WO2011066632A1 - Cellule électrochimique cylindrique avec anode coaxiale de diamant dopé obtenue par procédé de dépôt de films de diamant sur des substrats cylindriques mécaniquement résistants en vue d'une application dans des procédés de purification de solutions aqueuses - Google Patents

Cellule électrochimique cylindrique avec anode coaxiale de diamant dopé obtenue par procédé de dépôt de films de diamant sur des substrats cylindriques mécaniquement résistants en vue d'une application dans des procédés de purification de solutions aqueuses Download PDF

Info

Publication number
WO2011066632A1
WO2011066632A1 PCT/BR2010/000385 BR2010000385W WO2011066632A1 WO 2011066632 A1 WO2011066632 A1 WO 2011066632A1 BR 2010000385 W BR2010000385 W BR 2010000385W WO 2011066632 A1 WO2011066632 A1 WO 2011066632A1
Authority
WO
WIPO (PCT)
Prior art keywords
anode
cell
cell according
diamond
cylindrical
Prior art date
Application number
PCT/BR2010/000385
Other languages
English (en)
Portuguese (pt)
Inventor
Vitor Baranauskas
Alfredo Carlos Peterlevitz
Hudson Giovani Zanin
Reinaldo Francisco TEÓFILO
Helder José CERAGIOLI
Lauro Tatsuo Kubota
Original Assignee
Universidade Estadual De Campinas - Unicamp
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 Universidade Estadual De Campinas - Unicamp filed Critical Universidade Estadual De Campinas - Unicamp
Publication of WO2011066632A1 publication Critical patent/WO2011066632A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0254—Physical treatment to alter the texture of the surface, e.g. scratching or polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46147—Diamond coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/003—Coaxial constructions, e.g. a cartridge located coaxially within another

Definitions

  • the present invention is a cylindrical electrochemical cell for use in the purification of aqueous solutions using coaxial doped diamond anode obtained by chemical vapor deposition process where diamond films are deposited on mechanically resistant cylindrical substrates. , previously blasted, and such process allows to obtain uniform, homogeneous and adherent films.
  • the electrochemical cell containing said anode is capable of efficiently electrolyzing undesirable substances contained in aqueous waste or drinking water, rendering such compounds harmless and / or significantly lowering the concentration of toxic compounds; It is effective in direct and indirect oxidation. besides the anode does not undergo significant physical or chemical structural changes in its surface during long periods of operation.
  • the CVD technique is based on the transformation of gaseous molecules into solid materials in the form of thin films on substrate. These films cover different geometries and can be of excellent quality. While the High Pressure High Temperature (HPHT) technique produces diamond crystals that can be attached to, for example, abrasive tools, the CVD technique makes it possible to coat diamond films on surfaces. materials not having a melting or softening point at a temperature below at least 700 ° C.
  • HPHT High Pressure High Temperature
  • Silicon plates for example, are fragile to manipulate. To assemble an electrolytic cell with these plates containing deposited diamond films, they need to be packed in polymeric supports such as Teflon®. During the assembly process, these plates often break together with the diamond film deposited on them and the anode is lost.
  • U.S. 5,900,127; U.S. 5,399,247; EP 0659 691; U.S. 6,375,827 and BRPI0502246-0 describe the possibility of using doped diamond as an electrode for treating contaminants in water.
  • the electrochemical cells are made up of two plates in which the diamond can be used as anode or as anode and cathode.
  • US 5,900,127 describes an electrochemical cell using parallel plates, where neither the anode nor the cathode is cylindrical. In addition to the difference in cell configuration, the invention differs from this document for other reasons, which are listed below.
  • the cathode used in US 5,900,127 was constructed using materials such as platinum, palladium, iridium, ruthenium, osmium, rhodium, etc., and oxides of these metals, such as iridium oxide, etc.
  • the diamond in this patent was preferably grown on titanium or a metal or semi metal that allows carbide generation. Three electrochemical cell configurations were presented: two with double compartments and one with triple compartment.
  • the cell is divided by an ion exchange membrane intimately disposed between the anode and cathode or disposed at the connector portion having a small diameter and spaced from the cathode and anode.
  • the division consists of the following sequence: a cathode attached to an ion exchange membrane, a separation and an ion exchange membrane attached to the anode.
  • US 5,399,247; EP0659691 and BRPI0502246-0 show configurations of electrochemical cells mounted with parallel plates.
  • the boron-doped diamond anode was grown in silicon and purchased from the US company Advanced Technology Materials, Inc.
  • the anode having an area of 3 cm 2 , was fixed to a plate and disposed in parallel. to a 12 cm 2 304 stainless steel plate used as a cathode.
  • a nylon mesh was used between the plates to promote aqueous flow turbulence.
  • BRPI0502246-0 describes an electrochemical oxidation process of organic compounds using a reactor equivalent to that described in US 5,399,247 and EP 0659 691. Although the present invention has in common with BRPI0502246-0 the use of diamond conductor as anode for mounting the electrochemical cell differs in that the cell is assembled with parallel plates, where a silicon plate is glued onto a stainless steel plate using a conductive adhesive in an attempt to increase the mechanical resistance of the electrode. .
  • US 6,375,827 is characterized by the use of diamond as both anode and cathode material, in which the electrochemical cell is assembled with two parallel plates, and an ion exchange membrane can be added between the plates, thus obtaining a cell in two compartments.
