US3486992A - Process for electrolytic oxidation of thallium or cerium salts - Google Patents

Process for electrolytic oxidation of thallium or cerium salts Download PDF

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Publication number
US3486992A
US3486992A US616377A US3486992DA US3486992A US 3486992 A US3486992 A US 3486992A US 616377 A US616377 A US 616377A US 3486992D A US3486992D A US 3486992DA US 3486992 A US3486992 A US 3486992A
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thallium
solution
ion
anode
iii
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US616377A
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Alfred H Frye
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Milacron Inc
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Cincinnati Milling Machine Co
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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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/282—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium

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  • FIGURE I is a chart graphically showing the course of both oxidation and reduction of thallium sulfate solutions when subjected to electrolysis in an undivided cell.
  • FIGURES II, III and IV are diagrammatic representation of several prototypic cells. All of the drawings will be described in detail in connection with a more detailed description of the invention.
  • a cathode of platinized platinum foil having a surface area of 4 in. and an anode of bright platinum foil with a surface area of 8 in. were immersed in 200 ml. of a mechanically stirred aqueous solution of thallium(I) sulfate containing 0.07 g. ion of [Tl]+ and 0.24 g. ion [80 1- and electrolysis commenced using a current of 2.5 amps.
  • the electrolysis was interrupted periodically and samples of the aqueous solution were withdrawn and analyzed for their thallium(I) content. From FIGURE I it is evident that the percent conversion levels off in the neighborhood of 55-60% thallium(III) and thereafter remains constant.
  • a more specific object of this invention is to provide a method for the electrolytic reoxidation of solutions of salt of thallium(I) or of cerium(III) in such a way as not to introduce into those solutions any unwanted or deleterious materials, nor to alter the concentrations of the ions in such a way that their desired concentrations cannot easily and cheaply be reestablished.
  • suitable membranes may be selected from such materials as reinforced cation or anion exchange resins, as for example those described inv U.S. 2,962,454, and U.S. 2,800,445, microfibreglass matting of the type supplied by the Gelman Instrument Company for thin layer chromatography, and the hydrophilically modified microporous membranes of poly(propylene) or of poly(tetrafluoroethylene), such as supplied by Bel-Arts Products, Inc. and by Chemplast, Inc.
  • the electrode materials should, under the conditions in which they are to be used, have high resistance to chemical attack, and, in the case of the cathode, afford a sufficiently low hydrogen overvoltage to cause the liberation of hydrogen in preference to the reduction of the metal ion to its zero-valent state, whereas in the case of the anode, afford sufficiently high oxygen overvoltage to permit substantial oxidation of the metallic ion in competition with the liberation of oxygen and/or, via the intermediate agency of some adequately strong chemical oxidizing agent, e.g., lead dioxide or activated chemisorbed oxygen, being concomitantly generated at the anode-solution interface under the conditions of electrolysis.
  • suitable cathode materials are such materials as platinized platinum and platinized titanium, and for the anode, materials such as bright or platinized platinum, platinized titanium, and lead.
  • FIGURES II, III, and IV ari:l diagrammatic representations of several prototypic ce s.
  • FIGURE II shows a gravity flow cell in which the liquid, entering the cell through tube A, is caused to flow by hydrostatic pressure in a continuous stream through the cathode compartment and thence (via conduit C) into the base of the cells anode compartment Where it rises along the anode and finally issues from the cell through the tube at E.
  • Hydrogen liberated at the cathode rises against the downward stream of liquid and escapes from that compartment via a vent in its head, while oxygen liberated at the anode moves concurrently upward with the liquid and escapes from that compartment through another vent.
  • FIGURES III and IV are given two versions of forced flow cells, the first designed to operate horizontally and the second vertically.
  • the solution to be oxidized is pumped into the cathode compartment through a tube located at A.
  • the solution flows through that compartment and, together with the liberated hydrogen, leaves that compartment at B and is carried by conduit C to a surge tank where the hydrogen escapes through a vent.
  • the solution, now freed of hydrogen, is carried by conduit C to a pump which forces the solution into the cells anode compartment at D.
  • FIG. URE V is shown one such assembly in which a group of five forced flow cells is arranged in parallel as modular units within a pile or stack.
  • a further elaboration of the basic principle is possible by using two or more piles in series, each operating with a particularly advantageous current density and/ or a particular electrode material, and each carrying the oxidation through a different stage of completion (e.g., 20%, 2040%, etc.) such that an optimization of the process overall economics results.
  • the concentrations of the metallic ions and of their accompanying acid anions 'shall be maintained within certain limits.
  • concentrations of the thallium and of the sulfate ions should be maintained at such levels that the thallium(I) does not precipitate either as thallium(I) sulfate or as a complex salt with thallium(III) sulfate, nor the thallium(III) precipitate as the insoluble oxide in the event the sulfate ion concentration should become too low.
