EP2732073B1 - Cellule électrolytique non divisée et son utilisation - Google Patents

Cellule électrolytique non divisée et son utilisation Download PDF

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Publication number
EP2732073B1
EP2732073B1 EP12737524.4A EP12737524A EP2732073B1 EP 2732073 B1 EP2732073 B1 EP 2732073B1 EP 12737524 A EP12737524 A EP 12737524A EP 2732073 B1 EP2732073 B1 EP 2732073B1
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Prior art keywords
electrolyte
anode
approximately
sulfate
cathode
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German (de)
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EP2732073A2 (fr
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Michael Müller
Patrick Keller
Markus Schiermeier
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United Initiators GmbH and Co KG
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United Initiators GmbH and Co KG
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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
    • 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

Definitions

  • the present invention relates to a process for the preparation of an ammonium or alkali metal peroxodisulfate.
  • Sodium peroxodisulfate is produced at a current efficiency of 70-80% in an electrolytic cell having a diaphragm protected cathode and a platinum anode by providing a neutral aqueous anolyte solution having an initial content of 5 to 9% by weight of sodium ions, 12 to 30% by weight.
  • the mother liquor is mixed with the cathode product, neutralized and fed back to the anode.
  • EP-B 0 428 171 discloses a filter press-type electrolytic cell for producing peroxo compounds, including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • peroxo compounds including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • anodes here hot isostatically applied to a valve metal platinum foils are used.
  • the anolyte used is a solution of the corresponding sulfate containing a promoter and sulfuric acid. This method also has the aforementioned problems.
  • peroxodisulfates are prepared by anodic oxidation of an aqueous solution containing neutral ammonium sulfate.
  • the solution obtained from anodic oxidation containing ammonium peroxodisulfate is reacted with caustic soda or potassium hydroxide solution.
  • the mother liquor is recycled in admixture with the catholyte produced during the electrolysis.
  • the electrolysis is carried out in the presence of a promoter on a platinum electrode as the anode.
  • PA Michaud et al. teach in Electro Chemical and Solid State Letters, 3 (2) 77-79 (2000 ) the production of peroxodisulfuric acid by anodic oxidation of sulfuric acid using a boron doped diamond thin film electrode.
  • This document teaches that such electrodes have a higher overvoltage for oxygen than platinum electrodes.
  • the document gives no indication of the industrial production of ammonium and alkali metal peroxodisulfates using boron-doped diamond thin-film electrodes. Namely, it is known that sulfuric acid on the one hand and hydrogen sulfates in particular neutral sulfates on the other hand behave very differently in the anodic oxidation.
  • the major side reaction besides the anodic oxidation of sulfuric acid is the evolution of oxygen and, in addition, ozone.
  • the present application accordingly provides a process for producing an ammonium or alkali metal peroxodisulfate comprising an anodic oxidation of an aqueous electrolyte containing a salt selected from ammonium sulfate, alkali metal sulfate and / or the corresponding hydrogen sulfate in an electrolytic cell comprising at least one anode and a cathode using as the anode a diamond layer disposed on a conductive support and doped with a trivalent or pentavalent element, the electrolytic cell comprising a tube cell having an undivided electrolyzer space between the anode and the cathode, and the aqueous electrolyte not having a promoter to increase contains the decomposition voltage of water to oxygen.
  • ammonium sulfate, alkali metal sulfate and / or the corresponding bisulfate salt used for anodizing may be any of the alkali metal sulfate or corresponding bisulfate. In the context of the present application, however, the use of sodium and / or potassium sulfate and / or the corresponding hydrogen sulfate is particularly preferred.
  • Promoter or "polarizer” in the context of the present invention is any means known to those skilled in the art as an additive in carrying out an electrolysis to increase the decomposition voltage of water to oxygen or to improve the current efficiency.
  • An example of such a promoter used in the prior art is thiocyanate such as, for example, sodium or ammonium thiocyanate. According to the invention, such a promoter is not used.
  • the electrolyte in the process according to the invention has a promoter concentration of 0 g / l.
  • an anode which comprises a diamond layer arranged on a conductive support and doped with a 3- or 5-valent element.
  • the support material is selected from the group consisting of silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements and / or aluminum or combinations of the elements.
  • the doped with a 3- or 5-valent element diamond layer is applied on this substrate.
