 C. to about (1., preferably about 2050 C. and optimally about 25-35 C. is desired, while a current density at both anode and cathode within the range of about 0.2 to about 100 amperes per square foot of electrode area is disadvantageous.
  • Relatively low voltages of the order of about 20-30 volts, are usually preferred, although cell voltages of 50 volts and even higher may be utilized.
  • Cell pressures may range from subatmospheric to low superatmospheric, say 60 p.s.i.g., and the electrolysis may be conducted batchwise, continuously, or semi-batchwise with intermittent or continuous addition of reactants. It is particularly noted that the inventive cooling system is suitable for any and all of the foregoing variations, which illustrates its exceptional versatility.
  • FIGURE 1 an embodiment of the invention is depicted in simplified cross-sectional elevation.
  • the cell proper comprises an outer jacket 11 containing electrolyte 12, which is admitted via conduit 13 and withdrawn via conduit 14.
  • Anode 16, of lead or other consumable metal is connected in circuit with cathode 17, of steel or other conductive material, and with a direct current power source 18.
  • cathode 17 of steel or other conductive material
  • direct current power source 18 a direct current power source.
  • numerous arrangements of electrodes may be employed, including, without limitations, a plurality of flat plates, foraminous baskets containing lead shot, etc.
  • a coil or tube 19 is disposed in electrolyte 12 in indirect heat exchange contact; that is, coolant within coil 19 can conduct heat from electrolyte 12 and thereby reduce or maintain the temperature during electrolysis.
  • Coil 19 may be finned, wound into a plurality of return bends, connected with similar coils or tubes in parallel or series-parallel arrangements, or otherwise constructed to afford a relatively high surface area.
  • Coolant in coil 19 is passed via line 21 and pump 22 through heat exchanger 23, where the alkyl halide coolant is itself cooled by indirect heat exchange with an external coolant, as for example water, and then passes via line 24 to coil 19.
  • an external coolant as for example water
  • a suflicient pressure is maintained on the alkyl halide coolant in coil 19 to maintain substantially all of the alkyl halide in the liquid phase.
  • any leakage in coil 19 would merely result in alkyl halide coolant flowing into electrolyte 12, or vice versa, depending upon the relative pressures in coil 19 and in the electrolysis zone. Should pressure in coil 19 exceed that of the electrolysis zone, alkyl halide would leak into electrolyte 12, and would merely increase the volume and pressure thereof, while not causing any serious chemical or thermal disruptions. Similarly, should electrolyte leak into coil 19, there will be no adverse reaction produced.
  • FIGURE 2 the second or vapor compression refrigeration type embodiment is depicted. Identical elements in FIGURES 1 and 2 are designated with identical numbers. However, in this embodiment substantially all of the alkyl halide admitted to coil 29 is permitted to evaporate, and the resultant alkyl halide vapor is withdrawn via vapor line 31.
  • alkyl halide coolant in FIGURE 2 Tracing the flow of alkyl halide coolant in FIGURE 2, liquid alkyl halide, at a temperature equal to or below the boiling point at the particular pressure prevailing in coil or tube 29, is transported to coil 29 which is in heat exchange relationship with electrolyte 12. As the latter becomes heated during electrolysis, alkyl halide boils 01f. The resultant vapors pass through line 31 to back pressure control valve 32, which maintains a constant or controlled back pressure on line 31 and tube 29. Excess alkyl halide, over and above that necessary to maintain the constant back pressure, is conducted as a vapor via line 33 to compressor 34, which increases its pressure to that prevailing in tube 29. Compressed vapor leaving compressor 34 passes through line 36 and into heat exchanger 37, which functions as a condenser to condense the compressed vapor and provide a liquid recycle stream which collects in receiver 38 and is then sent to coil 29 via line 39. 7
  • the alkyl halide coolant or refrigerant in this FIGURE 2 embodiment is selected to correspond with the alkyl Grignard electrolyte 12 (e.g. methyl chloride for the electrolysis of methyl magnesium chloride), the pressure maintained by back pressure control valve 32 is selected to provide a desired constant temperature in coil 29, and thus a substantially constant temperature in electrolyte 12.
  • the alkyl Grignard electrolyte 12 e.g. methyl chloride for the electrolysis of methyl magnesium chloride
  • FIGURE 2 is particularly advantageous in that it permits a relatively small tube or coil 29 to remove large quantities of heat from the electrolysis zone due to the relatively high heat of vaporization of alkyl halides.
  • the vapor pressures of boiling alkyl halides at temperatures most highly desired for conducting electrolyses of alkyl Grignard electrolytes are generally fairly close to those prevailing in the electrolytic cell, and consequently even should there be any leakage in coil 12 only a small amount of alkyl halide or electrolyte will leak through.
  • the method of removing heat from the electrolysis zone which comprises passing a coolant stream of alkyl halide corresponding to the alkyl Grignard electrolyte in indirect heat exchange relationship with said electrolyte.
  • the method of removing heat from the electrolysis zone which comprises passing a coolant stream of alkyl halide corresponding to the alkyl Grignard electrolyte in indirect heat exechange relationship with said electrolyte, withdrawing said stream, cooling said stream by indirect heat exchange with an external coolant, and recycling said stream.
  • the method of removing heat from the electrolysis zone which comprises passing a liquid coolant stream of alkyl halide corresponding to the alkyl Grignard electrolyte in indirect heat exchange relationship with said electrolyte, permitting said stream to vaporize under controlled pressure, withdrawing the resultant alkyl halide vapors, compressing and cooling said vapors to condense the same, and recycling the resultant liquid.