  • the present invention has in common with US 6,375,827 the use of conductive diamond as anode for The electrochemical cell assembly differs in that the cell is assembled with parallel plates, where the cathode is also a conductive diamond.
  • U.S. 6,267,866 describes electrode construction using diamond deposition on a metal mesh. It is indicated for use as cathode or anode.
  • the term mesh is defined as a grid of interwoven metallic filaments. The goal would be to make the electrode hollow and with large surface area for electrochemical applications.
  • the present invention has in common with U.S. 6,267,866 the fact that it uses conductive diamond in the electrode assembly, it differs in that it is a plate-shaped assembly. It does not claim an electrochemical cell, but an electrode (anode and cathode).
  • the disadvantage of using this plate is the realization and isolation of the electrical contact and the assembly of the anode - cathode configuration of the cell, as both must be completely immersed in the electrolyte solution without the use of polymeric support.
  • US 7,217,347 describes the construction of the electrode on a Magneli titanium phase. The goal is to extend the life of the diamond when grown on this material.
  • the present invention has in common with US 7,217,347 the fact that it uses conductive diamond in the electrochemical cell assembly, it differs in that it is a wire mesh assembly using a different substrate, most of which of the figures shows the diamond powder mixed with titanium oxide powder. It does not claim an electrochemical cell, but an electrode (anode and cathode).
  • the disadvantage of this technology lies in the electrode manufacturing process, which requires the use of Magneli phase titanium oxide substrate, diamond powder, titanium powder and a catalyst layer. This makes the cost of manufacturing the process relatively high and complex.
  • US 6,306,270 and EP1031645 which refer to the same invention, relate to an electrochemical cell including an anode, a cathode and at least one bipolar electrode arranged between the anode and the cathode.
  • This cell is characterized by a bipolar electrode that includes a substrate and a doped diamond film.
  • Two cell configurations are presented, one with plate electrodes and one with spherical electrodes immersed in an electrolyte solution.
  • the present invention has in common with US 6,306,270 and EP1031645 the use of conductive diamond as a bipolar electrode for the treatment of solutes in liquid solution and one of the assemblies involves a cylindrical cell, it differs in that the cylindrical cell is assembled.
  • the cylinder is placed inside a container, unlike the proposed electrochemical cell, where the cylinder containing the diamond film (anode) is coaxially disposed within another stainless steel or other metal (cathode) cylinder.
  • Diamond-coated anode and cathode polarize diamond-coated spheres. Assembly requires a membrane through which the solution to be degraded crosses and the spheres do not. This is a complex and expensive assembly, unlike the present invention.
  • US 7,232,507 and CA2439744 which refer to the same invention, describe the use of a complex electrochemical reactor for treating low concentration contaminants in low electrical conductivity aqueous solutions and claim the use as a coating material. of cell, a semiconductor diamond.
  • the present invention has in common with US 7,232,507 and CA2439744 the fact that using semiconductor diamond for electrodegradation of organic compounds in water, it differs in that the configuration of the cell and the electrodes are completely different.
  • the complexity of the cell configuration would certainly increase the difficulties of its industrial fabrication, which would result in higher costs compared to the proposed technology. Certainly there would still be the difficulty of perfectly cutting the plates, which are usually imported in the form of silicon wafers.
  • the service life of stainless steel used as anode is a few hours, depending on the pH of the electrolyte used and the current density applied.
  • the metallic iron present in its steel composition undergoes oxidation and dissolves in solution and thus the anode self-oxidizes.
  • EP 1369384 describes the use of conductive plate diamonds as electrodes, but such document refers to the use of oxyacids or oxyacid salts, which should be used in the solution to be treated to improve treatment efficiency.
  • the present invention has in common with EP 1369384 the fact that it makes use of conductive diamond electrodes, it does not consider the effects of oxyacids or oxyacid salts in the solutions to be treated.
  • the focus of this invention is on mounting the electrochemical system and not on chemical additives to be added in the process.
  • BRPI0502245-2 describes a process for preparing an electrochemical cell using diamond electrodes grown on silicon plates. The opposite side of the diamond film is glued to a metal plate, such as stainless steel.
  • a metal plate such as stainless steel.
  • the present invention has in common with BRPI0502245-2 the use of doped diamonds deposited on substrates, it differs in that it avoids the inconvenience of performing a prior step to increase substrate strength and produce efficient electrical contact.
  • the substrate is mechanically strong enough to be easily manipulated.
  • the substrate where the diamond is deposited is protected by a stainless steel cylinder, which ensures greater protection against unwanted breakage.
  • the main problems of the electrochemical cell proposed in document BRPI0502245-2 present the same drawbacks already reported for parallel plates, mainly regarding leakage and difficulty in making electrical contacts.
  • Document BRPI0600897-6 describes a manufacturing process of electrochemically doped diamond electrodes comprising two main steps: i) diamond deposition and ii) the actual construction of the electrodes. In relation to the process of deposition of boron-doped diamond and carbon, it decreases or eliminates the formation of unaddressed carbons on the electrode surface.
  • the electrodes obtained by this process can be used in electrochemistry, electroanalysis and electrosynthesis with the advantage of being resistant to surface passivation by organic compounds.