  • the doped diamond layer is thus an n-conductor or a p-type conductor. It is preferred that a boron-doped and / or phosphorus-doped diamond layer is used.
  • the amount of doping is adjusted so that the desired, usually just the sufficient, conductivity is achieved.
  • the crystal structure may contain up to 10,000 ppm of boron.
  • the diamond layer may be applied over the entire surface or in sections, for example, exclusively on the front side or exclusively on the backside of the carrier material.
  • Methods for applying the diamond layer are known in the art.
  • the production of the diamond electrodes can be carried out in particular in two special CVD methods (chemical vapor deposition technique). These are the microwave plasma CVD and the hot wire CVD process.
  • the gas phase which is activated by microwave irradiation or thermally activated by hot wires to the plasma, from methane, hydrogen and optionally further additives, in particular a gaseous compound of the dopant.
  • a boron compound such as trimethylboron
  • a gaseous phosphorus compound as a dopant
  • an n-type semiconductor is obtained.
  • deposition of the doped diamond layer on crystalline silicon a particularly dense and non-porous layer is obtained - a film thickness of 1 ⁇ m is usually sufficient.
  • the diamond layer is preferably in a film thickness of about 0.5 .mu.m to 5 .mu.m, preferably about 0.8 .mu.m to about 2.0 .mu.m and more preferably about 1.0 .mu.m on the Applied according to the invention used anode support material.
  • the deposition can also take place on a self-passivating metal, such as titanium, tantalum, tungsten or niobium.
  • a self-passivating metal such as titanium, tantalum, tungsten or niobium.
  • anode comprising a niobium or titanium support with a boron-doped diamond layer, in particular a diamond layer boron-doped up to 10,000 ppm in the crystal structure, is particularly preferred.
  • the cathode used in the process according to the invention is preferably formed from lead, carbon, tin, platinum, nickel, alloys of these elements, zirconium and / or acid-resistant stainless steels, as known to the person skilled in the art. Spatially, the cathode can be configured arbitrarily.
  • the electrolyte space between anode and cathode is undivided, ie there is no separator between the anode and the cathode.
  • the use of an undivided cell allows electrolyte solutions with very high solids concentrations, which in turn significantly reduces the energy expenditure in salt recovery, essentially crystallization and water evaporation, directly proportional to the increase in solids content, but at least 25% of that of a divided cell.
  • a tube geometry ie a tube cell, consisting of an inner tube as the anode, preferably made of diamond-coated niobium, and an outer tube as the cathode, preferably made of acid-resistant stainless steel, represents, with low material costs, an advantageous construction.
  • the use of an annular gap as the common electrolyte space is preferred and leads to a uniform and thus flow loss-poor flow and thus to a high utilization of the available electrolysis areas, which in turn means a high current efficiency.
  • the manufacturing costs of such a cell are low in relation to a so-called flat cell.
  • the electrolyte used in the process according to the invention preferably has an acidic, preferably sulfur-acidic, or neutral pH.
  • the electrolyte is circulated through the electrolytic cell during the process. This prevents a, the decomposition of the persulfate accelerating and thus undesirable high electrolyte temperature in the cell.
  • the method comprises a discharge of electrolyte solution from the electrolyte circuit. This can be done in particular for the production of peroxodisulfate produced.
  • a further preferred embodiment therefore relates to the recovery of peroxodisulfates produced by crystallization and separation of the crystals from the electrolyte solution to form an electrolyte solution, wherein the electrolyte solution has been preferably previously discharged from the electrolyte circuit.
  • Another preferred embodiment comprises recirculating the electrolyte mother liquor, especially if previously produced peroxodisulfates were separated, increasing the content of acid, sulfate and / or hydrogen sulfate in the electrolysis cell.
  • the anodic oxidation is preferably carried out according to the invention at an anodic current density of 50-1500 mA / cm 2, and more preferably about 50-1200 mA / cm 2 .
  • a particularly preferred current density is in the range of 60-975 mA / cm 2 .
  • the electrolyte used in the process according to the invention preferably has a total solids content of about 0.5 to 650 g / l.
  • the (working) electrolyte preferably contains about 100 to about 500 g / L of persulfate, more preferably about 150 to about 450 g / L of persulfate, and most preferably 250-400 g / L of persulfate.
  • the inventive method thus enables in particular high solids concentrations in the electrolyte solution, without the addition of a potential-enhancing agent or promoter and the resulting requirements for exhaust gas and wastewater treatment at the same time high current yields in Peroxodisul father ein.
