EP1409767B1 - Preparation par electrochimie d'acide peroxo-pyrosulfurique a l'aide d'electrodes diamantees - Google Patents

Preparation par electrochimie d'acide peroxo-pyrosulfurique a l'aide d'electrodes diamantees Download PDF

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Publication number
EP1409767B1
EP1409767B1 EP00969410A EP00969410A EP1409767B1 EP 1409767 B1 EP1409767 B1 EP 1409767B1 EP 00969410 A EP00969410 A EP 00969410A EP 00969410 A EP00969410 A EP 00969410A EP 1409767 B1 EP1409767 B1 EP 1409767B1
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Prior art keywords
electrode
layer
diamond
electrodes
doped
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German (de)
English (en)
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EP1409767A1 (fr
Inventor
Christos Comninellis
Pierre-A. Michaud
Werner Hänni
André Perret
Matthias Fryda
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Adamant Technologies SA
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Adamant Technologies SA
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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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

Definitions

  • the present invention relates to the electrochemical production of peroxodisulfuric acid using diamond-coated electrodes.
  • peroxodisulfuric acid H 2 S 2 O 8
  • E 0 normal potential
  • peroxodisulfuric acid H 2 S 2 O 8
  • the most important fields of application of peroxodisulfuric acid include etching processes in the electronics industry and the production of certain plastics, for example the use in the polymerization of acrylonitrile.
  • peroxodisulfuric acid in wastewater treatment, oxidation of dyes and bleaching of fibers.
  • peroxodisulfuric acid is an important intermediate for the electrochemical production of hydrogen peroxide.
  • Oxygen may also be formed as by-products by decomposition of water, ozone, peroxomonosulfuric acid and hydrogen peroxide according to the following equations: H 2 S 2 O 8 + H 2 O ⁇ H 2 SO 5 + H 2 SO 4 (5) H 2 SO 6 + H 2 O ⁇ H 2 SO 4 + H 2 O 2 (6).
  • the electrode material must be corrosion resistant and stable against anodic dissolution.
  • the formation of peroxodisulfuric acid takes place in a potential range in which water is already decomposed to produce oxygen. Therefore, to suppress competing oxygen production, the electrode material must have a high overpotential for this reaction.
  • Peroxo-disulfuric acid Due to the necessary expenditure on equipment Peroxo-disulfuric acid is produced in specially designed companies and must be obtained from there. However, it would be desirable to be able to produce Peroxo-disulphuric acid directly on site, that is at the site, as needed, since peroxo-disulfuric due to their extremely reactive properties is difficult to store and also subject to free peroxodisulfuric in aqueous solution rapid hydrolysis.
  • Such electrodes in which a boron- or nitrogen-doped diamond layer is applied to a suitable carrier material, can be obtained in principle by means of the known CVD (Chemical Vapor Deposition) technique.
  • CVD Chemical Vapor Deposition
  • an intermediate layer is provided between the support material and the diamond layer, which consists of the decomposition products of a metallocene, preferably Biscyclopentadienyltitandichlorid.
  • ozone can be obtained with silicon-supported diamond microelectrodes ( A. Perret, W. Haenni, P. Niedermann, N. Skinner, Ch. Comninellis, D. Gandini: Electrochemical Society Proceedings Volume 97-32 (1997) 275 ).
  • the diamond-coated electrodes described above generally have the disadvantage that either the diamond layer can be deposited only on small areas (GM Swain loc. Cit.) Or as in US Pat EP 0 730 043 A1 described electrochemically stable electrodes with sufficiently adherent diamond layer can be obtained only using a specially applied intermediate layer.
  • the object of the invention is achieved by a method according to claim 1.
  • doped diamond-coated electrodes are outstandingly suitable for the electrochemical production of peroxodisulfuric acid or peroxodisulfates.
  • peroxodisulfuric acid is used in summary for the compounds prepared peroxodisulfuric and peroxodisulfates.
