US2094384A - Electrolysis apparatus and process - Google Patents

Electrolysis apparatus and process Download PDF

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Publication number
US2094384A
US2094384A US752636A US75263634A US2094384A US 2094384 A US2094384 A US 2094384A US 752636 A US752636 A US 752636A US 75263634 A US75263634 A US 75263634A US 2094384 A US2094384 A US 2094384A
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Prior art keywords
cell
anolyte
catholyte
cathode
electrolysis
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US752636A
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English (en)
Inventor
Carl W Tucker
Karl F Paul
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US752636A priority Critical patent/US2094384A/en
Priority to DEP72134D priority patent/DE668919C/de
Priority to GB31329/35A priority patent/GB465737A/en
Priority to FR797609D priority patent/FR797609A/fr
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Publication of US2094384A publication Critical patent/US2094384A/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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/29—Persulfates
    • 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
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides

Definitions

  • This invention relates to an electrolysis cell construction and the process of electrolysis carried out in that electrolysis cell. More specifically our invention relates to the preparation of persulfuric 5 acid and, persulfates, and materials derived there-,
  • the invention disclosed in this application is concerned with an improved construction for an electrolysis cell designed particularly for the preparation of the products above enumerated whereby these compounds may be produced more efficiently and more cheaply than heretofore possible.
  • Another object of our invention resides in so arranging the diflerent elements comprising our electrolysis cell that mechanical and/or chemical losses now incident a to the production of persulfuric acid and persulfates by electrolysis may be reduced to a substantial degree.
  • Still another and more specific object of our invention resides in preventing loss of the liquid containing persulfuric acid or a persulfate, which has been prepared by electrolysis, as a result of diffusion losses through'the porous diaphragm which is usually an element of such electrolysis cells and separates the chamber containing the anode liquid or anolyte fromthe chamber containing the cathode liquid or catholyte.
  • Persulfuric acid is now commercially prepared by the electrolysis of an aqueoussolution of sulfuric acid in an electrolysis cell having a platinum anode immersed in the anolyte (or liquid surrounding the anode) and a lead cathode in the catholyte (or liquid surrounding the cathode).
  • a persulfate salt electrolytically the same type of cell is utilized employing in lieu of the sulfuric acid usually an alkali metal sulfate or an acidulated solution of this invention is there a lower cell in the ammonium sulfate.
  • These cells contain a porous diaphragm which divides the space within the cell into two chambers, one containing the anolyte and the other containing the catholyte. It has beencustomary to form the porous diaphragm as a cylinder closed at the bottom, the space within the cylinder containing the anolyte and the anode assembly. The space external to the porous diaphragm contains the catholyte and the cathode,
  • This lead tube ordinarily functions both as cathode and as a means through which the cooling water may be circulated for the purpose of cooling the catholyte.
  • both the anolyte and the catholyte are permitted to flow trom one cell of the cascade arrangement after electrolysis into cascade arrangement where the liquids are again subjected to electrolysis thereby increasing the total overallconcentration of persulfuric acid or persulfate in the anolyte.
  • concentration of persulfuric acid or persulfate is built up in the anolyte and it is this liquor in which we are interested because of its subsequent distillation and hydrolysis to yield vapors of hydrogen peroxide.
  • Electrolysis cells as at.present employed are disclosed in the Baum Patent Nos. 1,837,177 and 1,937,621.
  • the anolyte is circulated as previously described, as is the catholyte.
  • the cathode consists of a coiled lead tube which surrounds the porous separating diaphragm and has the double function of acting as a cooling coil as well as an electrical element of the cell. It will be evident from the drawing forming a part of the patents previously referred to, illustrating the.
  • the porous diaphragm containing the anolyte it has been customary for the porous diaphragm containing the anolyte to project out of the catholyte. Therefore, in order for the anolyte liquid to flow over into the next succeeding cell it is essential in the cell illustrated in the patents referred to that the level of the anolyte within the porous diaphragm be higher than that of the catholyte in the cathode chamber.
  • Fig. I is a plan view on the line AA of Figs. II and III showing the electrolysis cell assembly.
  • the porous diaphragms are shown but the anodes and other elements within the porous diaphragm constituting the anode assembly have been omitted in each case.
  • the upper lip portion of the cathode box, described below, has been cut away to show the method by which the overflow tube for the anolyte is secured thereto.
  • Fig. II is a view partly in section and partly in elevation taken on the line B-B of Fig. I.
  • Fig. III is a view partly in section and partly in elevation taken on the line C-C of Fig. I.
  • the numeral 3 represents the cell container which is constructed of material resistant to the action of the electrolyte or is lined with such a material. Thus lead or a resinous compound is suitable since these materials are acid resistant.
