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US3222267A - Process and apparatus for electrolyzing salt solutions - Google Patents

Process and apparatus for electrolyzing salt solutions Download PDF

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Publication number
US3222267A
US3222267A US185424A US18542462A US3222267A US 3222267 A US3222267 A US 3222267A US 185424 A US185424 A US 185424A US 18542462 A US18542462 A US 18542462A US 3222267 A US3222267 A US 3222267A
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Prior art keywords
compartment
anode
cathode
feed
diaphragm
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US185424A
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English (en)
Inventor
Charles E Tirrell
Edgardo J Parsi
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Veolia WTS Systems USA Inc
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Ionics Inc
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Priority to NL278049D priority Critical patent/NL278049A/xx
Priority claimed from US108061A external-priority patent/US3135673A/en
Application filed by Ionics Inc filed Critical Ionics Inc
Priority to US185424A priority patent/US3222267A/en
Priority to GB17119/62A priority patent/GB963932A/en
Priority to FR896595A priority patent/FR1324549A/fr
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    • 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
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • 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
    • 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
    • C25B1/14—Alkali metal compounds
    • 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
    • C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
    • C25B1/46—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis in diaphragm 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
    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
    • C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • 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
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
    • C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms

Definitions

  • This invention relates to electrolytic processes and apparatus for the electrochemical conversion or oxidation and reduction of electrolytic solutions. More particularly it relates to processes and apparatus which employ three compartment or four compartment electrolytic cells.
  • the three compartment cell contains an ionexchange membrane which is hydraulically impermeable to solutions, but selectively permeable to cations, said membrane separating and defining the cathode compartment fromthe anode feed compartment and a spaced acid resistant hydraulically permeable diaphragm separating and defining the anode compartmentfrom the anode feed compartment.
  • the anode feed compartment therefore being defined by a cation-permeable membrane facing the cathode side and on 'the anode side 'by a hydraulically porous diaphragm.
  • the three compartment cell employs the following chamber arrangement; anode chamber/anode feed chamber/cathode chamber.
  • the electrolytic salt solution is passed into the anode feed chamber and tap water or other conducting solutionsare passed into the cathode compartment or chamber.
  • a direct electrical potential is impressed upon the cell causing migration of cationic ions of the electrolyte through the cation permselective membrane into the cathode compartment where combination with hydroxyl ions produced by the electrolysis of water at the cathode produces the corresponding metal hydroxide; and passage of the electrolyte solution containing the anionic groups plus a small portion of the cationic ions of said electrolyte through the hydraulically permeable diaphragm into the anode compartment where combination of the anionic groups with hydrogen ions produced by the electrolysis of water at the anode produces the corresponding acid which, mixed with the original electrolyte forms an anolyte effluent product, for example, acid salt.
  • a cathode feed chamber made by the addition of a second porous diaphragm. Said second diaphragm separates and defines the cathode chamber from the cathode feed chamber.
  • Electrolytic cells for example caustic-chlorine cells, now commonly employed for salt conversion are of two general types: (1) diaphragm and (2) mercury, and are distinguished chiefly by the purity of the corresponding metal hydroxide produced and production per unit floor space.
  • Mercury cells are of such design that the product hydroxide solution is of a high degree of purity, i.e., the hydroxide may have a contaminating foreign anion concentration of less than about 0.05% of the concentration of the hydroxide, this advantage being the mercury cells principal inducement toward its employment in commercial installations.
  • Mercury cells typically employed in the electrolysis of waste sodium sulfate spinning liquor consist of an electrolyzing chamber containing a sulfateresistant alloyed anode and a cathode consisting of a flowing bed or rotating vortex of mercury which reacts with sodium ions to form a sodium amalgam-film upon its surface; subsequently this sodium amalgam-mercury composition is withdrawn from the cell and passed through an amalgam decomposing chamber wherein a flow of water countercurrent to theflow of mercury effluent converts the amalgam to a substantially pure aqueous solution of sodium hydroxide.
  • Diaphragm type electrolytic cells overcome these cited disadvantages to a satisfactory extent. However, they are characterized by the production of aproduct metal hydroxide solution which has a considerably low degree ofpurity. Cells of this category employ one or more diaphragm permeable to flow of electrolyte solution, but impervious to passage of gas bubbles, thus separating the cell into' two or more compartments; for example, a threecompartment cell containing two porous diaphragms is described in US. Patent No. 1,126,627.