  • any process which is used to reoxidize the metallic ion to its higher valent state should do so in such a way that harmful or deleterious by-products are not introduced and which yet makes it possible to maintain or to re-establish the desired concentrations of the metallic ion and of its accompanying acid anion both cheaply and efiiciently.
  • M is the polyvalent metallic ion and n is an integer.
  • EXAMPLE 1 The electrolytic cell used was a gravity flow cell measuring 7" in height, 3" in breadth, and /1" in thickness, similar to the one illustrated in FIGURE II, except that in place of conduit C a pair of small apertures was made in the base of the dividing membrane (anion exchange membrane) to permit the solution to pass from the cathode compartment into the anode compartment.
  • a piece of platinized platinum sheeting measuring 6" in length by 1 /2" in width, sandwiched between a pair of plastic grids, each having a thickness of approximately and a length and breadth sufficient to extend from side-to-side and toptobottom of the compartment.
  • anode compartment In the anode compartment was inserted a similar sandwich, except that in this case the platinum was not platinized.
  • the two electrodes were connected to an electrical source and a ml. portion of an aqueous solution containing 0.344 g. ion (Tl)+ and 1.20 g. ion (SO per liter was placed in the cell.
  • a current of 5.0 amps was applied to the electrodes, and, simultaneously, additional thallium (I) sulfate solution was added dropwise to the cells cathode compartment at the rate of 2.6 ml. per minute, causing the solution to be expelled from an overflow near the top of the cells anode compartment.
  • Electrolysis was continued in this manner for a total of minutes, the efiluent solution being collected separately for the time intervals 050 minutes, 50- 100 minutes, and l00150 minutes. It was found that the efiluents collected during the second and third intervals, which are representative of the process in continuous operation, had 85% and 87% of their thallium content in the trivalent state, corresponding to current efiiciencies of 45% and 46% respectively.
  • the concentrations of the thallium or cerium ions present in the solutions should be as high as possible, but not so high as to incur the precipitation of any solids from the solutions as the electrolysis proceeds.
  • concentrations of the thallium or cerium ions present in the solutions should be as high as possible, but not so high as to incur the precipitation of any solids from the solutions as the electrolysis proceeds.
  • thallium sulphate I have found that solutions containing as much as 0.45 gram ion of thallium and 2.0 grams ion of sulphate per liter of solution can be employed at temperatures above about 20 C. and yet not cause the precipitation of either thallium (III) oxides, thallium (I) sulphate, nor any complexes of thallium (I) and thallium (III) sulphates.
  • EXAMPLE 2 The same cell, procedure, and thallium (I) sulfate solution were employed as in Example 10, except that cation exchange membrane was employed. It was found that the efiluents collected during the second and third intervals contained 84% and 86% of their thallium in the trivalent state, corresponding to an average current efficiency of 46%.
  • EXAMPLE 3 Eessentially the same cell, procedure, and thallium (I) sulfate solution were employed as in Example 2, except that the anode was platinized platinum and that the membrane was a cation exchange membrane. During the period of steady state operation the conversion was 86% and the current efficiency was 63 EXAMPLE 4 Essentially the same cell, procedure, and thallium (I) sulfate solution were employed as in Example 2, except that a microfibreglass mat, for thin layer chromatography, was used as the cell divider in place of the ion exchange membrane. It was found that during the period of steady state operation the conversion to thallium (III) amounted to 73% with a corresponding current efiicency of 52%.
  • EXAMPLE 5 The cell and procedure were the same as employed in Example 3, however, the membrane was a slightly different cationic exchange membrane and the solution was the nitrate salt of thallium (I) and contained 0.146 g. ion [Tl] and 1.6 g. ion [NO per liter. Additionally, a current of 2.6 amps, rather than 5 amps was used. During the period of steady state operation the conversion amounted to 83% while the current efiiclency was 38%.
  • EXAMPLE 6 The cell, procedure, and thallium (I) sulfate solution were essentially the same as in Example 2, but the anode was a sheet of lead. During the period of steady state operation the conversion was 75% and the efficienc was 50%.
  • EXAMPLE 7 The cell, procedure, and thallium (I) sulfate solution were essentially the same as in Example 2, but the membrane was a cellulose ester filter sheet. During the period of steady state operation the conversion was 82% and the efficiency 55% EXAMPLE 8 The cell and procedure were essentially the same as used in Example 2, however the solution was a cerium (III) sulfate solution containing 0.151 g. ion [Ce] per liter and approximately 1.1 g. ion [SO.,]* per liter. A current of 1.0 ampere was employed. Under these conditions it .was found that during the period of steady state operation the conversion to cerium (IV) was 68% with an average efliciency of 40%.
  • a continuous process for the electrolytic oxidation of a solution of a salt of a polyvalent metallic ion selected from the group consisting of solutions of thallium (I) and cerium (III) salts which comprises continuously passing the solution to be oxidized into the cathode compartment of a divided electrolytic cell across whose electrodes a difference in electrical potential is imposed, removing the cathodically generated hydrogen and passing said solution into the anode compartment of said cell wherein oxidation (of said polyvalent metallic ion occurs, removing anodically generated oxygen and recovering the resultant oxidized polyvalent metallic ion solution, the cells divider being a membrane which, while it impedes the back-migration of the oxidized metallic ion into the cells cathode compartment, permits transport therethrough of the electrical current-carrying hydrogen ion, the electrode materials being essentially chemically inert and, in the case of the cathode, providing a sufiiciently low hydrogen over-voltage as to prevent the reduction of the