  • the container has inserted therein a number of cylindrical porous diaphragms 4 of which six are shown. These porous diaphragms are spaced throughout the length of the cell container in line as shown in Fig. I.
  • a coiled tube 5 Surrounding the porous diaphragms and running parallel with the inner wall of the cell container is a coiled tube 5 which may be of lead or of some other acid-resistant metallic material. This tube functions both asthe cathode and as a means ject.
  • porous diaphra'gms- 4 which are closed at the bottom, rest on porcelain blocks 6 which support them from the bottom of cell. From each porous diaphragm at the upper end thereof, ex-
  • a cathode box 9 which may be formed of lead or some other acid-resistant conducting material.
  • This box which may be built of sheet material functions together with the coiled tube to serve as the cathode of the electrolysis cell.'
  • the lead or other material of this cathode box is continued across the top of the cell above the coiled tube electrode and the top of the cathode box is pierced by a number of openings for various purposes as will hereinafter beapparent. It is evident that the electrolysis cell comprises a number of anodes of which six are illustrated and but one cathode which functionsfor all the anodes.
  • the cell container may be omitted and the outside of the cell formed by the lead cathode box 9.
  • this is generally unsatisfactory as the problem of suitably insulating the cathode boxes of adjacent cells becomes difiicult to solve.
  • each porous diaphragm there are openings in the top surface ill of the cathode box through which the diaphragms and anode assemblies pro- At each opening an edge or lip portion l l is turned downwardly into the cell close up against and surrounding the porous diaphragm fora purpose which will be explained subsequently.
  • the lead box is formed withan upstanding lip orflange portion 33 which is bent outwardly into a series of lip portions i l at which each anolyte overflow spout projects outwardly.
  • These lip portions M are shaped to allow the tubes l to extend through the cathode box assembly.
  • the overflow tubes or pipes may be cemented to the cathode box as shown at l5 and are thereby securely retained in place.
  • the upstanding lip or flange portion l3 of the cathode box is bent outwardly at one portion to form a sort of enlarged receiving spout through which the catholyte of the next higher cell in the cascade arrangement flows into the cell after leaving the catholyte outlet pipe 8 of the next higher cell.
  • Figs. IIand III -the elevation of the central part of the lip portions It is lower than that of the remaining portions of upstanding flange it,
  • the anolyte discharge tubes or spouts i may merely be positioned in the lip portions It and not securely held thereto by the cement it;
  • the space between the lip portion and the tube should be regulated so that any While as shown catholyte liquid which may travel up between flanges ii and anode assemblies 4 will be prevented from flowing down the outside of the dis-' charge spout l by surface tension.
  • This may be a preferable way of preventing seepage of liquid down the outside of the discharge tube as we have found that some cements tend to aid the flow of catholyte out through the space between lip M-and tube 7.
  • Openings l6, 18, Hand 20 are provided at one end of the electrolytic cell in the top portion ii! of the cathode box. Opening. it is surrounded by a cylindrical sleeve 2
  • the liquid surrounding the cathode or the catholyte is maintained at a higher level than previously usual at those portions of the electrolytic cell surrounding the porous diaphragms. This is'accomplished by means of the elevating lips or flanges 53 attached to the cathode box 9. It is evident that the level/of the catholyte at each porous diaphragm may be as high as the top of the cell container 3 since the flanges l3 permit the catholyte to reach this level. Obviously then, the catholyte level is very close to a the level of the anolyte which latter level is determined by the level of the discharge tubes 1.
  • the cathode liquid can therefore fill up the space at those portions of the cell surrounding each porous diaphragm between the upstanding flange l3 and the wall of the cell container. 3, thus in- At this time it may be suring practical identity of level between the anolyte and catholyte.
  • the depending flange or edge portions ll surrounding each porous diaphragm and inserted into the catholyte within the cathode box prevent any hydrogen evolved within the catholyte from escaping around the porous diaphragms. Any hydrogen-set free by electrolysis is thus confined within the cathode box and is allowed to escape through the discharge opening Hi. It may be mentioned that hydrogen is not electrically evolved in the space between the anode assembly and the depending portions it as the active portion of each anode (not shown) is below the level of the flanges, as illustrated in the drawings of 'the patents previously referred to. .A; small amount of hydrogen may escape thru the space between flange ill and the anode assembly d of each anode, but this amount is, in general, very small.
  • the catholyte in addition to filling up the space Within the cathode box also fills up the annular chamber between the cathode box it and the cell container 3.
  • the catholyte of the next higher cell is permitted to flow through discharge spout 8 over into the receiving spout l2 the catholyte obviously flows down into the interior of .the cathode box through the narrow inlet space between the depending flanges H and porous diaphragm d.