  • the processes associated with this type of cell comprise the steps of transferring from either orboth the anode and the center compartment to the cathode compartment by means of permeation through the diaphragrn(s) a relatively concentrated aqueous salt solution which is passed into the anode or center compartment at a rate sufiicient'to repress the migration of hydroxyl ions toward the anode, thereby producing as a catholyte effluent the corresponding metal hydroxide and free hydrogen gas, while at the anode, free oxygen or chlorine gas is produced and, in the case of the original salt solution consisting of sodium sulfate, a mixture of the salt and the corresponding acid.
  • diaphragm-type electrolytic cells achieves relatively high production'of products per unit' floor space, lower energy requirements and higher current elficiencies, but incurs the serious disadvantage of producing as the catholyte efiluent product the hydroxide solution in "a very dilute and impure form, i.e., the product may consist of about 12% hydroxide and about 12% of the original salt.
  • concentration and separation of the hydroxide by the use of three-stage evaporators is required wherein the salt crystallizes out, and a final NaOH concentration of about 50% is achieved.
  • the center compartment which is comparable to the anode feed compartment of the three-compartment cell of the present invention, is bounded on the [anode side by an anion-permselective membrane, the same phenomenon of migration toward the cathode of hydrogen ions formed at the anode through the intervening anion-permeable membrane will occur due to the inherent inefliciency toward repression of hydrogen ion permeation of those anion-permselective membranes known in the art.
  • a comparatively high efficient anion membrane will function in such a manner that about 50% of the current passing through said membrane is conveyed by the passage of hydrogen ions through said membrane toward the cathode, the remaining cur-rent being carried by the anions migrating toward the anode. Consequently, the insertion of an anionpermselective membrane in place of a non-permselective diaphragm in this case, is of no value due to the membranes low anion permselectivity.
  • the minimizing of the migration of hydrogen ions toward the cathode by a countercurrent flow of electrolytic solutions is effected substantially by means of a porous non-permselective diaphragm inserted between the anode and the influent electrolytic solution.
  • Another object of this invention is the provision of a method for electrochemical conversion of aqueous electrolyte solutions of high purity products overcoming many of the disadvantages of the prior art.
  • Another object of the present invention is to provide an improved process for the regeneration of waste sodium sulfate liquor obtained from the spinning operations in the viscose rayon industry.
  • FIGURE 1 is a diagrammatic representation in vertical cross section of a three-compartment electrolytic cell of the present invention containing a self-supporting diaphragm.
  • FIGURE 2 is a slight variation of the cell of FIGURE 1 wherein the anode is of foraminous or expanded metal and forms the support for the porous diaphragm.
  • FIGURE 3 is also .a diagrammatic representation of a four-compartment cell in vertical cross section, employing self-supporting porous diaphragms.
  • FIGURE 4 is a variation of the cell of FIGURE 3 wherein both foraminous electrodes are used as porous diaphragm supports with said electrodes opera-ting unsubmerged.
  • FIGURE 5 is an enlarged further representation of the configuration of expanded metal electrodes.
  • the anode compartment 8 of cell A contains a chemically resistant anode 2 and is provided with outlet 3 for the anolyte efiiuent product and outlet 4 for gaseous anode products such as oxygen.
  • the anode compartment is separated from the anode feed compartment 5 by means of an acid resistant hydraulically permeable non-permselective diaphragm 6, said anode feed compartment 5 containing an inlet 7 through which the electrolytic feed solution is introduced.
  • the cathode compartment 9 is separated from the anode feed compartment by a cation-exchange membrane 10 selectively permeable to cations and such cathode compartment is provided with a conventional cathode 11 and conduit 12 through which water is passed into the cathode compartment.
  • Outlet 13 serves to withdraw the catholyte effluent product, and exit pipe 14 removes gaseous cathodic products such as hydrogen.
  • FIGURE 2 the cell configuration and method of operation is fairly similar to that described in FIGURE 1.
  • the difference being that the cell of FIGURE 2 had an important added feature in that the porous diaphragm.6 is supported on a foraminous or porous anode 2a.
  • the foraminous electrode is constructed in that its pore sizes are larger than the pore size of the supported diaphragm so that the resistance of electrode to hydraulic flow of electrolyte solution is negligible as compared to that of the microporous diaphragm.
  • the use of a supporting porous electrode allows the electrode to be operated partially or completely unsubmerged in liquid, that is, the liquid level in the electrode compartment need not completely cover the electrode.
  • the electrolyte solution for example, -a nearly saturated solution of sodium sulfate
  • the cell is introduced into the cell through conduit 7 at a rateand pressure sufficiently high so that the passage of said electrolyte through the porous diaphragm 6 is at a rate sufficiently rapid to curt-ail substantially the migration of hydrogen ions from the anode toward the cathode.