  • the electrodes now treated have electrical contacts with wires embedded or welded in the doped diamond, and with insulated metal parts, which improves the practicality and ohmic contact of these electrodes in electroanalysis or electrosynthesis as working electrode.
  • the present invention has in common with document BRPI0600897-6 the fact that boron-doped diamond films are deposited using HFCVD reactor, it differs in that in area BRPI0600897-6 the area and size of the substrate are reduced ( wires with a diameter of approximately 238 pm and a length of approximately 30 mm). This is because the application proposed in this document is to obtain electrodes with small areas (approximately 0.030 cm "2 ) in order to be polarizable in electrochemical analysis and studies. In addition, there is no claim of electrochemical cell but of electrode production.
  • the dimensions (diameter from 4.0 mm and length from 30.0 mm) and electrode area are larger (from 4.0 cm 2 ) as it is desired to avoid polarization during
  • the cylindrical configuration of the entire cell including the stainless steel cathode and the production of a doped diamond film on mechanically resistant cylindrical substrates is further claimed, and the cell proposed here has another purpose, ie , electrochemical degradation of persistent chemical compounds.
  • the present invention is interesting since the electrochemical cell proposed for the purification of aqueous solutions simultaneously meets the advantages offered by i) electrochemical cells designed in cylindrical shape; ii) by electrochemical cells using doped diamond anode; and iii) the fact that the diamond anode used is obtained by a chemical deposition process from the vapor phase, where said diamond films are deposited on mechanically resistant cylindrical substrates of larger diameters (from 4.0 mm), previously blasted with iron or steel grit as detailed below.
  • Electrochemical cells designed in cylindrical shape have the following advantages: space minimization; ease in making electrical contacts; easy assembly of large-scale cells - serial or parallel connection - and prevents leaks during cell use.
  • the use of doped diamond anode in the assembly of electrochemical cells, regardless of their shape, has the following advantages: mechanical strength; chemical inertia; operating potential in harsh environments; broad overpotential for oxygen evolution; efficiency to withstand anodic oxygen transfer reactions; high thermal conductivity; High dimensional stability and constant sensitivity.
  • US 5,387,447 describes a diamond coating process on thin strands (diameters ranging from 0.025 to 2.5 mm) of general materials that support the conditions under which the diamond is deposited.
  • the present invention differs from this document in that it proposes a process of depositing uniform, homogeneous and adherent diamond films on cylindrical substrates of larger diameters (from 4.0 mm).
  • the obtained films were uniform and of good quality, but they were peeled, which makes them unfeasible for the application contemplated in the present invention, once that the turbulent flow needed to perform the renovation of the solution on the anode surface would remove all diamond film from the substrate.
  • WO 2004009498-A1 U.S. 20060124453-A1 and U.S. 7422668-B2 describe a cylindrical electrochemical cell that resembles the shape of the object cell of the present invention, however, some differences may be observed. The main difference is in the composition of the materials used.
  • the documents describe the use of ruthenium-coated titanium and iridium oxide and the use of a ceramic material composed of aluminum, zirconium and yttrium oxide. However, the documents do not mention the use of doped diamond. Furthermore, sealing technical details of the invention of the cited documents are different from the present invention.
  • doped diamond films for electrochemical degradation of persistent compounds in aqueous solutions is well described in the literature, as well as the use of titanium electrodes.
  • the working potential window of electrodes mounted with doped diamond anodes is much larger than those of titanium.
  • diamond is an inert material, robust in aggressive solutions and has high passivation resistance, unlike titanium electrodes.
  • Titanium electrodes are not as efficient as diamond electrodes in the total mineralization of persistent organic compounds in aqueous solutions due to anode deactivation (S. Yoshihara and M. Murugananthan, Decomposition of various endocrine-disrupting chemicals at boron-doped diamond electrode. Electrochimic Acts Vol. 54, pp. 2031-2038, 2009).
  • Diamond film coatings are generally performed at temperatures no lower than 500 ° C. Since the coefficient of thermal expansion of the diamond is quite low, when shutting down the CVD reactor, which produces the diamond film, there is a temperature variation large enough to cause cracking in the film. Although the diamond is generally mechanically stronger, it is significantly smaller in thickness than the substrate tube.
  • RK Singh, DR Gilbert, J Fitz-Gerald, S Harkness, Engineered Interfaces for Adherent Diamond Coatings on Large Thermal-Expansion Coefficient Mismatched Substrates. Science Vol. 272, No. 5260, Page 396-398, 1996 discusses the difficulty of obtaining integrally adherent diamond film on some materials due to differences in the coefficient of thermal expansion. Diamond has one of the lowest coefficients of thermal expansion that exists in nature, which provides, even with large temperature variations, very little contraction or expansion of the material.
  • the present invention differs from the state of the art by proposing to obtain a diamond film and doped diamond materials which have adequate adhesion to mechanically resistant cylindrical substrates (which support the substrate pretreatment conditions, in this case blasting with iron or steel grit; and the conditions of the chemical vapor deposition process) such as quartz, titanium, tungsten and stainless steel.
  • Sticking diamond films over large areas is not a trivial task, and the difficulty becomes even greater if the surface is curved.
  • the difference in coefficients of thermal expansion between substrates and movies is the main critical point.