  • the electrolytic solution preferably contains about 0.1 to about 3.5 moles of sulfuric acid per liter of (I) electrolytic solution, more preferably 1-3 moles of sulfuric acid per liter of electrolyte solution, and most preferably 2.2 to 2.8 moles of sulfuric acid per liter of electrolyte solution.
  • an electrolyte having the following composition: per liter of electrolyte 150 to 500 g of persulfate and 0.1 to 3.5 mol of sulfuric acid per mole of electrolyte solution.
  • the total solids content is preferably 0.5 g / L to 650 g / L, more preferably 100-500 g / L, and most preferably 250-400 g / L, with the sulfate content being variable.
  • the promoter content is 0 g / l.
  • Also described is a built from individual components, undivided electrolysis cell, an electrolysis device constructed from a plurality of such electrolysis cells, and their use for the oxidation of an electrolyte.
  • electrolysis is meant a chemical change caused by the passage of electricity through an electrolyte, which is expressed in a direct conversion of electrical energy into chemical energy through the mechanism of electrode reactions and ion migration.
  • the technically most important electrochemical conversion is the electrolysis of saline solution, which produces caustic soda and chlorine gas.
  • the production of inorganic peroxides is nowadays carried out industrially in electrolysis cells.
  • anode and cathode materials must meet the mechanical requirements at high solids concentrations and therefore be extremely resistant to wear.
  • the electrolysis cells must be designed so that the electrolysis can be carried out at the highest possible current densities. This is only possible if anode and cathode have good electrical conductivity and are chemically inert to the electrolyte. Typically, graphite or platinum is used as the anode material. However, these materials have the disadvantage that they do not have sufficient abrasion resistance at high solids concentrations.
  • electrodes are coated with an electrically conductive diamond layer, wherein the diamond layer is applied by a chemical vapor deposition method (CVD).
  • CVD chemical vapor deposition method
  • the task was to provide an electrolysis cell which enables a continuous and optimized electrolysis process at high solids concentrations (up to about 650 g / l) and at high current density ranges (up to about 1500 mA / cm 2 ).
  • the electrolysis cell should be adapted to the electrochemical reactions to be performed and individual components can be easily replaced without the actual cell body is destroyed.
  • anode and cathode are arranged concentrically to each other, so that preferably the electrolyte space forms as an annular gap between the inside anode and the outside cathode.
  • the diameter of the cathode is larger than that of the anode.
  • the electrolyte space contains no membrane or no diaphragm.
  • it is an electrolytic cell with a common electrolyte space, i. the electrolysis cell is undivided.
  • the distance between the anode outer surface and the cathode inner surface is between 1-20 mm, more preferably between 1-15 mm, even more preferably between 2-10 mm, and most preferably between 2-6 mm.
  • the inner diameter of the cathode is preferably between 10-400 mm, more preferably between 20-300 mm, even more preferably between 25-250 mm.
  • the anode and cathode are each independently between 20-120 cm, more preferably between 25-75 cm long.
  • the length of the electrolyte space is preferably at least 20 cm, more preferably at least 25 cm, and most preferably 120 cm, more preferably 75 cm.
  • the cathode is preferably made of lead, carbon, tin, platinum, nickel, alloys of these elements, zirconium and / or iron alloys, in particular of stainless steel, in particular acid-resistant stainless steel.
  • the cathode is made of acid-resistant stainless steel.
  • the base material of the rod-shaped or tubular, preferably tubular, anode is preferably silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements, and / or aluminum, or combinations of the elements.
  • the anode support material may be identical to or different from the anode base material.
  • the anode base material functions as a conductive carrier.
  • the conductive support any conductive material known in the art can be used. Particularly preferred support materials are silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements, and / or aluminum, or combinations of the elements. Silicon, titanium, niobium, tantalum, tungsten or carbides of these elements, more preferably niobium or titanium, even more preferably niobium, is particularly preferably used as the conductive support.
  • a conductive diamond layer is applied on this substrate.
  • the diamond layer may be doped with at least one 3- or at least one 5-valent main or subgroup element.
  • the doped diamond layer is thus an n-conductor or a p-type conductor. It is preferred that a boron-doped and / or phosphorus-doped diamond layer is used.
  • the amount of doping is adjusted so that the desired, usually just the sufficient, conductivity is achieved.
  • the crystal structure may contain up to 10,000 ppm, preferably from 10 ppm to 2,000 ppm, of boron and / or phosphorus.
  • the diamond layer may be applied over the entire surface or in sections, preferably on the entire outer surface of the rod-shaped or tubular anode.