  • the electrodes doped with diamond doped are also abbreviated as “doped diamond electrodes”.
  • the concentration of the sulfuric acid solution is preferably set in a range of 0.1 mol, in particular 1 mol, to 7.5 mol. If the concentration is less than 0.1 mol, the yields become uneconomical.
  • the doped diamond electrodes used according to the invention are suitable in principle for use in highly concentrated sulfuric acid solutions due to their high stability and electrochemical properties, however, one can be used Sulfuric acid solution with more than 7.5 mol technically difficult to handle.
  • a current density suitable for the method according to the invention is in a range from 10 mA / cm 2 to 5000 mA / cm 2 , in particular 100 mA / cm 2 to 1000 mA / cm 2 , preferably 100 mA / cm 2 to 400 mA / cm 2 .
  • the diamond electrodes used can be of any desired design. It can be used plate, expanded metal, mesh or grid electrodes application. Particularly suitable for industrial installations is a so-called expanded metal mold. Advantageous properties such as good electrolyte exchange, cost-saving use of expensive base metals as well as a largely homogeneous current output through homogeneously distributed preferred sites for the anode reaction, such as tips and edges, come into play. In addition, this form can be coated very reliable. This electrode form is particularly suitable for electrolyte solutions with low H 2 SO 4 concentration.
  • plate electrodes sintered plate electrodes can be used, which may be porous or dense.
  • Ball electrodes may be formed from a plurality of coated spherical electrodes, which are flowed through by the electrolyte in the manner of a fluidized bed.
  • the cell type is not subject to any particular restrictions.
  • Monopolar or bipolar cells with or without separation or division of the electrode spaces by, for example, ion-selective membranes can be used.
  • a separation of the electrode spaces by, for example, ion-selective membranes is recommended for reducing a cathodic reaction of the peroxodisulfuric acid formed.
  • the measure can improve the yields even further.
  • suitable metallic base bodies are niobium, tantalum, titanium and zirconium, with tantalum being particularly preferred.
  • suitable ceramic bodies are silicon, silicon carbides such as silicon-filtered SiSiC or SiC, and silicon nitride, which have sufficient conductivity.
  • a self-passivating material in particular a self-passivating metal, is used for the base body, whereby an impairment or damage of the electrode or the base body due to electrolyte solution, by the possibly resulting in the vapor deposition in the deposited pores or cracks in the deposited layer in the inside of the electrode could penetrate.
  • self-passivating metals are the aforementioned elements titanium, niobium, tantalum or zirconium and alloys of these materials or other self-passivating metals. For cost reasons, however, titanium is the first choice.
  • the diamond layer may be doped with boron, nitrogen, phosphorus or sulfur, with boron and nitrogen being particularly preferred.
  • the content of boron can be between 0.05 ppm and 10 ppm and 10000 ppm, preferably between 0.05 ppm and 100 ppm, which are between 5 ppm and 100 ppm of nitrogen.
  • an adhesion improvement can also be improved by a carbonitride layer on the interface, with particularly good results being observed with ceramic base bodies.
  • the electrode may be formed as a composite electrode, wherein the core 1 of the electrode is formed for example of a copper or aluminum core, which is characterized by particularly high conductivity and relatively low cost.
  • This core 1 is coated with a tight shell 2 of a preferably self-passivating metal, in particular titanium.
  • the electrically conductive doped diamond layer 3 is then deposited.
  • the core 1 and the shell 2 together form the main body 1, 2 on which the electrically conductive diamond layer 3 is deposited.
  • a carburized metal layer 4 which in the above-mentioned example consists of titanium carbide.