  • the resultant anolyte effluent product will be -a stoichiometric solution of sodium bisulf'ate, such solution being suitable for use in rayon spinning operations.
  • a fourcompartment cell minimizes this back migration of these ions by placing a porous .acid resistant diaphragm 6 between the anode 2 and anode feed chamber 5, and similarly inserting a caustic-resistant second diaphragm 16 between the cathode 11 and cathode feed chamber 15. Both diaphragms are hydraulically permeable to the flow of a liquid solution.
  • the ion-exchange membrane 10 divides the cell into two distinct sections, each section being a mirror image of the other.
  • the respective solutions are directed to the feed chambers and are allowed to percolate through the diaphragm in a direction which is opposite to that of the migrating ions, at a velocity greater than that of the moving ions.
  • the ions are flushed back into their respective electrode chambers.
  • FIGURE 4 which is the preferred apparatus of carrying out the purposes of this invention, employs foraminous electrodes 2a and 11a on which a porous diaphragm 6 and 16 are deposited respectively thereon.
  • the electrodes are operated unsubmerged; that is, the level of the anolyte solution 48 and catholyte solution 49 is below the lowest section of the electrodes, said solutions accumulating in their respective collection sections 60 and 61.
  • the cell of FIGURE 4 is operated as follows:
  • the negatively-charged hydroxyl ions produced at the cathode 11a are attracted through the porous cathode diaphragm 16 in the direction of the anode 2a. Due to the cation-membrane barrier, the negative ions are substantially prevented from further migration into the anode feed chamber 5. However, when the concentration of these hydroxyl ions accumulates sufficiently within the cathode feed chamber 15, many will pass through the membrane 10 due to diffusion and also to the inherent inefiiciency of the membrane to prevent anion exclusion. The greater the concentration of negative ions in contact with the membrane, the greater the rate of loss through said membrane.
  • water is directed by conduit 12 into cathode feed chamber 15 and allowed to flow through the diaphragm-cathode.combination 16 and 11a and trickle down the unsubmerged side of the porous cathode grid 11a, rapidly flushing down cathodic products into the cathode collection chamber 61 where it is withdrawn through outlet 13.
  • the sweep of the water through the diaphragm will minimize back migration of hydroxyl ions and also pass to the cathode collection section any hydroxyl ions which may have migrated into the cathode feed chamber.
  • the current that is wasted by being carried by the hydroxyl ions migrating in the direction of the anode is minimized, thus achieving higher efficiencies and production rates.
  • the concentration in the cathode feed chamber be kept down to a minimum. It has been found that by using a diaphragm of sufiiciently small porosity in conjunction with a feed solution of sufficiently high pressure and velocity, the concentration of hydroxide in the cathode feed chamber can be maintained at less than A the concentration of caustic recovered from the cathode collection chamber.
  • the use of an unsubmerged foraminous cathode has an added advantage in that gas disengagement from the cathode surface, for example, hydrogen, is more readily accomplished since there is no bulk liquid present to entrap or make difficult the release of cathodically formed gases.
  • the relationship at the anode is analogous to the cathode arrangement.
  • the electrolytic solution for example, a saturated brine
  • the anolyte is then removed at outlet 3.
  • the sweep of the feed electrolyte through the porous diaphragm-anode combination 6 and 2a carries anodic oxidation products, for example, chlorine, away from the anode metal where such products can be extremely destructive to the metal.
  • the sweep of the electrolyte assures a maximum concentration of fresh feed electrolyte at the anode surface, and also at the surface of the membrane 10.
  • the use of a diaphragm separating the anode from the membrane will also prevent attack and erosion of the membrane surface by oxidants of the anolyte solution, especially dissolved and gaseous chlorine. The oxidants formed at the anode are prevented from contacting the membrane surface since the sweep of electrolyte feed solution will essentially flush back these highly corrosive products.
  • the cell of FIGURE 4 can be modified so that only one electrode whether cathode or anode is used as a porous support medium for the diaphragm with the remaining electrode being of the conventional type. Also, both electrodes can be operated completely or partially submerged or varied so that only one electrode remains submerged in liquid.
  • the electrolyte employed may be any water soluble electrolytic material such as inorganic salts, acids and bases and organic salts.
  • the processes disclosed herein are applicable toward its purification of ionic impurities; such as cationic impurities, in the instance of the electrolyte being of acidic nature, and anionic impurities in the instance of the electrolyte being of basic character.
  • an electrolytic salt whose corresponding acid is weakly ionized, for example, sodium acetate or potassium fluoride, permits, as a result of such anodic formation of the slightly ionized acid a relatively small quantity of free hydrogen ions available for migration toward the cathode, with a corresponding reduction in the flow rate of the feed electrolytic solution to conform to the degree of ionization of the corresponding acid, whereby said reduction in fiow rate permits a comparatively high degree of transference of the alkali metal cation into the cathode compartment, and correspondingly, less of the original electrolyte solution passing through the diaphragm into the anolyte compartment.