  • the conductive diamond layer is preferably non-porous.
  • the preparation of the diamond electrodes can be carried out in particular in two special CVD processes (Chemical Vapor Deposition). These are the microwave plasma CVD and the hot wire CVD method. In both cases, the gas phase, which is activated by microwave irradiation or thermally activated by hot wires to the plasma, from methane, hydrogen and optionally further additives, in particular a gaseous compound of the dopant.
  • CVD Chemical Vapor Deposition
  • a p-type semiconductor By using the boron compound such as trimethylboron, a p-type semiconductor can be provided. By using a gaseous phosphorus compound as a dopant, an n-type semiconductor is obtained. By depositing the doped diamond layer on crystalline silicon, a particularly dense and nonporous layer is obtained.
  • the diamond layer is preferably applied in a film thickness of about 0.5-5 .mu.m, preferably about 0.8-2.0 .mu.m and particularly preferably of about 1.0 .mu.m to the conductive support used according to the invention. In another embodiment, the diamond layer is preferably applied in a film thickness of 0.5-35 ⁇ m, preferably 5-25 ⁇ m, most preferably 10-20 ⁇ m, on the conductive support used according to the invention.
  • the deposition can also be carried out on a self-passivating metal, such as titanium, tantalum, tungsten, or niobium.
  • a self-passivating metal such as titanium, tantalum, tungsten, or niobium.
  • PA Michaud Electrochemical and Solid State Letters, 3 (2) 77-79 (2000 )
  • anode comprising a niobium or titanium support with a boron-doped diamond layer, in particular with a diamond layer doped with up to 10,000 ppm boron, is particularly preferred.
  • the diamond-coated electrodes are characterized by a very high mechanical strength and abrasion resistance.
  • the anode and / or the cathode more preferably the anode and the cathode, even more preferably the anode is connected to the power source via the distributor means.
  • the distributor device is correspondingly electrically insulated. In any case, ensure good electrical contact between anode and / or cathode and distribution device.
  • the distribution device further ensures a homogeneous feed of the electrolyte from the inlet pipe into the electrolyte space. After the electrolyte has passed the electrolyte space, the reacted electrolyte (electrolysis product) is effectively collected by means of at least one upstream distributor device and discharged via a drainage pipe.
  • the distributor devices preferably consist of silicon, germanium, titanium, zirconium, niobium, tantalum, molybdenum, tungsten, carbides of these elements and / or aluminum or combinations of the elements, particularly preferably of titanium.
  • the distribution devices preferably have at least one connection point for at least one discharge or supply pipe and a connection point for the anode.
  • the connection point for the anode forms an optionally closed hollow cylinder, which is flush with the anode tube or -stab completes.
  • the hollow cylinder in the distributor devices can close off the anode tube so that no electrolyte can get into the interior of the anode.
  • the connection point of the distributor device to the anode can have a relief bore into the anode tube. This prevents electrolyte from flowing into the anode tube if the pressure on the distributor element is too high.
  • the optionally closed hollow cylinder of the distributor device can be mounted on the support material of the anode or directly on the diamond-coated carrier. In the latter case, therefore, the carrier and the distributor device are separated from one another by the conductive diamond layer.
  • the distributor device is irreversibly connected to the anode, particularly preferably welded. This is particularly advantageous when working at high currents.
  • the anode and the manifold may be welded by diffusion bonding, electron beam welding or laser welding.
  • Radial bores are distributed over the circumference of the hollow cylinder of the distributor device.
  • the distributor device 3 more preferably 4 and even more preferably has 5 radial bores. Due to the radial bores in the distributor device, the electrolyte can be distributed homogeneously and in a streamlined manner into the electrolyte space and, after passage of the electrolyte space, the electrolysis product can be effectively removed.
  • the electrolyte is preferably supplied via the inlet pipe of the electrolytic cell and in particular the distributor device.
  • the electrolysis product is preferably removed from the electrolysis cell via the outlet pipe, in particular after the electrolysis product has been collected in the distributor device.
  • the manifold is designed to seal the tubular cathode so that no electrolyte or electrolysis product can escape from the cathode.
  • anode, cathode, distribution device, inlet and outlet pipe can be assembled by an appropriate, known in the art, mounting devices to an electrolytic cell.
  • the tubular electrolysis cell is also characterized by high Strength with low material usage. Parts that wear over time, for example due to the abrasive electrolytes, can be replaced individually, so that in this respect an economical use of materials is guaranteed.