  • diamond is one of the least swelling materials of all known materials, generally this type of film swells less than the substrates on which it is deposited. Therefore, in the case of substrates with relatively large area (between 10 and 50 cm 2 ) or curved, during the process of finishing the chemical deposition the diamond film ends up cracking or peeling. In the case of coating of relatively large diameter cylindrical substrates, the diamond film may crack.
  • quartz as a substrate is an interesting alternative because it supports the deposition conditions of diamond films very well, and still has a coefficient of thermal expansion similar to that of diamond.
  • the present invention was only possible when diamond films could be efficiently, evenly and evenly adhered to the surfaces of quartz tubes, which had to go through a blasting step (substrate pre-grinding).
  • the purpose of the blasting was to increase the roughness and surface area that would receive the CVD film, thus allowing to obtain well adherent films, even in relatively large dimensions (between 10 and 50 cm 2 ).
  • the present invention provides a cylindrical electrochemical cell capable of efficiently electrolyzing undesirable substances contained in aqueous waste or drinking water, rendering such compounds harmless and / or significantly lowering the concentration of toxic compounds.
  • the proposed electrochemical cell which uses a coaxial doped diamond anode obtained by chemical vapor deposition process, where said diamond films are deposited uniformly, homogeneously and adherently on mechanically resistant cylindrical substrates of larger diameters (from previously blasted, provides favorable conditions and ease of handling for industrial applications involving electrochemical treatments related to the decomposition of substances in contaminated waters.
  • the cylindrical shape Cell (closed) allows space minimization, facilitates electrical contacts, facilitates large-scale cell assembly (serial or parallel connection), and prevents leakage during cell assembly. Additionally, the use of the proposed cell in the purification of aqueous solutions presents substantial improvements compared to the prior art similar geometries.
  • the proposed cylindrical electrochemical cell offers the advantage for treatment of low conductivity aqueous solutions, ie, with conductivities between 0.005 S / m and 0.010 S / m and for the treatment of aqueous solutions containing low concentrations of contaminants, ie compounds in concentration at pg range L "1.
  • the anode used in the assembly of said cell can work in extremely acidic or basic solutions ie between pH 1 to 14, which is a characteristic of the diamond anode and stainless steel cathode AISI 304, which are resistant to these conditions.
  • the proposed electrochemical cell allows an external electrical contact to the region where the solution treatment occurs and thus the electrical contact remains protected and immune to any aggressive liquid.
  • the proposed electrochemical cell allows the coupling of electrode series connections.
  • the cylindrical shape has the advantage that it can be arranged in a small cell array and thus gain time in treating large volumes of aqueous solution in an optimized physical space.
  • the configuration of the proposed electrochemical cell allows for ease of handling, ease of assembly and disassembly due to threaded connections and an extremely efficient seal that prevents the leakage of liquids and gases without the use of resins or adhesives.
  • the present invention provides a process of depositing uniform, homogeneous and adherent diamond films on larger diameter tough cylindrical substrates (at from 4.0 mm), preferably between 4 and 20 mm, previously blasted with iron or steel grit, performed by the CVD (Chemical Vapor Deposition) technique to obtain coaxial doped diamond anodes.
  • the process treated here consists basically of two steps. The first stage comprises the preparation of the mechanically resistant cylindrical substrate, and the second stage comprises the deposition of doped diamond films on said substrates.
  • Quartz has a number of advantages when used to receive CVD diamonds, as it can withstand the deposition conditions of diamond films and has a coefficient of thermal expansion similar to that of diamonds.
  • diamond quartz films may crack or peel.
  • the increase of quartz surface roughness is a possible solution to this problem.
  • a sandpaper polish was first performed to increase substrate roughness, but did not give satisfactory results. In this sense, it was decided to blast iron and steel shot, which significantly increased the roughness and surface area of the quartz surface. The results of diamond deposition on the blasted quartz substrate were satisfactory.
  • the growth parameters used for the growth of boron-doped diamond films is well described in the literature (Teófilo et al. Improvement of the electrochemical properties of "as-grown" boron-doped polycrystalline diamond electrodes deposited on tungsten wires using ethanol (J. Solid State Electrochem., 11, pp. 1449-1457, 2007); except for pre-treatment with shot.
  • the deposition was performed in a reactor developed for the growth of carbonic structures (including diamond) on tubes.
  • Conventional HFCVD reactors are generally designed for the growth of diamond films on flat structures.
  • the differential of this reactor is the viability of growing diamond structures in cylindrical or conical geometry, ie, on tubular or conical substrates, due to: (i) implantation of a magnetic coupling system between the substrate and a small electric motor, and (ii) implementation of a thermomechanical filament expansion balance system developed to provide this capability to conventional reactors.
  • the present invention provides the coaxial doped diamond anodes obtained by the chemical deposition process from the thermally decomposed hot phase vapor (CVD) phase of organic compounds from mechanically resistant cylindrical substrates of larger diameter. (from 4.0 mm), preferably between 4 and 20 mm, previously blasted with iron or steel shot.
  • the anodes thus produced have excellent durability.
  • the aqueous tailings should preferably be at pH 2 to 7.