  • assembly which trated at 28, 29 may be placed in the top surface In of the cathode box for the purpose of permitting the catholyte liquid to get down within the cathode box.
  • Figs. II and III show that portion of the anode projects out of the porous diaphragms.
  • These parts comprise principally the anolyte tube Zlwhich carries the anolyte from the next higher cell in the cascade arrangement into the anode chamber within the cylindrical glass member 26.
  • Surrounding the cylindrical glass member is metallic ring 23 to which are attached tantalum strips 22 which extend down within the porous diaphragm to platinum anodes '(not shown).
  • the glass cylinder 26 provides a chamber through which cooling water .may be circulated for the purpose of cooling the anolyte.
  • Attached to the coiled cathode and serving as a plurality of conducting members through which the electrical connections are made to the cell is a series of metallic strips which should be formed of a metal which is resistant to the action of the catholyte. Thesestrips are shown in Fig. I and are indicated by the numeral 25. On the drawing the electrical connection for the positive pole is indicated by a mark, whereas the conductors electrically connected marked by a sign.
  • sulfuric acid solutions we mean to include therein not only aqueous solutions of sulfuric acid alone but tain various addition from whichpersulfuric also solutions which conagents, stabilizers, etc., acid or persalts can be to the cathode are I minute apertures in 2,094,384 an additional aperture or apertures such as illusobtained by anodic action.
  • an electrolysis cell By an electrolysis cell is meant a cell in which electrical power is converted into chemical action as for the manufacture of desired chemical compounds.
  • An electrolysis cell including an anode and a cathode, said cell comprising in combination, a cell container, anolyte and catholyte liquids positioned within said cell container, and means secured to said cathode to maintain said anolyte and said catholyte liquids at approximately the same level.
  • An electrolysis cell including an anode and cathode, said cathode being formed as a coiled lead tube, said cell comprising in combination a cell container, anolyte and catholyte liquids positioned within said cell container, and means secured to and forming a. part of said cathode for maintaining said anolyte and catholyte liquids at approximately the same level.
  • An electrolysis cell including an anode and a cathode, said cathode comprising a coiled lead tube, said cell comprising in combination a cell container, anolyte and catholyte liquids positioned within said cell container, a lead box positioned below the level of said anolyte surrounding said coiled lead tube'cathode, and elevating flanges attached to the upper portion of said lead box to maintain said anolyte and catholyte liquids at approximately the same level.
  • An electrolysis cell formed with an anode, and a cathode in the form of a coiled lead tube, said cell comprising in combination a cell container, anolyte and catholyte liquids positioned within said cell container, a porous diaphragm surrounding an anode of said cell, a lead box positioned below the level of said anolyte surrounding said coiled tube cathode-and forming therewiththe cathode of said cell, an elevating flange secured to said lead box for the purpose of maintaining said catholyte at approximately the level of said anolyte liquid at those portions of the cell adjacent the porous diaphragm.
  • An electrolysis cell formed with an anode
  • An electrolysis cell formed with a plurality of anodes and a cathode, said anodes being positioned within a plurality of porous cylinders, and said cathode comprising, in part, a coiled lead tube, said electrolysis cell comprising in combination, a cell container, anolyte and catholyte liquids positioned within said container and kept separate by said porous diaphragms, a plurality of anolyte discharge tubes, a lead box surrounding said coiled tube cathode and functioning therewith as the cathode of said electrolysis cell,
  • trolysis cell adjacent said lead box being provided with elevating flanges, for the purpose of maintaining the catholyte at alevel approximately equal to that of the anolyte at those portions of said eleceach of said porous diaphragms, said elevating flange being shaped at portions adjacent "to each of said diaphragms so as to permit said anolyte discharge tubes to carry said anolyte over the top of said cell container, and depending flanges closely adjacent to and surrounding each of said'porous diaphragms for the purpose of preventing the escape of any gasv which may be formed within said catholyte around said porous diaphragms.
  • An electrolysis cell in which the catholyte and anolyte liquids are circulated which comprises, in combination, an anode, a coiled tube cathode, conducting means sm'rounding said coiled cathode tube and providing a chamber within which the catholyte is contained, a porous diaphragm positioned within said conducting means and surrounding said anode, the anolyte liquid being positioned within said diaphragm, means attached to said conducting means for maintaining said catholyte at approximately the level of said anolyte at those portions of said electrolysis cell adjacent to said porous diaphragm, and means adjacent the porous diaphragm for preventing the escape of gases developed within said catholyte at those portions'of said cell adjacent said diaphragm.
  • an electrolysis cell including an anode and a cathode of the type in which the anolyte and the catholyte liquids are separated by a po-' rous diaphragm, means adjacent to said porous diaphragm for elevating the level of said catholyte so that it is substantially at the same level as said anolyte, said means being secured to and forming a part of the cathode of said cell.
