EP0066663A1 - Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen - Google Patents

Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen Download PDF

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Publication number
EP0066663A1
EP0066663A1 EP81870029A EP81870029A EP0066663A1 EP 0066663 A1 EP0066663 A1 EP 0066663A1 EP 81870029 A EP81870029 A EP 81870029A EP 81870029 A EP81870029 A EP 81870029A EP 0066663 A1 EP0066663 A1 EP 0066663A1
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EP
European Patent Office
Prior art keywords
compartment
cathode
electrolysis cell
cell according
anode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP81870029A
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English (en)
French (fr)
Inventor
Henri Lemoyne
Philippe Duquet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LA CELLULOSE DES ARDENNES
Original Assignee
LA CELLULOSE DES ARDENNES
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LA CELLULOSE DES ARDENNES filed Critical LA CELLULOSE DES ARDENNES
Priority to EP81870029A priority Critical patent/EP0066663A1/de
Publication of EP0066663A1 publication Critical patent/EP0066663A1/de
Withdrawn legal-status Critical Current

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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
    • C25B1/30—Peroxides

Definitions

  • the present invention relates to the production of hydrogen peroxide, and more specifically an electrochemical process for production in an alkaline medium.
  • the invention applies preferably, but not exclusively, to bleaching operations for paper pulp with hydrogen peroxide in soda or other alkali solutions.
  • Oxygenated water (or hydrogen peroxide) is used in particular in industry as an oxidation and bleaching agent, and, for this application, and unlike chlorine derivatives, has the advantage of not being the origin of the formation of no corrosive or polluting waste. Its selective action is also easily controllable, which explains why its use is particularly sought after in a certain number of activities where the quality of the finished product is of great importance. This is the case, in particular, of the industries for treating vegetable and artificial textile fibers, or the bleaching of paper pulps.
  • the present invention offers considerable advantages in this respect. insofar as it allows the production, by electrochemical means, of hydrogen peroxide directly in a sodium hydroxide solution or other base which can be intended for the bleaching of paper pulps, therefore at the same place of use, which allows d '' eliminate the operations of purification and concentration then of dilution and mixing, as well, naturally, as those of transport and other manipulations.
  • the invention relates on the one hand to the embodiment of an electrode, and on the other hand to the design of the electrolysis cell.
  • the cell in which the electrochemical production of hydrogen peroxide is carried out is divided into three compartments, separated by two electrodes and a separator, as shown in the single figure.
  • An oxygen or air emulsion is introduced at 1 into compartment A where a vortex can be created, with the effect of perfecting this emulsion while imposing rapid circulation on the surface of the cathode D.
  • Part of the emulsion is forced to pass through the cathode, while a nozzle 2 allows, while controlling the flow rate of the passage through the electrode, to eliminate the excess gas by evacuating a part of the emulsion which is recycled to be sent back to the by means of a pump 3 to the same compartment A, after a new supply of oxygen or air in 5.
  • the pipe 4 allows the supply of the circuit with soda or other alkali whose concentration varies between 0.1 and 2.5 moles / 1 approximately.
  • the emulsion which passes through the porous electrode D in the direction of the cathode compartment B undergoes, in contact with the cathode, an electrochemical reduction reaction of the oxygen contained, which causes the formation of hydrogen peroxide in the electrolytic medium.
  • the mixture is enriched with oxy- hindered during electrolysis; it is recycled to compartment A by the nozzles 6 and 7 until the desired concentration of hydrogen peroxide is obtained in this circuit.
  • compartment B Against the face of compartment B opposite the cathode, between B and a third compartment C, anodic, are arranged a porous separator E and a perforated metal anode F.
  • the medium which circulates in compartment C and the anodic circuit 8 animated by the pump 9, is a solution of sodium hydroxide or another base, of the same kind as that in which the oxygen or air emulsion introduced into the cell at 1 is made, that is to say the concentration vary from about 0.1 to 2.5 moles / liter.
  • compartment C in contact with the anode, the electrolysis reaction causes a release of gaseous oxygen, which is evacuated on the anode circuit, at 10, to be optionally returned at 5.
  • the cathode is a porous graphite or carbon electrode. It is constituted by a coherent fibrous network which is a felt or a fabric. It may preferably be a graphite felt which has better electrical conduction qualities than a carbon felt, as well as good mechanical strength.
  • the felts used preferably have a thickness at least equal to 2 mm in order to obtain a large active surface.
  • the porosity of these felts is generally around 98%. It is necessary to subject these felts to a preliminary treatment so that they can be used as cathodes in cells of the type of that which is the subject of the present invention. In fact, these felts have a clear hydrophobic tendency which would prevent sufficient passage of the electrolyte through its thickness, which would lead to limiting the admissible cathode current densities. It is therefore advisable to carry out a preliminary hydrophilization treatment. This can be done in three different ways.
  • the first possibility consists in immersing the felt in an alcohol, for example pure ethanol, at boiling point for a period of approximately two hours.
  • the second possibility leads to carrying out the treatment by immersion of the felt in sulfochromic acid at approximately 50%, hot and preferably at a temperature close to that of boiling, for approximately one to five minutes.
  • the third way consists in successively associating the first two methods, the immersion in the sulfochromic acid being carried out after the treatment in alcohol, in order to oxidize the traces of alcohol which could possibly remain in the fibrous structure.
  • the fibrous structure is then washed and rinsed with water to be used as a cathode.
  • the cathode thus prepared is sandwiched between two charge collectors made of perforated sheet metal of nickel or nickel plated steel, or any other material capable of withstanding the effects of the environment. , to work potential.
  • the reaction which is caused on contact with the felt cathode in compartment A is a reduction in the oxygen transported
  • the percolating electrode is penalized, in addition to a fairly delicate implementation, by a cost greater than that of a felt or fabric electrode. This is as much the fact of the existence in the trade of felts which can fulfill the function of electrode when there are not in the same way of percolating electrodes, as the fact that a percolating carbon electrode requires the 'use of a quantity of this material much greater than that used in the manufacture of a felt.
  • the triple contact electrode As for the triple contact electrode, it too suffers from considerable defects. Its production is made particularly difficult due to the marked tendency of carbon to hydrophylize gradually during use. Extremely balanced sharp should be sought between two opposing risks: a tendency to rapid wetting, and a tendency to excessively hydrophobic. This type of electrode is generally subject to fairly rapid aging, characterized by progressive wetting and a pearling phenomenon at the level of the gas phase. Finally, here again, the fact that no triple contact electrode is marketed constitutes a handicap, marked by the high cost of this technology.
  • the emulsion introduced in the fluid supply compartment A can be perfected by creating a vortex which forces it to sweep, at high flow rate. , the surface of the electrode.
  • the excess gas in the emulsion is discharged through the nozzle 2.
  • the separator E which is interposed between the cathode compartment B and the anode F, it may be either a cation exchange membrane or a microporous.
  • the cationic membrane ensures perfect separation of the species, up to a maximum concentration of hydrogen peroxide in the neighboring cathode compartment. 25 g / liter.
  • it is the site of an electrodialysis reaction leading to a variation in pH, which decreases in the anode compartment C while it increases in the cathode compartment B.
  • this phenomenon is likely to represent a disadvantage since, the normality of the electrolyte increasing in B, the concentration of the solution alca line in oxygenated water tends to decrease.
  • the drop in pH in the anode compartment must not be such that its value becomes less than 11, in order to avoid corrosion of the anode when it is made of a non-precious metal such as nickel. .
  • Microporous allowing free passage of OH2 ions to the anode compartment, does not cause an electrodialysis reaction.
  • the tendency of the HO2 ions to migrate to the anode compartment C increases as the concentration of hydrogen peroxide in the cathode compartment B increases. This does not however prevent excellent results being obtained since for a high concentration of hydrogen peroxide, of the order of 20 g / liter, the faradaic yields remain at a level of around 80%.
  • microporous preferably used are made of polypropylene, this because of their very good chemical stability in alkaline solution.
  • the microporous marketed under the name CELGARD 2400 hydrophilic version lends itself particularly well to this type of application, with a porosity of 38% and a pore size of 200 ⁇ .
  • microporous causes only a very low ohmic drop and therefore only a very limited increase in the voltage across the terminals of the cell.
  • the anode consists of a perforated sheet, which can be either nickel or nickel-plated steel. This structure gives it excellent mechanical strength.
  • the temperature at which the electrochemical production of hydrogen peroxide takes place according to the technology which is the subject of the present invention is preferably fixed at approximately 25 ° C.