  • the flow rate of the eletrolytic solution may be regulated so that the salt content of the anolyte product is of a desired value, for example, in the case of sodium sulfate, the flow of an aqueous solution of the same into the anode feed compartment may be regulated so that the anolyte effiuent product is solely a solution of sodium bisulfate, i.e., the rate will be controlled so that the equivalents of the original salt entering the anode compartment are equal to the equivalents of sulfuric acid being formed therein.
  • the temperature of the electrolytic feed solution and the catholyte infiuent water may vary from above its freezing point to below its boiling point. However, in general, it is preferred that relatively high temperatures be employed, i.e., above about 60 C., since the impressed voltage required to pass a specific current through an electrolytic cell tends to vary inversely with the temperature of the electrolytic medium.
  • the anode employed is a chemically-resistant conductive material and may be, for example, of platinum, rhodium, or noble metal coated tantalum or titanium.
  • the cathode of FIGURES 1 and 2 is of conventional construction, being conveniently of steel or nickle.
  • the electrodes may properly be positioned in either of two methods. An electrode may be fixed to a side of its compartment as shown in FIGURES 1 and 2 or suspended in it by conventional means. It may, depending upon the nature of the diaphragm or permselective membrane employed, be necessary or desirable to utilize the electrode as a support for such diaphragm or membrane in which case a foraminous electrode is constructed, preferably in the form of a screen mesh or expanded metal and positioned contiguous to the partition being supported.
  • FIGURES 2 and 4 Such a cell incorporating expanded metal electrodes is diagrammed in FIGURES 2 and 4 and a section of the expanded metal itself in FIGURE 5.
  • Expanded metal is the preferred material for use as foraminous supporting electrodes and is readily available commercially.
  • the expanded mesh is made by cutting in alternately placed rows a series of fine slits in a sheet of the desired metal and pulling the sheet perpendicular to the direction of the slits, resulting in the expansion of the slits to form essentially diamondor other shaped holes.
  • the diamond-shaped holes 21 can be made in various dimensions so that the total available surface area of the metal 22 will vary correspondingly.
  • the expanded material is fabricated from an electrolytic valve metal preferably tantalum, titanium, or niobium, which is coated with a noble metal such as platinum or rhodium.
  • the dimension of the diamond-shaped holes should be small enough to allow proper support of a microporous diaphragm, but also sufficiently large so as to not offer any appreciable resistance to hydraulic flow therethrough.
  • the holes are of a size larger than the pore size of the porous diaphragm.
  • the non-permselective diaphragm is of such design and porosity that it will allow passage of electrolyte solution but permeable to ions carrying a. positive charge.
  • Permselectivity toward cations is defined as the membranes possession of a higher transport number for cations than that of the solution in which it performs. It is essential that the membrane employed in the processes of the present invention. have as high a cation transport number as possible and be substantially nonpermeable to anions.
  • the art contains many examples of cation-exchange materials which can be formed into cation-permselective membranes.
  • the mechanism underlyingthe operation of an ion-exchange membrane is determined from its construction which consists of a polymeric structure containing dissoluble ionizable radicals, one ionic compound being fixed into the polymeric matrix, the other. a mobile and replaceable ion electrostatically associated with the fixed compound.
  • the replacement of the mobile ions by ions of like sign in the solution: in which the membrane is immersed is the particular property of such membranes which characterizes it as an ion exchange material.
  • the type of cation is determined from its construction which consists of a polymeric structure containing dissoluble ionizable radicals, one ionic compound being fixed into the polymeric matrix, the other. a mobile and replaceable ion electrostatically associated with the fixed compound.
  • the replacement of the mobile ions by ions of like sign in the solution: in which the membrane is immersed is the particular property of
  • the solid polymeric material recovered is then saturated with water or an aqueous solution of an acid or base to convert the anhydride, ester, or acid radicals in the polymeric matrix to their acidic or alkali metal salt form.
  • cation exchange materials may be prepared by the condensation of resorcylic acid with formaldehyde, by the use of sulfonated or. carboxylated humic materials, etc.
  • the resinous material is incorporated into'a sheet-like reinforcing matrix in order'to increase the mechanical strength and heat resistance of the membranes.
  • Suitable reinforcing materials include, for example, woven or felted materials, such as glass filter cloth, polyvinylidene chloride screen, cellulose paper, asbestos, polytetrofluoroethylene or Saran cloth and similar porous materials of adequate strength.