  • the Elekrolytraum is flow streamlined, thereby avoiding flow losses and the surface for the electrochemical mass transfer are optimally utilized. A continuous and homogeneous electrolysis process at high solids concentrations and current density ranges is possible due to the electrode materials and electrode arrangement.
  • Another aspect is an electrolysis apparatus which comprises at least two electrolysis cells, wherein the electrolyte passes through the electrolysis cells in succession and the electrolysis cells are operated in an electrochemically connected manner in parallel.
  • the plant services are flexible and feasible without limits.
  • the electrolytic cell or the electrolysis device is particularly suitable for the oxidation of an electrolyte.
  • the undivided electrolytic cell is particularly suitable for the oxidation of an electrolyte when neither electrolytic nor electrolysis product, which are manufactured or implemented at the anode or cathode, are changed in a disturbing way by the respective other electrode process or react with each other.
  • the electrolysis cells can be operated with a current density between 50-1500 mA / cm 2 , preferably 50-1200 mA / cm 2 , more preferably 60-975 mA / cm 2 and thus enable large-scale and economical processes.
  • the electrolysis cells / electrolysis devices according to the invention can moreover be used at very high solids contents of between 0.5-650 g / l, preferably 100-500 g / l, more preferably 150-450 g / l and even more preferably 250-400 g / l.
  • the electrolysis cells / devices are particularly suitable for the anodic oxidation of sulfate to peroxodisulfate.
  • the electrolysis cells / electrolysis devices have been proven especially for the production of peroxodisulfates.
  • Sodium peroxodisulfate is produced at a current efficiency of 70-80% in an electrolytic cell having a diaphragm protected cathode and a platinum anode by providing a neutral aqueous anolyte solution having an initial content of 5 to 9% by weight of sodium ions, 12 to 30% by weight.
  • Sulfate ions 1 to 4 wt .-% ammonium ions, 6 to 30 wt .-% peroxodisulfate ions and a potential-increasing promoter, in particular thiocyanate, using a Sulfuric acid solution is electrolyzed as a catholyte at a current density of at least 0.5 to 2 A / cm 2 .
  • the mother liquor is mixed with the cathode product, neutralized and fed back to the anode.
  • EP-B 0 428 171 discloses a filter press-type electrolytic cell for producing peroxo compounds, including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • peroxo compounds including ammonium peroxodisulfate, sodium peroxodisulfate and potassium peroxodisulfate.
  • anodes here hot isostatically applied to a valve metal platinum foils are used.
  • the anolyte used is a solution of the corresponding sulfate containing a promoter and sulfuric acid. This method also has the aforementioned problems.
  • peroxodisulfates are prepared by anodic oxidation of an aqueous solution containing neutral ammonium sulfate.
  • the solution obtained from anodic oxidation containing ammonium peroxodisulfate is reacted with caustic soda or potassium hydroxide solution.
  • the mother liquor is recycled in admixture with the catholyte produced during the electrolysis.
  • the electrolysis is carried out in the presence of a promoter on a platinum electrode as the anode.
  • PA Michaud et al. teach in Electro Chemical and Solid State Letters, 3 (2) 77-79 (2000 ) the production of peroxodisulfuric acid by anodic oxidation of sulfuric acid using a boron doped diamond thin film electrode.
  • This document teaches that such electrodes have a higher overvoltage for oxygen than platinum electrodes.
  • the document gives no indication of the industrial production of ammonium and alkali metal peroxodisulfates using boron-doped diamond thin-film electrodes. Namely, it is known that sulfuric acid on the one hand and hydrogen sulfates in particular neutral sulfates on the other hand behave very differently in the anodic oxidation.
  • the major side reaction besides the anodic oxidation of sulfuric acid is the evolution of oxygen and, in addition, ozone.
  • ammonium sulfate, alkali metal sulfate and / or the corresponding bisulfate salt used for anodizing may be any of the alkali metal sulfate or corresponding bisulfate. In the context of the present application, however, the use of sodium and / or potassium sulfate and / or the corresponding hydrogen sulfate is particularly preferred.
  • the electrolyte space between anode and cathode is undivided, i. there is no separator between anode and cathode.
  • the use of an undivided cell allows electrolyte solutions with very high solids concentrations, which in turn significantly reduces the energy expenditure in salt recovery, essentially crystallization and water evaporation, directly proportional to the increase in solids content, but at least 25% of that of a divided cell.
  • the use of a promoter is not necessary.
  • Promoter in the context of the present invention is any means known to those skilled in the art as an adjunct in the performance of electrolysis to increase the decomposition voltage of water to oxygen or to improve current efficiency.