  • a gas mixture which contains a carbon source, hydrogen and a source of the dopant, which is a boron source according to the example described here.
  • a preferred carbon source is methane and a preferred boron source is trimethyl borate, these compounds preferably being used in the ratio of 1: 1. It is also possible to use trimethylboron in an amount of 0.05 ppm to 100 ppm.
  • the boron content of the diamond layer can be adjusted.
  • the information on the proportion of the individual components in the gas phase refer to the volume.
  • the gas phase consists of 95% to 99.9%, in particular 99%, hydrogen (H 2 ) and 0.1% to 5%, in particular from 0.5% to 1%, methane (CH 4 ) and from trimethyl borate at a level of from about 1 ppm to 1%, wherein the ratio trimethyborate: methane does not exceed 1: 1.
  • the amount of carbon source may be chosen to be lower or higher depending on the type of carbon source used. For methane, a proportion of about 0.5% to 2% in the gas phase has proved to be particularly advantageous. If the proportion is lower, the growth rate becomes uneconomical, the proportion is too high, suffers the quality of the layer obtained.
  • trimethylborate or trimethylboron used as the boron source simultaneously represents another carbon source.
  • the process pressure is set to 5 to 50 hPa, but can be up to 300 hPa if required.
  • the temperature of the heating or filaments used (also referred to as “filaments”) is usually 2000 ° C to 2400 ° C, and it may be up to 2800 ° C, in particular for electrodes with a ceramic body. As a result, a high activation of the gas phase for the Coating process achieved. On the substrate side, however, it is ensured that, depending on the material, temperatures of 600 ° C. to 950 ° C. are not exceeded.
  • the adjustment of the substrate temperature can be done by adjusting the filament diameter, the filament distances and / or the filament-substrate distance. External heating or cooling can also be used.
  • the content of boron in the diamond layer is preferably between 10 ppm and 10000 ppm, so it can be up to 1%, wherein the boron content in the diamond layer is generally well below 1%.
  • doped diamond layers with a thickness of between 0.5 ⁇ m and 50 ⁇ m can be obtained. If the base body is not ceramic, somewhat thicker layers are preferred, for example with a thickness of preferably 2 ⁇ m to 50 ⁇ m, although smaller thicknesses are also possible.
  • the carburization at the boundary layer (interface) between the base body 1, 2 and the diamond layer 3 deposited thereon can take place, for example, before the actual deposition of the diamond layer or, alternatively, integrated into the vapor deposition process.
  • the surface carburization of the body metals occurs by heating them in discrete steps to the process temperature in the presence of hydrocarbon and hydrogen.
  • metal carbide Due to the presence of methane and possibly trimethyl borate in the gas phase due to chemical reactions, metal carbide also forms in the interface region during the coating of the base metal metals without prior separate carburization according to the second alternative, up to the simultaneous deposition of diamond and the resulting insulation of the existing metal surface compared to Methane and the trimethylborate the metal carbide is terminated.
  • a nitrogen source preferably nitrogen as such, is first added as reactive gas, which reacts with the base body surface, in this case preferably a ceramic base body, under nitride formation.
  • the base body consisting of the core 1 with the copper or aluminum core and the shell 2 of the preferably passivating metal surface roughened, for example by sand or shot peening.
  • the roughening serves to support the liability. This is followed by pre-germination in a suspension of nanodiamond and 0.25 ⁇ m diamond powder in ethanol.
  • doped diamond electrodes are used which have not been subjected to complete oxidative pretreatment prior to initial startup.
  • the term "complete oxidation" means that the surface of the electrode, which is hydrogenated in the untreated state, is oxidized to the highest possible oxidation state, it being assumed that carbonyl groups are formed here.