  • the cathode compartment 9 contained a nickel sheet cathode 11 and was separated from the anode feed cell 5 by a self-supporting carboxylic type cationexchange membrane 10 made as a copolymer of acrylic acid and divinyl benzene.
  • the spacing between electrodes was about A".
  • a 10% solution of sodium sulfate was introduced into the anode feed compartment through conduit 7 at such a rate and pressure that the percolation of this electrolyte through the porous diaphragm 6 and expanded anode 2 was sufiicient so as to appreciably prevent the back migration or ditfusion of anodic products into the anode feed, compartment. Since the positively charged hydrogen ions formed at the anode surface tend to. travel in the direction of the negatively charged cathode, the sodium sulfate electrolyte is allowed to percolate through the microporous diaphragm at a velocity greater than that of the opposing migrating hydrogen ions.
  • Example 2 The cell configuration indicated by FIGURE 4 was employed to electrolyze a solution of sodium chloride using unsubmerged operation of both porous electrodes as shown by the liquid levels at 48 and 49.
  • the same type cation-exchange membrane 10 was used in'this example as that of Example 1.
  • the cathode 11a was made of 8 mesh nickel screen which supported a .010" thick microporous polyvinyl chloride diaphragm containing average pore sizes in the order of 10-16 microns.
  • the anode 2a consisted of platinized expanded tantalum having diamond-shaped holes measuring A" in its longest dimension and 4;" across.
  • the electrolysis was conducted at 125 amps per square foot of membrane area, at a total cell voltage of 4.1 and at a temperature of C.
  • the steady state cathode product was 4.4 normal rayon grade caustic, representing a current etficiency of 95%.
  • the caustic in the cathode feed chamber analyzed to less than 1.2 normal.
  • Another novel application of the processes of the present invention is directed toward the removal of carbon dioxide from air or other gases, said application being of particular significance with respect to purification of air in closed systems wherein it is either inconvenient or impossible to introduce a continuing supply of materials such as carbon dioxide absorbing fluids; an example of such a closed system being a submarine.
  • This application comprises the following steps and installations:
  • An electrolytic cell equivalent in design and function to those described herein is constructed and operated with an electrolytic infiuent feed solution of sodium sulfate, for example, 3 N.
  • the catholyte effluent product is aqueous sodium hydroxide and the anolyte efiluent product is sodium bisulfate.
  • the anode compartment is also the site for the production of oxygen which is passed into the atmosphere of the particular system being purified.
  • the product sodium hydroxide solution is conducted to a scrubbing apparatus wherein the atmosphere or particular gas whose purification is desired is passed and its content of carbon dioxide absorbed by the caustic, forming sodium carbonate.
  • the carbonate-containing solution is then (3) combined with an equivalent amount of the anolyte effiuent product sodium bisulfate to regenerate the original sodium sulfate feed solution.
  • This sodium sulfate solution is recycled (4) to the electrolytic cell. Since the sodium sulfate is thus substantially regenerated, the production of oxygen is dependent wholly upon the electrolysis of water, whose source is ordinarily readily available.
  • a four-compartment electrolytic cell comprising a terminal anode compartment, an adjacent anode feed compartment, a next adjacent cathode feed compartment and a terminal cathode compartment, said terminal compartments containing therein an anode and cathode repectively, the terminal anode compartment separated from its adjacent anode feed compartment by a first liquid-permable porous diaphragm, the terminal cathode compartment separated from its adjacent cathode feed compartment by a second liquid-permeable porous diaphragm, said feed compartments of anode and cathode being separated and defined from each other by a cations'elective ion-exchange membrane, inlet means only for passing an electrolyte solution into said anode feed compartment with means for maintaining pressure in said feed compartment greater than the pressure in the adjacent anode compartment to cause said electrolyte solution to pass through said first liquid-permeable diaphragm into said anode compartment, inlet
  • At least one electrode is comprised of a foraminous material on the surface of which is deposited a porous diaphragm, said porosity of the electrode being greater than that of said porous diaphragm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US185424A 1961-05-05 1962-04-05 Process and apparatus for electrolyzing salt solutions Expired - Lifetime US3222267A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
NL278049D NL278049A (zh) 1961-05-05
US185424A US3222267A (en) 1961-05-05 1962-04-05 Process and apparatus for electrolyzing salt solutions