  • cylindrical electrochemical cell conceived in the present invention proposes to provide an electrochemical treatment for oxidizing substances contained in aqueous solution, which can be accomplished by introducing the solution containing substances to be treated into the electrochemical cell with a cylindrical anode and cathode and passing An electric current through them is therefore an additional object of the present invention the use of said cylindrical electrochemical cell in the purification of aqueous solutions, which utilizes coaxial diamond anode obtained by depositing uniform, homogeneous and adherent diamond films on mechanically resistant cylindrical substrates of larger diameters (from 4.0 mm), preferably between 4 and 20 mm, previously blasted with iron or steel grit, performed by the CVD technique.
  • coaxial diamond anode obtained by depositing uniform, homogeneous and adherent diamond films on mechanically resistant cylindrical substrates of larger diameters (from 4.0 mm), preferably between 4 and 20 mm, previously blasted with iron or steel grit, performed by the CVD technique.
  • the compounds to be degraded by the present invention should preferably be in an aqueous solution having some electrical conductivity, preferably between 0.005 S / m and 0.010 S / m with a pH preferably between 2 and 7.
  • the electrolytes providing the conductance may be any inorganic salt. high solubility in water (> 15% w / v), preferably Na 2 SO 4 .
  • FIG. 1 Diagrammatic view illustrating an example of an electrolysis cell for use in the method of the invention for decomposing organic compounds contained in an aqueous solution.
  • the solution to be treated placed in the compartment (1) is transferred by the pump (2) to the cell (3) where the electrolysis occurs following a defined flow (F).
  • the cell is connected to a current source (5) by conductor cables (4) external to the reaction region.
  • the solution recirculates following the defined flow (F), until complete cleaning and is directed to the disposal (6).
  • FIG. 1 Diagrammatic view illustrating an example of a set of electrolysis cells connected in parallel.
  • the solution to be treated passes through a plurality of cells (3) connected in series by conductor cables (4) to a current source (5) and arranged in a compartment (7).
  • Item 8 represents an immediate disposal, without recirculation: the solution goes through the arrangement only once.
  • FIG. 3 Cross-sectional schematic view showing a detailed example of the electrochemical cell (3) with the flow (FE) through the interior of an inner cylindrical electrode (9).
  • the cell is composed of a hollow cylindrical anode, composed of a semiconductor material, in which the doped diamond (10) is deposited on its surface. This anode is placed internally and in the center of a hollow cylinder (11) of conductive material, the cathode.
  • An internal screw cap (12) of inert and non-conductive material, with a conical central opening of a diameter slightly larger than the anode diameter; and an internal screw cap (13) for flow outlet, composes one of the cell sealing items.
  • a high density tapered rubber (14) with a central opening of anode diameter and laterally opening is used to make the seal.
  • Another internal screw cap (15) and a high density inner rubber (16), both with a central opening, are responsible for the complete sealing of the system by pressing the conical rubber (14) over the diamond tube that passes through it. the central openings described.
  • an internal screw cap (17) of inert, nonconductive material is used for sealing on this side.
  • This cap is composed of a hollow, hollow, centered inner tapered pin (18) for supporting the anode and escaping the solution to be treated into the cell.
  • the solution to be treated enters the cylinder (19) that makes up the anode and leaks through holes (18) into the reaction region (20), where the compounds present in the solution to be treated are oxidized between the anode and the cathode.
  • the anode is connected by a positive pole (21) and the cathode by a negative pole (22). Liquid flow follows the indicative arrows (F).
  • FIG 4. Cross-sectional schematic view showing a detailed example of the electrochemical cell with the flow entering through the interior of the inner cylindrical electrode and the presence of a helical turbulence promoter.
  • a helical turbulence promoting device (23) of non-conductive inert material is placed between the anode and the cathode to assist in the contact time of the solution in the reaction medium (20).
  • Figure 5. Cross-sectional schematic view showing a detailed example of the electrochemical cell to be used in which the substrate (9) where the diamond is grown may or may not be hollow, with flow (FE) entering laterally into the cell.
  • the cylindrical substrate is pierced axially by the stainless steel tube (11) and on both open sides of the stainless steel tube, the sealing systems are identical.
  • the solution flow inlet and outlet occur at (24) and (25), respectively.
  • the arrows (FE, FS) indicate the direction of flow.
  • FIG. 6 Cross-sectional schematic view showing a detailed example of the electrochemical cell with the flow entering laterally to the cell and the presence of a helical turbulence-promoting cylindrical device.
  • the helical turbulence promoting device of non-conductive and inert material (23) is placed between the anode and cathode to assist in the contact time of the solution in the reaction medium (20).
  • FIG. 7 Cross-sectional schematic view showing a detailed example of the electrochemical cell with the flow entering laterally to the cell and the presence of an ion exchange membrane intimately bonded to the electrode walls.
  • the membrane is closely adhered to the diamond surface (26) and also to the inner surface of the cathode (27).
  • FIG. 10 Cross-sectional schematic view showing a detailed example of the electrochemical cell sealing system emphasizing the upper cover assembly and the lower cover.
  • the upper cover assembly comprises an internal screw cap (12) made of inert and non-conductive material with a tapered central opening (28) in diameter slightly larger than the anode; a high density conical rubber (14) with a central aperture of a diameter equal to said anode; and an inner screw cap (15) containing a high density inner rubber (16), both with a central opening.