  • An example of such a promoter used in the prior art is thiocyanate, such as, for example, sodium or ammonium thiocyanate.
  • the electrolyte used preferably has an acidic, preferably sulfur-acidic, or neutral pH.
  • the electrolyte may be circulated through the electrolytic cell during the process. This prevents a, the decomposition of the persulfate accelerating and thus undesirable high electrolyte temperature in the cell.
  • a discharge of electrolyte solution from the electrolyte circuit takes place to obtain generated peroxodisulfate.
  • the produced peroxodisulfate can be obtained by crystallizing and separating the crystals from the electrolytic solution to form an electrolyte liquor.
  • the electrolyte used preferably has a total solids content of about 0.5 to 650 g / l at the beginning of the electrolysis.
  • the electrolyte preferably contains from about 100 to about 500 g / L of sulfate, more preferably from about 150 to about 450 g / L of sulfate, and most preferably 250-400 g / L of sulfate at the beginning of the reaction.
  • the use of the electrolysis cell / device according to the invention thus enables high solids concentrations in the electrolyte solution, without the addition of a potential-enhancing agent or promoter and the resulting requirements for exhaust gas and wastewater treatment at the same time high current yields in Peroxodisul father ein.
  • the electrolytic solution preferably contains about 0.1 to about 3.5 moles of sulfuric acid per liter of (I) electrolytic solution, more preferably 1-3 moles of sulfuric acid per liter of electrolyte solution, and most preferably 2.2 to 2.8 moles of sulfuric acid per liter of electrolyte solution.
  • an electrolyte having the following composition: per liter of starting electrolyte, 150 to 500 g of sulphate and 0.1 to 3.5 mol of sulfuric acid per liter of electrolyte solution.
  • the total solids content is preferably 0.5 g / L to 650 g / L, more preferably 100-500 g / L, and most preferably 250-400 g / L.
  • the promoter content is 0 g / l.
  • FIG. 3 shows a possible embodiment of an electrolytic cell according to the present invention.
  • FIG. 4 A cross section of this model is in FIG. 4 shown schematically.
  • the electrolyte passes into the distributor device (2a) and is supplied from there aerodynamically to the electrolyte space (3).
  • the electrolyte space (3) is formed by the annular gap between the outer surface of the anode (4) and the inner surface of the cathode (5).
  • the electrolysis product is collected by distributor device (2b) and transferred into the discharge pipe (6). Seals (7) close the electrolyte space between inlet and outlet pipe and inner surface of the cathode.
  • the distributor device (2) can be designed such that the distributor device simultaneously undertakes the sealing of the electrolyte space.
  • FIG. 5 shows the individual components of the electrolysis cell. The numbering is analog FIG. 4 , Other components for sealing the electrolysis cell and for mounting are in FIG. 5 shown but not numbered. These components are known in the art and can be replaced as desired.
  • FIG. 6 is an enlarged view of the distributor device (2).
  • the distribution devices has a connection point (21) for a waste or inlet pipe and a connection point (22) for the anode (4).
  • the connection point for the anode forms a hollow cylinder which terminates flush with the anode tube or rod (4).
  • Radial bores (23) are distributed over the circumference of the hollow cylinder of the distributor device. Through the radial bores (23) in the distributor device, the electrolyte can be homogeneously fed into the electrolyte space and be effectively removed after passage of the electrolyte space.
  • the distributor device 3, more preferably 4 and even more preferably has 5 radial bores.
  • a 2-dimensional and on the other a three-dimensional cell consisting of a boron-doped diamond-coated niobium anode (diamond anode according to the invention) was used.
  • Electrolyte initial composition :
  • the electrolyte was concentrated accordingly by circulating (see FIGS. 1 and 2 ).
  • the current efficiency of a diamond-coated niobium anode is about 10% higher even without the addition of a potential-enhancing agent than in a cell with conventional platinum-titanium anode and adding a potential-increasing agent and about 40% higher than in a conventional cell Platinum-titanium anode without adding a potential-enhancing agent.
  • the voltage drop across a diamond-coated anode is about 0.9 volts higher than for a comparable cell with a platinum-titanium anode. Furthermore, it was found that the current yield in a diamond electrode to be used according to the invention without the addition of a promoter with increasing total content of sodium peroxodisulfate in the electrolyte only slowly decreases - under the experimental conditions, for example, at a current efficiency of equal to or above 65% electrolyte solutions with a Natriumperoxodisulfatgehalt of about 400 - 650 g / l win.
  • the working current density can be significantly reduced compared to platinum anodes with the same amount of production, whereby less ohmic losses occur in the system and thus reduces the cooling effort and the degree of freedom in the design of the electrolysis cells and the cathodes is increased.