  • An electrolysis cell comprising a cathode, a plurality of anodes, a plurality of porous diaphragms surrounding said anodes, a catholyte liquid adjacent to said cathode, a plurality of anolyte liquids positioned within said porous diaphragms and separated from said catholyte thereby, means for removing said anolyte from each of said porous diaphragms, and means adjacent to each of said porous diaphragms for elevating the level of said catholyte to approximately the level I of said anolytes which is determined in each case by the level of said anolyte outlet means.
  • An electrolysis cell comprising a plurality of anodes, a plurality of porous diaphragms surrounding said anodes, a-catholyte liquid, a plurality of anolyte liquids positioned within said porous diaphragms and separated from said catholyte thereby, a cathode positioned below the level of said anolyte liquid, means for removin said anolyte from within each of said porous diaphragms, and means adjacent toeach of said porous diaphragms for elevating the level of said catholyte to approximately the level of said anolyte, said level being determined by the level of said anolyte outlet means, said elevating means including an elevating flange secured to and forming a part of said cathode.
  • An electrolysis cell which comprises an anode and a cathode, a cell container, anolyte and catholyte liquids positioned container, a porous diaphragm surrounding said anode, said anolyte extending above the level of the major portion of said catholyte, and means for maintaining said anolyte and said catholyte liquids at approximately the same level at that portion of the cell adjacent said porous diaphragm.
  • a two-liquid electrolysis cell including an anolyte and a catholyte
  • the combination which comprises a cathode positioned below the level of said anolyte liquid, an anode, a porous diaphragm separating said catholyte liquid from said anolyte liquidand means comprising an elevating flange attached to and forming a part of said cathode for maintaining said catholyte and anolyte liquids at substantially the same level at that portion of said cell adjacent'said porous diaphragm.
  • a process for preparing persulfuric acid or persulfates by electrolysis which comprises treating a solution of sulfuric acid or a sulfate successively in atplurality of electrolysis cells arranged in cascade arrangement, said electrolysis cells being provided with porous diaphragms arranged to separate said electrolyte into a catholyte and anolytes positioned interiorly of said catholyte, circulating said catholyte and anolyte liquids from cell to cell in said cascade arrangement and maintaining said catholyte and said anolytes at substantially the same level in each of said electrolysis cells of said cascade arrangement throughout the entire electrolysis.
  • i l/An electrolysis cell including anolyte and catholyte liquids, an anode and a cathode, said anode extending substantially above the level of the major portion of said catholyte liquid, and means for maintaining said anolyte and catholyte liquids at approximately the same level only at that portion of said cell adjacent said anode.
  • An electrolysis cell which comprises anolyte and catholyte liquids, an anode, a cathode positioned substantially below the level of the upper portion of said anode and means cooperating with said cathode for maintaining said anolyte and catholyte liquids at approximately the same level only at that portion of said cell adjacent said anode.
  • An electrolysis cell including an anode and a cathode, a. cell container, anolyte and catholyte liquids within said cell container, the major portion of said catholyte liquid being positioned within said cell container below the upper level of said anolyte,and means cooperating with said cathode for maintaining said anolyte and said catholyte liquids at approximately the same level at that portion of said cell adjacent said anode.
  • An electrolysis cell including an anode and a cathode, anolyte and catholyte liquids, said anolyte liquid being positioned so as to have a level higher than the level of the major portion of said catholyte liquid, and means for maintaining said anolyte and catholyte liquids at approximately the same level at that portion of said cell adja cent said anode.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrolytic Production Of Metals (AREA)
US752636A 1934-11-12 1934-11-12 Electrolysis apparatus and process Expired - Lifetime US2094384A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US752636A US2094384A (en) 1934-11-12 1934-11-12 Electrolysis apparatus and process
DEP72134D DE668919C (de) 1934-11-12 1935-11-10 Zelle zur Durchfuehrung von Elektrolysen
GB31329/35A GB465737A (en) 1934-11-12 1935-11-12 Improvements in or relating to electrolytic processes and apparatus
FR797609D FR797609A (fr) 1934-11-12 1935-11-12 Dispositif et procédé pour la mise en oeuvre des électrolyses

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US752636A US2094384A (en) 1934-11-12 1934-11-12 Electrolysis apparatus and process

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DE (1) DE668919C (de)
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GB (1) GB465737A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2589982A (en) * 1947-05-12 1952-03-18 Porte Chemicals Ltd Electrolytic production of ammonium persulfate solutions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2589982A (en) * 1947-05-12 1952-03-18 Porte Chemicals Ltd Electrolytic production of ammonium persulfate solutions

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FR797609A (fr) 1936-05-01
DE668919C (de) 1938-12-13
GB465737A (en) 1937-05-13

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