  • the lower cap (17) comprises an internal screw cap, made of inert and non-conductive material, containing a hollow, hollow centralized inner tapered pin (18) when said anode is hollow; or containing a recess for centering said anode when it is not hollow.
  • FIG. 11 Cross-sectional schematic view showing a detailed example of the helical turbulence-promoting cylindrical device (23).
  • a device comprises a hollow cylinder of inert and non-conductive material configured to provide the formation of a turbulent flow in a helical path within said cylinder.
  • a "cylindrical electrochemical cell” means an electrochemical cell composed of a conductive diamond electrode connected to the positive terminus of a direct current source and defined as anode, as well as a metal electrode connected to the negative terminus of a direct current source and defined as a cathode.
  • undivided cylindrical electrochemical cell is understood to mean a cell where the anode and cathode are not separated by plates or membranes but only by an aqueous solution.
  • mechanically resistant cylindrical substrate means quartz substrates, or those selected from metal conductors in general, such as stainless steel, and having a cylindrical or tubular cylindrical shape.
  • blasting means mechanically resistant cylindrical substrates subjected to a homogeneous blasting process with iron or steel grit. This process is performed to increase the contact surface between the deposited diamond film and the resistant cylindrical substrate and thereby increase the friction between the parts.
  • coaxial doped diamond anode means an anode obtained by a chemical vapor deposition process, wherein said diamond films are uniformly, homogeneously and adherently deposited on mechanically resistant cylindrical substrates of diameter upper (from 4.0 mm), preferably between 4 and 20 mm, previously blasted, and said obtained anode is inserted into another hollow cylindrical: the cathode. In this case, both have a common axis.
  • chemical vapor deposition process is a technique based on the transformation of gaseous molecules into solid materials in the form of thin films on a given substrate.
  • All CVD deposition systems share basically the same principle of operation. They require continuous flow feeding of carbon-containing molecules in their structure. These molecules are usually in the gaseous state and usually flow with molecular hydrogen.
  • An energy activation source is used by the system for two purposes: dissociating the precursor molecules into radicals so that they react on the substrate surface; and dissociate hydrogen molecules into atoms.
  • “persistent inorganic and organic compounds” are understood to be highly stable chemical compounds due to the strength of their covalent bonds and structural configuration. They are poorly reactive compounds and do not donate electrons easily and are therefore complicated to oxidize to less toxic or inert products.
  • “treatment and purification of aqueous solutions or treatment of aqueous waste” means the degradation of undesirable organic and inorganic compounds present in said solutions or waste.
  • the present invention provides a cylindrical electrochemical cell for treatment and purification of aqueous solutions or treatment of aqueous waste using coaxial doped diamond anode obtained by chemical deposition process from the vapor phase, where the Said diamond films are uniformly, homogeneously and adherently deposited on mechanically resistant cylindrical substrates of larger diameters (from 4.0 mm), preferably between 4 and 20 mm, previously blasted with iron or steel grit.
  • H optionally means for connecting a plurality of cells to one another (4).
  • the cathode comprises a metallic material, whether or not coated with a doped diamond material.
  • the metal material constituting the cathode should be selected from a stainless material, preferably from the group comprising stainless steel.
  • the doped diamond material optionally lining the cathode metal material comprises a diamond material subjected to electrical conduction by doping with preferably boron.
  • the doped diamond material optionally lining the metal material constituting the cathode may be a p-type, n-type or co-doped semiconductor (donor, electron receptor or both, respectively).
  • the cathode must be less than said anode in length.
  • the cathode must have a diameter larger than said anode.
  • the cathode must be stable at negative potential.
  • the anode may be hollow or not.
  • the mechanically resistant cylindrical substrate constituting the anode comprises an outside diameter from 4 mm, preferably from 4 to 20 mm.
  • the mechanically resistant cylindrical substrate constituting the anode is selected from the group comprising a conductive or insulating material capable of withstanding the conditions of the blasting processes; able to withstand the conditions of chemical deposition processes from the vapor phase; and which may be made of cylindrical or spherical or cylindrical tubular shape.
  • the mechanically resistant cylindrical substrate constituting the anode may be quartz, titanium, tungsten or stainless steel.
  • - doped diamond material lining the anode comprises diamond material subjected to electrical conduction by doping with some selected impurity from the chemical elements boron, phosphorus, bismuth, nitrogen or sulfur.
  • the doped diamond material lining the anode may be a p-type, n-type or co-doped semiconductor (donor, electron receptor or both, respectively).
  • the doped diamond material lining the anode comprises a film of thickness preferably ranging from 0.5 to 50 ⁇ .
  • the cylindrical electrochemical cell can be mounted with a doped diamond cylindrical anode obtained by chemical vapor deposition process, wherein said diamond films are uniformly, homogeneously and adherently deposited on a mechanically resistant quartz cylindrical substrate of 6 mm outside diameter, arranged coaxially inside a 9 mm inside diameter stainless steel cathode.
  • the seals are made with rubber threaded snap rings.
  • In the cathode body there are two connections for inlet and outlet of the solution to be treated. Hoses connect these connections in series with a mechanical pump (to establish solution flow through the system) and a storage container (for solution collection or exchange). Electrical contacts are made on the anode body.
  • Conductive glue is used to establish contact between the conductive wires and the diamond film when the substrate used is insulating. Power is supplied by a direct current stabilized voltage source.