  • Diamond electrodes which have undergone such anodic pretreatment or polarization are generally considered to be particularly stable and are said to behave electrochemically unchanged for a very long time.
  • Theoretical considerations can be found in HB Martin, A. Arguitia, U. Landau, AB Anderson, JC Angus, in: J. Electrochem. Sok 143 (1996) L.133 ,
  • the voltage must be kept in a range in which there is no complete pre-polarization.
  • the method is thus always operated in the potential range below that voltage at which oxygen can develop, that is, polarization occurs.
  • the voltage should be kept as close as possible below this potential range.
  • Partial oxidation in the sense of the invention means that the oxidation is stopped at a lower oxidation state than that which occurs during the complete pre-polarization. It is assumed that hydroxyl groups form on the electrode surface.
  • FIG. 3 This unexpected behavior of diamond electrodes is illustrated by a cyclo-wiring diagram. To the right, the potential is plotted against a standard hydrogen electrode (SHE) in volts, to the top Current density in A / cm 2 . The temperature prevailing at the time of recording this cyclovoltagram was 25 ° C., the counterelectrode consisted of platinum and the electrolyte used was 1N H 2 SO 4 . The measuring speed was 200 mV / s.
  • SHE standard hydrogen electrode
  • the cyclovoltagram shows in the solid line the behavior of a diamond electrode after it has been pre-polarized. So here there has been an oxidative pretreatment, for example, by applying a very high voltage over a longer period of time.
  • the non-reversible, electrochemical reaction thus increases in intensity with each cycle, and then decreases again.
  • the solid black line at the same time is a trend trend, which is then sought as limit value in further cycles.
  • the optimum amount of charge per unit area varies. This is because the surface structure, for example, the crystal orientation or the shape of the electrode affect this maximum range.
  • this charge content is determined experimentally for a certain type of electrode by passing through several cycles, the charge can be selectively supplied in the case of further electrodes of the same type, ie not in several cycles, but by correspondingly charging each electrode precisely with this charge.
  • a boron-doped diamond layer was produced by means of HF-CVD (Hot Filament Chemical Vapor Deposition) technique on monocrystalline p-Si (100) wafers (0.1 ⁇ cm, sold under the name Siltronix).
  • HF-CVD Hot Filament Chemical Vapor Deposition
  • the temperature of the filaments ranged from 2440 ° C to 2560 ° C, the substrate was maintained at 830 ° C.
  • methane was used in an excess of hydrogen (1% methane in H 2 ).
  • trimethylborane was used in a concentration of 3 ppm.
  • the gas mixture was added to the reaction chamber at a flow rate of 5 dm 3 / min, resulting in a growth rate of 0.24 ⁇ m / h for the diamond layer.
  • the obtained diamond layer had a thickness of about 1 ⁇ m. Columnar, randomly textured polycrystalline layers were obtained.
  • peroxodisulfuric acid was prepared.
  • the preparation was carried out in a single-cell electrolytic flow cell A ( FIG. 4 ) with H 2 SO 4 as electrolyte 7 with an electrolyte inlet 8 and a drain 9 and electrical connections 10, 11.
  • the diamond electrode was the anode 5 and zirconium the cathode 6. Both electrodes were round with a diameter of 80 mm and a surface of 50 cm 2 each. The distance between the electrodes was 10 mm.
  • a thermoregulated glass storage tank of 500 cm 3 was used and circulated by means of a pump through the cell A.
  • the electrolysis was carried out under galvanostatic conditions and an electrolyte temperature of 25 ° C.
  • concentration of peroxodisulfuric acid was determined by means of iodometric titration and recorded as a function of the specific electrical charge (Ah / dm 3 ) used ( FIG. 5 ).
  • the formation of peroxodisulfuric acid was confirmed by the specific Ni (OH) 2 test in the presence of silver nitrate to avoid interference with other oxidants such as H 2 O 2 .
  • the electrolysis was carried out at a low sulfuric acid conversion ( ⁇ 5%) and short electrolysis times ( ⁇ 1 h).