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Claims (15)

  1. Procédé de préparation d'un peroxodisulfate d'ammonium ou de métal alcalin, comprenant
    l'oxydation anodique d'un électrolyte aqueux contenant un sel choisi parmi le sulfate d'ammonium, le sulfate de métal alcalin et/ou l'hydrogénosulfate correspondant dans une cellule électrolytique,
    comprenant au moins une anode et une cathode,
    dans lequel une couche de diamant dopée avec un élément trivalent ou pentavalent et disposé sur un support conducteur est utilisée comme anode,
    caractérisé en ce que
    une cellule tubulaire est utilisée comme cellule électrolytique, laquelle comprend une chambre électrolytique non divisée entre l'anode et la cathode, et l'électrolyte aqueux ne contient pas de promoteur pour augmenter la tension de décomposition de l'eau en oxygène.
  2. Procédé selon la revendication 1,
    caractérisé en ce que
    le sulfate de métal alcalin et/ou l'hydrogénosulfate correspondant est choisi parmi le sulfate de sodium et/ou de potassium et/ou l'hydrogénosulfate correspondant.
  3. Procédé selon la revendication 1 ou 2,
    caractérisé en ce que
    le matériau support anodique est choisi dans le groupe constitué du silicium, du germanium, du titane, du zirconium, du niobium, du tantale, du molybdène, du tungstène, des carbures de ces éléments et/ou de l'aluminium.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce que
    une couche de diamant dopée au bore et/ou dopée au phosphore, de préférence dopée jusqu'à 10 000 ppm dans le squelette cristallin, est utilisée.
  5. Procédé selon l'une des revendications 1 à 4,
    caractérisé en ce que
    la couche de diamant possède une épaisseur de film d'environ 0,5 µm à environ 5,0 µm, de préférence environ 0,8 µm à environ 2,0 µm et de manière particulièrement préférée d'environ 1,0 µm.
  6. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce que
    une couche de diamant dopée au bore sur un support de niobium ou de titane est utilisée comme anode.
  7. Procédé selon l'une des revendications 1 à 5,
    caractérisé en ce que
    la cathode est formée de plomb, de carbone, d'étain, de platine, de nickel, d'alliages de ces éléments, de zirconium et/ou d'aciers inoxydables résistants aux acides.
  8. Procédé selon l'une des revendications 1 à 7,
    caractérisé en ce que
    plusieurs cellules électrolytiques sont rassemblées, de préférence sous la forme d'un ensemble de doubles tubes ou bien bidimensionnelle.
  9. Procédé selon l'une des revendications 1 à 8,
    caractérisé en ce que
    l'électrolyte présente un pH neutre ou acide.
  10. Procédé selon l'une des revendications 1 à 9,
    caractérisé en ce que
    l'électrolyte se déplace en circuit à travers la cellule électrolytique pendant le procédé.
  11. Procédé selon la revendication 10,
    comprenant un éclusage de la solution électrolytique hors du circuit électrolytique.
  12. Procédé selon l'une des revendications 10 ou 11,
    comprenant l'obtention des peroxodisulfates produits par cristallisation et séparation des cristaux à partir de la solution électrolytique en formant une solution mère électrolytique et comprenant de préférence une recirculation de la solution mère électrolytique, en augmentant la teneur en acide, sulfate et/ou hydrogénosulfate, dans la cellule électrolytique.
  13. Procédé selon l'une des revendications 1 à 12,
    caractérisé en ce que
    l'oxydation anodique est réalisée à une densité de courant anodique d'environ 50 à environ 1500 mA/cm2, de préférence d'environ 250 à environ 1350 mA/cm2, de manière davantage préférée d'environ 400 à environ 1200 mA/cm2.
  14. Procédé selon l'une des revendications 1 à 13,
    caractérisé en ce que
    l'électrolyte présente une teneur en solides totale d'environ 0,5 à environ 650 g/litre.
  15. Procédé selon l'une des revendications 1 à 14,
    caractérisé en ce que
    l'électrolyte comprend environ 100 à environ 500 g/litre de persulfate et/ou environ 0,1 à environ 3,5 moles d'acide sulfurique par litre de solution électrolytique.
EP12737524.4A 2011-07-14 2012-07-13 Cellule électrolytique non divisée et son utilisation Active EP2732073B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12737524.4A EP2732073B1 (fr) 2011-07-14 2012-07-13 Cellule électrolytique non divisée et son utilisation