  • the cylindrical electrochemical cell may be divided by one or more ion exchange membranes or resin.
  • the configuration comprising the ion exchange membrane (s) or resin may be used in situations where the solution to be treated has low electrical conductivity.
  • the ion exchange membrane may be fluororesin or hydrocarbon based. In practice, however, a corrosion resistant resin is desired.
  • Commercially available membranes for use in the present invention are: Nafion (DuPont), Aciplex (Asahi Chemical Industry Co., Ltd.), Flemion (Asahi Glass Co., Ltd.), etc.
  • the membrane or resin is preferably used in close contact with the anode and / or cathode.
  • the membrane must be mechanically bonded to each electrode.
  • the ion exchange membrane, if used, should be pressed from 0.1 to 30 kg cm- 2 during electrolysis.
  • the solution containing one substance or many substances to be treated it is used as an electrolyte solution.
  • the solution is placed in contact with the anode made of doped diamond and the cathode made of a conductive material, whether or not doped diamond.
  • Substances may be directly or indirectly oxidized to low molecular weight substances or mineralized to CO 2 .
  • Electrolysis conditions vary depending on the solution to be used, etc., but the temperature is preferably from 5 to 40 ° C and the current density is preferably from 1 to 100 mA cm 2 .
  • the materials that can be used in the construction of the electrochemical cell are glass, titanium, stainless steel, PTFE (Teflon ® ) resin, quartz, tungsten and high density rubber.
  • the goal is to use materials with excellent corrosion resistance, durable and stable when in the presence of strong oxidizers that are produced during the process.
  • the present invention provides for a process of depositing uniform, homogeneous and adherent diamond films on larger diameter tough cylindrical substrates (from 4.0 mm), preferably between 4 and 20 mm, previously shot blasted with grit. iron or steel, made by the CVD (Chemical Vapor Deposition) technique to obtain coaxial doped diamond anodes.
  • CVD Chemical Vapor Deposition
  • c) perform the "sowing” process, which includes the insertion of small diamond grains in the substrate to enable the growth of diamond structures.
  • This process can be performed via ultrasonic bathing on tough (clean and sandblasted) cylindrical substrates in hexane solution with diamond dust;
  • the substrates are inserted into the hot-filament chemical vapor deposition (HFCVD) assisted chemical deposition reactor chamber.
  • Diamond films can be grown from a carbon source in the presence of hydrogen. using the CVD technique.
  • the carbon sources may be organic gases such as methane (CH 4 ), the most commonly used, or liquid gases such as ethanol (C 2 H 5 OH), which was used in the present invention.
  • Diamond synthesis can be performed by the process of chemical deposition from the hot filament vapor phase (HFCVD) with thermal decomposition of organic compounds such as ethanol, methanol, methane, etc. as carbon source in a reducing atmosphere such as as hydrogen gas.
  • HFCVD hot filament vapor phase
  • the doped diamond on the substrate constitutes the active part of the electrode, which thus produced has high potential to be used.
  • j as anode or cathode is excellent durability.
  • said electrode should preferably be used as anode.
  • pretreatment was performed using motor oil. Scanning electron microscope analyzes were performed and it was verified that the film did not present cracks, besides presenting excellent quality and homogeneity.
  • the present invention provides the coaxial doped diamond anodes obtained by the chemical deposition process from the hot filament vapor phase (HFCVD) with thermal decomposition of organic compounds from larger diameter resistant cylindrical substrates, preferably between 4 and 20 mm, previously blasted with iron or steel shot.
  • HFCVD hot filament vapor phase
  • the anodes thus produced have excellent durability.
  • anode comprises a mechanically resistant, hollow or unblasted, uniformly coated, homogeneous and adherent cylindrical substrate adhered by at least one layer of diamond thin film. doped, where:
  • the mechanically resistant cylindrical substrate constituting the anode comprises an outside diameter from 4 mm, preferably from 4 to 20 mm.
  • the mechanically resistant cylindrical substrate constituting the anode is selected from the group comprising a conductive or insulating material capable of withstanding the conditions of the blasting processes; able to withstand the conditions of chemical deposition processes from the vapor phase; and which may be made of cylindrical or spherical or cylindrical tubular shape.
  • the mechanically resistant cylindrical substrate constituting the anode may be quartz, titanium, tungsten or stainless steel.
  • - doped diamond material lining the anode comprises diamond material subjected to electrical conduction by doping with some selected impurity from the chemical elements boron, phosphorus, bismuth, nitrogen or sulfur.
  • the doped diamond material lining the anode may be a p-type, n-type or co-doped semiconductor (donor, electron receptor or both, respectively).
  • the doped diamond material lining the anode comprises a film of thickness preferably ranging from 0.5 to 50 pm.
  • the doped diamond material lining the anode is preferably deposited by the chemical deposition process from the vapor phase.