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US616377A 1967-02-15 1967-02-15 Process for electrolytic oxidation of thallium or cerium salts Expired - Lifetime US3486992A (en)

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AT (1) AT286937B (de)
BE (1) BE710813A (de)
CH (1) CH505758A (de)
DE (1) DE1667835B2 (de)
ES (1) ES349961A1 (de)
FR (1) FR1556518A (de)
GB (1) GB1209991A (de)
LU (1) LU55472A1 (de)
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SE (1) SE347497B (de)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312721A (en) * 1980-05-15 1982-01-26 B.C. Research Council Electrolytic oxidation process
FR2570087A1 (fr) * 1984-09-13 1986-03-14 Rhone Poulenc Spec Chim Procede d'oxydation electrolytique et ensemble d'electrolyse pour sa mise en oeuvre
US4639298A (en) * 1986-05-05 1987-01-27 W. R. Grace & Co. Oxidation of organic compounds using ceric ions in aqueous methanesulfonic acid
US4647349A (en) * 1986-05-05 1987-03-03 W. R. Grace & Co. Oxidation of organic compounds using ceric ions in aqueous trifluoromethanesulfonic acid
US4670108A (en) * 1986-10-10 1987-06-02 W. R. Grace & Co. Oxidation of organic compounds using ceric methanesulfonate in an aqueous organic solution
US4692227A (en) * 1986-12-01 1987-09-08 W. R. Grace & Co. Oxidation of organic compounds using thallium ions
US4701245A (en) * 1986-05-05 1987-10-20 W. R. Grace & Co. Oxidation of organic compounds using a catalyzed cerium (IV) composition
US4794172A (en) * 1986-10-10 1988-12-27 W. R. Grace & Co.-Conn. Ceric oxidant
US5385648A (en) * 1992-07-28 1995-01-31 Nippon Shokubai Co., Ltd. Process for preparing a ceric ion-containing aqueous acid solution