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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)
EP81870029A 1981-06-10 1981-06-10 Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen Withdrawn EP0066663A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP81870029A EP0066663A1 (de) 1981-06-10 1981-06-10 Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP81870029A EP0066663A1 (de) 1981-06-10 1981-06-10 Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen

Publications (1)

Publication Number Publication Date
EP0066663A1 true EP0066663A1 (de) 1982-12-15

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EP81870029A Withdrawn EP0066663A1 (de) 1981-06-10 1981-06-10 Elektrolytische Zelle zur Herstellung von Wasserstoffsuperoxid in alkalischen Lösungen

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758317A (en) * 1986-11-20 1988-07-19 Fmc Corporation Process and cell for producing hydrogen peroxide
DE4311665C1 (de) * 1993-04-08 1994-08-18 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid-Lösungen
DE4317349C1 (de) * 1993-05-25 1994-10-13 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid/Percarbonat-Lösungen
DE19516304C1 (de) * 1995-05-04 1996-07-25 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid-Hydrat

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2020671A1 (de) * 1968-10-14 1970-07-17 Koninkl Ind
US3969201A (en) * 1975-01-13 1976-07-13 Canadian Patents And Development Limited Electrolytic production of alkaline peroxide solutions
EP0002423A1 (de) * 1977-12-06 1979-06-13 Battelle Memorial Institute Verfahren und Maschine zum Waschen und Bleichen von Textilstoffen

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2020671A1 (de) * 1968-10-14 1970-07-17 Koninkl Ind
US3969201A (en) * 1975-01-13 1976-07-13 Canadian Patents And Development Limited Electrolytic production of alkaline peroxide solutions
EP0002423A1 (de) * 1977-12-06 1979-06-13 Battelle Memorial Institute Verfahren und Maschine zum Waschen und Bleichen von Textilstoffen

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758317A (en) * 1986-11-20 1988-07-19 Fmc Corporation Process and cell for producing hydrogen peroxide
DE4311665C1 (de) * 1993-04-08 1994-08-18 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid-Lösungen
DE4317349C1 (de) * 1993-05-25 1994-10-13 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid/Percarbonat-Lösungen
DE19516304C1 (de) * 1995-05-04 1996-07-25 Metallgesellschaft Ag Verfahren zur Herstellung von Alkaliperoxid-Hydrat

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