GB17119/62A GB963932A (en) 1961-05-05 1962-05-04 The process and apparatus for electrodialyzing solutions
FR896595A FR1324549A (fr) 1961-05-05 1962-05-05 Procédé et installation pour la décomposition de solutions salines aqueuses par voie électrolytique

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US108061A US3135673A (en) 1961-05-05 1961-05-05 Process and apparatus for electrolyzing salt solutions
US185424A US3222267A (en) 1961-05-05 1962-04-05 Process and apparatus for electrolyzing salt solutions

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Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3438879A (en) * 1967-07-31 1969-04-15 Hooker Chemical Corp Protection of permselective diaphragm during electrolysis
US3496077A (en) * 1967-12-18 1970-02-17 Hal B H Cooper Electrolyzing of salt solutions
US3515513A (en) * 1969-02-03 1970-06-02 Ionics Carbonation process for so2 removal
US3523880A (en) * 1967-12-27 1970-08-11 Ionics Electrolytic cell for removal and recovery of so2 from waste gases
US3523755A (en) * 1968-04-01 1970-08-11 Ionics Processes for controlling the ph of sulfur dioxide scrubbing system
US3524801A (en) * 1968-02-09 1970-08-18 Ionics Process for producing sulfuric acid from so2 containing waste gas
US3525643A (en) * 1966-04-13 1970-08-25 Anita Ryhiner Process for producing electrical energy in a fuel cell
US3547791A (en) * 1967-03-16 1970-12-15 Ici Ltd Manufacture of chlorine and caustic alkali in diaphragm cells
US3899403A (en) * 1973-11-01 1975-08-12 Hooker Chemicals Plastics Corp Electrolytic method of making concentrated hydroxide solutions by sequential use of 3-compartment and 2-compartment electrolytic cells having separating compartment walls of particular cation-active permselective membranes
US3904495A (en) * 1974-01-02 1975-09-09 Hooker Chemicals Plastics Corp Electrolytic-electrodialytic and chemical manufacture of chlorine dioxide, chlorine and chloride-free alkali metal hydroxide
JPS50120492A (zh) * 1974-03-07 1975-09-20
US3954579A (en) * 1973-11-01 1976-05-04 Hooker Chemicals & Plastics Corporation Electrolytic method for the simultaneous manufacture of concentrated and dilute aqueous hydroxide solutions
US4036717A (en) * 1975-12-29 1977-07-19 Diamond Shamrock Corporation Method for concentration and purification of a cell liquor in an electrolytic cell
US4040919A (en) * 1974-10-29 1977-08-09 Hooker Chemicals & Plastics Corporation Voltage reduction of membrane cell for the electrolysis of brine
DE2747381A1 (de) * 1976-10-22 1978-04-27 Asahi Denka Kogyo Kk Verfahren zum elektrolysieren von waessrigen alkalihalogenidloesungen
DE3020260A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren zur herstellung von chromsaeure unter verwendung von zweiraum- und dreiraum-zellen
DE3020261A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren und vorrichtung zur herstellung von chromsaeure
US4268366A (en) * 1979-04-23 1981-05-19 Occidental Research Corporation Method of concentrating alkali hydroxide in three compartment hybrid cells
US4290864A (en) * 1979-05-29 1981-09-22 Diamond Shamrock Corporation Chromic acid production process using a three-compartment cell
US4308123A (en) * 1979-11-30 1981-12-29 Hydro-Chlor International, Inc. Apparatus for the small-scale manufacture of chlorine and sodium hydroxide or sodium hypochlorite
US4861555A (en) * 1985-03-11 1989-08-29 Applied Automation, Inc. Apparatus for chromatographic analysis of ionic species
US5242552A (en) * 1990-03-21 1993-09-07 Eltech Systems Corporation System for electrolytically generating strong solutions by halogen oxyacids
US6375824B1 (en) 2001-01-16 2002-04-23 Airborne Industrial Minerals Inc. Process for producing potassium hydroxide and potassium sulfate from sodium sulfate
US20080245660A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Renewable energy system for hydrogen production and carbon dioxide capture
WO2010067310A1 (en) * 2008-12-09 2010-06-17 Hydrox Holdings Limited Method and apparatus for producing and separating combustible gasses
US20100313794A1 (en) * 2007-12-28 2010-12-16 Constantz Brent R Production of carbonate-containing compositions from material comprising metal silicates
US20120085657A1 (en) * 2010-10-07 2012-04-12 Sai Bhavaraju Chemical systems and methods for operating an electrochemical cell with an acidic anolyte
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US8491858B2 (en) 2009-03-02 2013-07-23 Calera Corporation Gas stream multi-pollutants control systems and methods
US8603424B2 (en) 2008-09-30 2013-12-10 Calera Corporation CO2-sequestering formed building materials
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US8894830B2 (en) 2008-07-16 2014-11-25 Celera Corporation CO2 utilization in electrochemical systems
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US9493881B2 (en) 2011-03-24 2016-11-15 New Sky Energy, Inc. Sulfate-based electrolysis processing with flexible feed control, and use to capture carbon dioxide

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1235063A (en) * 1915-02-16 1917-07-31 Elektro Osmose Ag Electro-osmotic process of treating liquid mixture.