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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)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Motor Or Generator Cooling System (AREA)
US84209A 1961-01-23 1961-01-23 Electrolysis of alkyl grignardcontaining electrolytes Expired - Lifetime US3131135A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL273589D NL273589A (de) 1961-01-23
US84209A US3131135A (en) 1961-01-23 1961-01-23 Electrolysis of alkyl grignardcontaining electrolytes
DEST18771A DE1153753B (de) 1961-01-23 1962-01-19 Verfahren zur Herstellung von Metallalkylen durch Elektrolyse einer Alkyl-Grignard-Verbindung
FR885378A FR1311057A (fr) 1961-01-23 1962-01-19 Perfectionnements apportés à l'électrolyse des composés de grignard
GB2232/62A GB998024A (en) 1961-01-23 1962-01-22 Electrolytic processes employing alkyl grignard electrolytes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US84209A US3131135A (en) 1961-01-23 1961-01-23 Electrolysis of alkyl grignardcontaining electrolytes

Publications (1)

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US3131135A true US3131135A (en) 1964-04-28

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US (1) US3131135A (de)
DE (1) DE1153753B (de)
FR (1) FR1311057A (de)
GB (1) GB998024A (de)
NL (1) NL273589A (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991002359A1 (en) * 1989-08-04 1991-02-21 Drexler Technology Corporation Distributed accumulator for energy conversion
US5273635A (en) * 1992-06-04 1993-12-28 Thermacore, Inc. Electrolytic heater

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2202551B (en) * 1987-02-13 1990-12-19 Sanden Corp Apparatus and method for producing sodium hypochlorite
DE102010049300A1 (de) * 2010-10-22 2012-04-26 Emitec Gesellschaft Für Emissionstechnologie Mbh Halbleiterelemente bestehend aus thermoelektrischem Material zum Einsatz in einem thermoelektrischen Modul

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US788315A (en) * 1904-11-30 1905-04-25 William Hoopes Method of electrolytic separation.
US1027495A (en) * 1909-09-25 1912-05-28 Roessler & Hasslacher Chemical Electrolytic process.
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US788315A (en) * 1904-11-30 1905-04-25 William Hoopes Method of electrolytic separation.
US1027495A (en) * 1909-09-25 1912-05-28 Roessler & Hasslacher Chemical Electrolytic process.
US2985568A (en) * 1954-11-26 1961-05-23 Ziegler Electrolytic process for the production of metal alkyls

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991002359A1 (en) * 1989-08-04 1991-02-21 Drexler Technology Corporation Distributed accumulator for energy conversion
US5273635A (en) * 1992-06-04 1993-12-28 Thermacore, Inc. Electrolytic heater

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Publication number Publication date
GB998024A (en) 1965-07-14
NL273589A (de)
FR1311057A (fr) 1962-11-30
DE1153753B (de) 1963-09-05

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