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  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
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Claims (17)

  1. Procédé de préparation par électrochimie d'acide peroxo-pyrosulfurique et de peroxodisulfates par oxydation électrochimique de l'acide sulfurique,
    caractérisé en ce que l'on utilise comme anode (5) une électrode ayant une couche de diamant (3) dopée, en ce que l'électrolyse est réalisée à une densité située dans une plage allant de 10 mA/cm2 à 5000 mA/cm2, de préférence 100 mA/cm2 à 1000 mA/cm2, et en ce que la tension sur l'électrode se situe pendant le service en dessous de celle juste dans la plage de potentiel à laquelle un dégagement d'oxygène commence.
  2. Procédé selon la revendication 1,
    caractérisé en ce
    que la concentration en acide sulfurique de l'électrolyte (7) se situe dans une plage allant de 0,1 mole à 7,5 moles.
  3. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que l'on utilise une cellule monopolaire comme cellule d'électrolyse.
  4. Procédé selon l'une des revendications 1 à 3,
    caractérisé en ce
    que l'on utilise des cellules bipolaires comme cellule d'électrolyse.
  5. Procédé selon la revendication 3 ou 4,
    caractérisé en ce
    que l'espace destiné aux électrodes des cellules est divisé.
  6. Procédé selon la revendication 5,
    caractérisé en ce
    que l'espace destiné aux électrodes des cellules est divisé par une membrane sélective d'ions.
  7. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que la forme des électrodes est choisie parmi une électrode plate, une électrode fil, une électrode métallique, une électrode grille, une électrode réseau ou une électrode tridimensionnelle.
  8. Procédé selon la revendication 7,
    caractérisé en ce
    que l'on utilise une électrode plate poreuse frittée ou une électrode plate dense frittée comme électrode plate.
  9. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que l'anode (5) présente une couche de grande surface constituée de diamant dopé (3) sur un corps de base (1, 2).
  10. Procédé selon la revendication 9,
    caractérisé en ce
    que le corps de base (1, 2) présente, en dessous de la couche en diamant (3), une matière (2) qui est choisie parmi un métal auto-passivant, notamment le titane, le niobium, le tantale, le zircon ou un alliage avec au moins un de ces métaux, le silicium, le carbure de silicium, le carbure de silicium infiltré avec du silicium (SiSiC) et une céramique à base de silicium.
  11. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que, entre le corps de base (1, 2) et la couche de diamant (3), on prévoit une couche intermédiaire carburée (4), en particulier une couche de carbure métallique ou une couche de nitrure de carbone.
  12. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que la couche de diamant (3) est dopée avec un élément choisi parmi le bore, l'azote, le phosphore ou le soufre.
  13. Procédé selon la revendication 12,
    caractérisé en ce
    que la couche de diamant (3) est dopée au bore.
  14. Procédé selon la revendication 13,
    caractérisé en ce
    que la teneur en bore dans la couche de diamant (3) est située dans une plage allant de 10 pm à 10000 ppm.
  15. Procédé selon la revendication 12,
    caractérisé en ce
    que la teneur en azote dans la couche de diamant (3) se situe dans une plage allant de 5 à 100 ppm.
  16. Procédé selon l'une des revendications précédentes,
    caractérisé en ce
    que l'électrode avec une couche de diamant (3) dopée n'est pas soumise à une prépolarisation complète.
  17. Procédé selon la revendication 16,
    caractérisé en ce
    que l'électrode a été soumise avant l'électrolyse à une charge de 0,01 C/cm2 à 1C/cm2 de la surface de l'électrode avant la première mise en service, notamment à une charge de 0,05 C/cm2 à 0,2 C/cm2.
EP00969410A 1999-10-06 2000-10-04 Preparation par electrochimie d'acide peroxo-pyrosulfurique a l'aide d'electrodes diamantees Expired - Lifetime EP1409767B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19948184A DE19948184C2 (de) 1999-10-06 1999-10-06 Elektrochemische Herstellung von Peroxo-dischwefelsäure unter Einsatz von diamantbeschichteten Elektroden
DE19948184 1999-10-06
PCT/EP2000/009712 WO2001025508A1 (fr) 1999-10-06 2000-10-04 Preparation par electrochimie d'acide peroxo-pyrosulfurique a l'aide d'electrodes diamantees

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EP1409767A1 EP1409767A1 (fr) 2004-04-21
EP1409767B1 true EP1409767B1 (fr) 2009-12-02

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US (1) US6855242B1 (fr)
EP (1) EP1409767B1 (fr)
JP (1) JP4856337B2 (fr)
AT (1) ATE450635T1 (fr)
DE (2) DE19948184C2 (fr)
ES (1) ES2333514T3 (fr)
WO (1) WO2001025508A1 (fr)

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US6855242B1 (en) 2005-02-15
ATE450635T1 (de) 2009-12-15
JP2003511555A (ja) 2003-03-25
DE19948184C2 (de) 2001-08-09
DE50015813D1 (de) 2010-01-14
WO2001025508A1 (fr) 2001-04-12
JP4856337B2 (ja) 2012-01-18
EP1409767A1 (fr) 2004-04-21
DE19948184A1 (de) 2001-05-03

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