US1235064A (en) * 1915-02-16 1917-07-31 Elektro Osmose Ag Electro-osmotic purification of gelatinous substances.
US2198045A (en) * 1936-02-20 1940-04-23 Ig Farbenindustrie Ag Process for the electrolysis of sulphate solutions
US2794776A (en) * 1954-03-16 1957-06-04 Robert E Briggs Water purification process
US3017338A (en) * 1958-03-03 1962-01-16 Diamond Alkali Co Electrolytic process and apparatus
US3057794A (en) * 1961-10-10 1962-10-09 Pittsburgh Plate Glass Co Electrolytic cell diaphragm
US3084113A (en) * 1960-02-01 1963-04-02 Gen Electric Methods of and apparatus for demineralizing water
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3135673A (en) * 1961-05-05 1964-06-02 Ionics Process and apparatus for electrolyzing salt solutions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1235063A (en) * 1915-02-16 1917-07-31 Elektro Osmose Ag Electro-osmotic process of treating liquid mixture.
US1235064A (en) * 1915-02-16 1917-07-31 Elektro Osmose Ag Electro-osmotic purification of gelatinous substances.
US2198045A (en) * 1936-02-20 1940-04-23 Ig Farbenindustrie Ag Process for the electrolysis of sulphate solutions
US2794776A (en) * 1954-03-16 1957-06-04 Robert E Briggs Water purification process
US3017338A (en) * 1958-03-03 1962-01-16 Diamond Alkali Co Electrolytic process and apparatus
US3124520A (en) * 1959-09-28 1964-03-10 Electrode
US3084113A (en) * 1960-02-01 1963-04-02 Gen Electric Methods of and apparatus for demineralizing water
US3135673A (en) * 1961-05-05 1964-06-02 Ionics Process and apparatus for electrolyzing salt solutions
US3057794A (en) * 1961-10-10 1962-10-09 Pittsburgh Plate Glass Co Electrolytic cell diaphragm

Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3525643A (en) * 1966-04-13 1970-08-25 Anita Ryhiner Process for producing electrical energy in a fuel cell
US3547791A (en) * 1967-03-16 1970-12-15 Ici Ltd Manufacture of chlorine and caustic alkali in diaphragm cells
US3438879A (en) * 1967-07-31 1969-04-15 Hooker Chemical Corp Protection of permselective diaphragm during electrolysis
US3496077A (en) * 1967-12-18 1970-02-17 Hal B H Cooper Electrolyzing of salt solutions
US3523880A (en) * 1967-12-27 1970-08-11 Ionics Electrolytic cell for removal and recovery of so2 from waste gases
US3524801A (en) * 1968-02-09 1970-08-18 Ionics Process for producing sulfuric acid from so2 containing waste gas
US3523755A (en) * 1968-04-01 1970-08-11 Ionics Processes for controlling the ph of sulfur dioxide scrubbing system
US3515513A (en) * 1969-02-03 1970-06-02 Ionics Carbonation process for so2 removal
US3954579A (en) * 1973-11-01 1976-05-04 Hooker Chemicals & Plastics Corporation Electrolytic method for the simultaneous manufacture of concentrated and dilute aqueous hydroxide solutions
US3899403A (en) * 1973-11-01 1975-08-12 Hooker Chemicals Plastics Corp Electrolytic method of making concentrated hydroxide solutions by sequential use of 3-compartment and 2-compartment electrolytic cells having separating compartment walls of particular cation-active permselective membranes
US3904495A (en) * 1974-01-02 1975-09-09 Hooker Chemicals Plastics Corp Electrolytic-electrodialytic and chemical manufacture of chlorine dioxide, chlorine and chloride-free alkali metal hydroxide
JPS50120492A (zh) * 1974-03-07 1975-09-20
JPS551351B2 (zh) * 1974-03-07 1980-01-12
US4357218A (en) * 1974-03-07 1982-11-02 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane and use thereof in the electrolysis of sodium chloride
US4040919A (en) * 1974-10-29 1977-08-09 Hooker Chemicals & Plastics Corporation Voltage reduction of membrane cell for the electrolysis of brine
US4036717A (en) * 1975-12-29 1977-07-19 Diamond Shamrock Corporation Method for concentration and purification of a cell liquor in an electrolytic cell
US4093531A (en) * 1975-12-29 1978-06-06 Diamond Shamrock Corporation Apparatus for concentration and purification of a cell liquor in an electrolytic cell
DE2747381A1 (de) * 1976-10-22 1978-04-27 Asahi Denka Kogyo Kk Verfahren zum elektrolysieren von waessrigen alkalihalogenidloesungen