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP11173916A EP2546389A1 (fr) 2011-07-14 2011-07-14 Procédé de fabrication de peroxodisulfate alcalin ou d'ammonium dans une pièce d'électrolyse non divisée
EP12737524.4A EP2732073B1 (fr) 2011-07-14 2012-07-13 Cellule électrolytique non divisée et son utilisation
PCT/EP2012/063783 WO2013007816A2 (fr) 2011-07-14 2012-07-13 Cellule électrolytique non divisée et son utilisation

Publications (2)

Publication Number Publication Date
EP2732073A2 EP2732073A2 (fr) 2014-05-21
EP2732073B1 true EP2732073B1 (fr) 2017-04-26

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EP11173916A Withdrawn EP2546389A1 (fr) 2011-07-14 2011-07-14 Procédé de fabrication de peroxodisulfate alcalin ou d'ammonium dans une pièce d'électrolyse non divisée
EP12737524.4A Active EP2732073B1 (fr) 2011-07-14 2012-07-13 Cellule électrolytique non divisée et son utilisation

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Country Status (12)

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US (1) US9556527B2 (fr)
EP (2) EP2546389A1 (fr)
JP (1) JP6151249B2 (fr)
KR (1) KR20140054051A (fr)
CN (1) CN103827354B (fr)
CA (1) CA2841843A1 (fr)
DK (1) DK2732073T3 (fr)
ES (1) ES2626642T3 (fr)
PL (1) PL2732073T3 (fr)
RU (1) RU2014105424A (fr)
TR (1) TR201707950T4 (fr)
WO (1) WO2013007816A2 (fr)

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* Cited by examiner, † Cited by third party
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EP2546389A1 (fr) 2011-07-14 2013-01-16 United Initiators GmbH & Co. KG Procédé de fabrication de peroxodisulfate alcalin ou d'ammonium dans une pièce d'électrolyse non divisée
JP5818732B2 (ja) * 2012-03-29 2015-11-18 旭化成ケミカルズ株式会社 電解セル及び電解槽
CN104487615B (zh) * 2012-07-13 2017-08-25 联合引发剂有限责任两合公司 不分离的电解槽及其应用
US9540740B2 (en) 2012-07-13 2017-01-10 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use thereof
KR101686138B1 (ko) * 2014-12-23 2016-12-28 (주) 테크윈 전해모듈
CN112301366A (zh) * 2020-10-30 2021-02-02 福建省展化化工有限公司 一种基于钛基铂金阳极电极电解法制备过硫酸铵的方法
CN116354556B (zh) * 2023-04-07 2024-05-03 湖南新锋科技有限公司 一种太阳能增强电化学处理高盐废水的资源循环利用方法
CN116789236B (zh) * 2023-07-19 2024-06-18 北京大学 一种硫酸钠型高盐废水电解资源化利用方法

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Also Published As

Publication number Publication date
TR201707950T4 (tr) 2018-11-21
JP6151249B2 (ja) 2017-06-21
RU2014105424A (ru) 2015-08-20
EP2546389A1 (fr) 2013-01-16
EP2732073A2 (fr) 2014-05-21
WO2013007816A3 (fr) 2013-06-20
KR20140054051A (ko) 2014-05-08
US9556527B2 (en) 2017-01-31
DK2732073T3 (en) 2017-08-28
ES2626642T3 (es) 2017-07-25
CN103827354B (zh) 2017-05-24
PL2732073T3 (pl) 2017-09-29
CN103827354A (zh) 2014-05-28
CA2841843A1 (fr) 2013-01-17
US20140131218A1 (en) 2014-05-15
JP2014523490A (ja) 2014-09-11
WO2013007816A2 (fr) 2013-01-17

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