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA703750B (en) * 1969-06-06 1971-01-27 Australian Iron And Steel Ltd Addition of metal ions to plating bath
FR2077830A1 (de) * 1970-02-17 1971-11-05 Rhone Poulenc Sa
DE3360378D1 (en) * 1982-04-12 1985-08-14 Rhone Poulenc Spec Chim Process for the preparation of cerium carboxylates
GB2332210B (en) * 1997-12-10 2000-07-19 Toshiba Kk Processing method of waste water and processing apparatus thereof
DE102005038970A1 (de) * 2005-05-11 2006-11-16 Over-Eloxal Gmbh Vorrichtung zum Behandeln eines Metalls in einem Elektrolytbad und Verfahren zum Verringern einer Aerosolabgabe
RU2520490C2 (ru) * 2012-06-08 2014-06-27 Государственное научное учреждение Всероссийский научно-исследовательский институт электрификации сельского хозяйства (ГНУ ВИЭСХ РОССЕЛЬХОЗАКАДЕМИИ) Способ и устройство для получения водорода из воды
CN111115767A (zh) * 2020-01-19 2020-05-08 中南大学 一种连续式深度净化处理含铊工业废水的方法及装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US729502A (en) * 1902-09-04 1903-05-26 Hoechst Ag Oxidizing organic compounds.
US1707450A (en) * 1929-04-02 Bbschbgwkteb haetttng
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1707450A (en) * 1929-04-02 Bbschbgwkteb haetttng
US729502A (en) * 1902-09-04 1903-05-26 Hoechst Ag Oxidizing organic compounds.
US3147203A (en) * 1961-09-21 1964-09-01 Pure Oil Co Process for the production of carbonyl compounds

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4312721A (en) * 1980-05-15 1982-01-26 B.C. Research Council Electrolytic oxidation process
FR2570087A1 (fr) * 1984-09-13 1986-03-14 Rhone Poulenc Spec Chim Procede d'oxydation electrolytique et ensemble d'electrolyse pour sa mise en oeuvre
EP0178958A1 (de) * 1984-09-13 1986-04-23 Rhone-Poulenc Chimie Verfahren und Vorrichtung für elektrolytische Oxydation
AU576263B2 (en) * 1984-09-13 1988-08-18 Rhone-Poulenc Specialites Chimiques Electrolytic oxidation of inorganic compounds
US4639298A (en) * 1986-05-05 1987-01-27 W. R. Grace & Co. Oxidation of organic compounds using ceric ions in aqueous methanesulfonic acid
US4647349A (en) * 1986-05-05 1987-03-03 W. R. Grace & Co. Oxidation of organic compounds using ceric ions in aqueous trifluoromethanesulfonic acid
US4701245A (en) * 1986-05-05 1987-10-20 W. R. Grace & Co. Oxidation of organic compounds using a catalyzed cerium (IV) composition
US4670108A (en) * 1986-10-10 1987-06-02 W. R. Grace & Co. Oxidation of organic compounds using ceric methanesulfonate in an aqueous organic solution
US4794172A (en) * 1986-10-10 1988-12-27 W. R. Grace & Co.-Conn. Ceric oxidant
US4692227A (en) * 1986-12-01 1987-09-08 W. R. Grace & Co. Oxidation of organic compounds using thallium ions
US5385648A (en) * 1992-07-28 1995-01-31 Nippon Shokubai Co., Ltd. Process for preparing a ceric ion-containing aqueous acid solution

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CH505758A (de) 1971-04-15
FR1556518A (de) 1969-02-07
SE347497B (de) 1972-08-07
NL139015B (nl) 1973-06-15
ES349961A1 (es) 1969-04-16
DE1667835B2 (de) 1976-10-14
LU55472A1 (de) 1968-04-29
NL6802165A (de) 1968-08-16
AT286937B (de) 1970-12-28
GB1209991A (en) 1970-10-28
DE1667835A1 (de) 1972-03-16
BE710813A (de) 1968-08-16

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