US4137136A (en) * 1976-10-22 1979-01-30 Asahi Denka Kogyo Kabushiki Kaisha Method for electrolyzing alkali metal halide aqueous solution
US4268366A (en) * 1979-04-23 1981-05-19 Occidental Research Corporation Method of concentrating alkali hydroxide in three compartment hybrid cells
US4384937A (en) * 1979-05-29 1983-05-24 Diamond Shamrock Corporation Production of chromic acid in a three-compartment cell
US4273628A (en) * 1979-05-29 1981-06-16 Diamond Shamrock Corp. Production of chromic acid using two-compartment and three-compartment cells
US4290864A (en) * 1979-05-29 1981-09-22 Diamond Shamrock Corporation Chromic acid production process using a three-compartment cell
DE3020261A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren und vorrichtung zur herstellung von chromsaeure
DE3020260A1 (de) * 1979-05-29 1980-12-11 Diamond Shamrock Corp Verfahren zur herstellung von chromsaeure unter verwendung von zweiraum- und dreiraum-zellen
US4308123A (en) * 1979-11-30 1981-12-29 Hydro-Chlor International, Inc. Apparatus for the small-scale manufacture of chlorine and sodium hydroxide or sodium hypochlorite
US4861555A (en) * 1985-03-11 1989-08-29 Applied Automation, Inc. Apparatus for chromatographic analysis of ionic species
US5242552A (en) * 1990-03-21 1993-09-07 Eltech Systems Corporation System for electrolytically generating strong solutions by halogen oxyacids
US6375824B1 (en) 2001-01-16 2002-04-23 Airborne Industrial Minerals Inc. Process for producing potassium hydroxide and potassium sulfate from sodium sulfate
US20080245672A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Electrochemical methods to generate hydrogen and sequester carbon dioxide
US20080248350A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Electrochemical apparatus to generate hydrogen and sequester carbon dioxide
US20080245660A1 (en) * 2007-04-03 2008-10-09 New Sky Energy, Inc. Renewable energy system for hydrogen production and carbon dioxide capture
WO2008124538A1 (en) * 2007-04-03 2008-10-16 New Sky Energy, Inc. Electrochemical system, apparatus, and method to generate renewable hydrogen and sequester carbon dioxide
US8227127B2 (en) * 2007-04-03 2012-07-24 New Sky Energy, Inc. Electrochemical apparatus to generate hydrogen and sequester carbon dioxide
AU2008237264B2 (en) * 2007-04-03 2012-09-20 Sulfurcycle Intellectual Property Holding Company Llc Electrochemical system, apparatus, and method to generate renewable hydrogen and sequester carbon dioxide
US20100313794A1 (en) * 2007-12-28 2010-12-16 Constantz Brent R Production of carbonate-containing compositions from material comprising metal silicates
US9260314B2 (en) 2007-12-28 2016-02-16 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
US8333944B2 (en) 2007-12-28 2012-12-18 Calera Corporation Methods of sequestering CO2
US8894830B2 (en) 2008-07-16 2014-11-25 Celera Corporation CO2 utilization in electrochemical systems
US8470275B2 (en) 2008-09-30 2013-06-25 Calera Corporation Reduced-carbon footprint concrete compositions
US8603424B2 (en) 2008-09-30 2013-12-10 Calera Corporation CO2-sequestering formed building materials
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
WO2010067310A1 (en) * 2008-12-09 2010-06-17 Hydrox Holdings Limited Method and apparatus for producing and separating combustible gasses
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US9267211B2 (en) 2009-02-10 2016-02-23 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
US8883104B2 (en) 2009-03-02 2014-11-11 Calera Corporation Gas stream multi-pollutants control systems and methods
US8491858B2 (en) 2009-03-02 2013-07-23 Calera Corporation Gas stream multi-pollutants control systems and methods
US20120085657A1 (en) * 2010-10-07 2012-04-12 Sai Bhavaraju Chemical systems and methods for operating an electrochemical cell with an acidic anolyte
US9611555B2 (en) * 2010-10-07 2017-04-04 Ceramatec, Inc. Chemical systems and methods for operating an electrochemical cell with an acidic anolyte
US9493881B2 (en) 2011-03-24 2016-11-15 New Sky Energy, Inc. Sulfate-based electrolysis processing with flexible feed control, and use to capture carbon dioxide

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