  • cylindrical electrochemical cell conceived in the present invention proposes to provide an electrochemical treatment for oxidizing substances contained in aqueous solution, which can be accomplished by introducing the solution containing substances to be treated into the electrochemical cell with a cylindrical anode and cathode and passing An electric current through them is therefore an additional object of the present invention the use of said cylindrical electrochemical cell in the purification of aqueous solutions, which utilizes coaxial diamond anode obtained by depositing uniform, homogeneous and adherent diamond films on Cylindrical substrates of larger diameters, preferably between 4 and 20 mm, previously blasted with iron or steel grit, performed by the CVD technique. It is therefore an object of the present invention a cylindrical electrochemical cell assembled with cylindrical electrodes, wherein said cell comprises:
  • an aqueous waste from domestic sewage with the boron-doped diamond coated anode and the stainless steel cathode (AISI 304), an aqueous waste from domestic sewage, with electrolyte (Na 2 SO 4 ) added at pH 2 and compounds phenol, catechol, hydroquinone, p-cresol, m-cresol and guaiacol were oxidized. Concentrations of the compounds in the solution were 94 pg ml -1 for phenol, 10 pg ml -1 for hydroquinone, guaiacol and catechol and 53 pg ml -1 for p-cresol and m-cresol. Therefore, a total concentration of 530 pmol mL "1 .
  • FIG. 8 shows the removal of both. With a current of 35 mA and an average voltage of 6 V the energy cost was 7.56 kW hm "3 for the removal of 64.40% of TOC and 94.95% of molecular fluorescence intensity, the latter being measures total aromaticity removal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

La présente invention concerne une cellule électrochimique destinée à la purification de solutions aqueuses, faisant intervenir une anode coaxiale de diamant dopé obtenue par procédé de dépôt chimique en phase vapeur, des films de diamant étant déposés sur des substrats cylindriques mécaniquement résistants préalablement soumis à un jet, ledit procédé permettant d'obtenir des films uniformes, homogènes et adhérents. Plus particulièrement, la cellule électrochimique contenant ladite anode permet d'électrolyser efficacement des substances indésirables contenues dans des rejets aqueux ou de l'eau potable, de manière à rendre ces composés inoffensifs et/ou à réduire de façon importante la concentration en composés toxiques. En outre, elle est efficace pour les oxydations directes et indirectes, outre le fait que l'anode ne subit pas de modifications structurales physiques ou chimiques importantes sur sa surface pendant de longues durées de fonctionnement.
PCT/BR2010/000385 2009-12-01 2010-11-17 Cellule électrochimique cylindrique avec anode coaxiale de diamant dopé obtenue par procédé de dépôt de films de diamant sur des substrats cylindriques mécaniquement résistants en vue d'une application dans des procédés de purification de solutions aqueuses WO2011066632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BRPI0905277-1 BRPI0905277B1 (pt) 2009-12-01 2009-12-01 célula eletroquímica cilíndrica com anodo de diamante dopado coaxial
BRPI0905277-1 2009-12-01

Publications (1)

Publication Number Publication Date
WO2011066632A1 true WO2011066632A1 (fr) 2011-06-09

Family

ID=44114567

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/BR2010/000385 WO2011066632A1 (fr) 2009-12-01 2010-11-17 Cellule électrochimique cylindrique avec anode coaxiale de diamant dopé obtenue par procédé de dépôt de films de diamant sur des substrats cylindriques mécaniquement résistants en vue d'une application dans des procédés de purification de solutions aqueuses

Country Status (2)

Country Link
BR (1) BRPI0905277B1 (fr)
WO (1) WO2011066632A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013007816A3 (fr) * 2011-07-14 2013-06-20 United Initiators Gmbh & Co. Kg Cellule électrolytique non divisée et son utilisation
WO2014009536A1 (fr) * 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Cellule électrolytique dépourvue de séparateur et son utilisation
WO2014019991A1 (fr) * 2012-07-30 2014-02-06 Elta Cellule d'electrolyse et chaine de detection avec ladite cellule et cellule de detection electrochimique de metaux lourds
GB2544267A (en) * 2015-11-04 2017-05-17 Charles Llewelyn Thomas Robert Waste water treatment
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
WO2018100357A1 (fr) * 2016-11-29 2018-06-07 Roseland Holdings Limited Électrode et cellule électrochimique comprenant celle-ci
WO2018100359A1 (fr) * 2016-11-29 2018-06-07 Roseland Holdings Limited Électrode et cellule électrochimique la comprenant

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186973A (en) * 1990-09-13 1993-02-16 Diamonex, Incorporated HFCVD method for producing thick, adherent and coherent polycrystalline diamonds films
US6306270B1 (en) * 1999-02-25 2001-10-23 Csem Centre Suisse D'electronique Et De Microtechnique Sa Electrolytic cell with bipolar electrode including diamond
JP2004358452A (ja) * 2003-06-04 2004-12-24 Ebara Corp 電解処理装置
KR20060046358A (ko) * 2004-06-01 2006-05-17 인하대학교 산학협력단 붕소 도핑 다이아몬드 전극을 이용한 전기화학적 폐수처리방법
BRPI0502246A (pt) * 2005-05-31 2007-01-23 Unicamp processo eletroquìmico de oxidação de compostos orgánicos utilizando um reator composto de um anodo de diamante
EP1411143B1 (fr) * 2002-10-14 2007-07-18 Adamant Technologies SA Procédé de fabrication de pieces tubulaires avec revêtement interne de diamant
BRPI0600897A (pt) * 2006-03-16 2007-11-20 Unicamp processo de fabricação de eletrodos de diamante dopado para eletroquìmica
MXPA06014912A (es) * 2006-12-18 2008-10-08 Univ Autonoma Metropolitana Procedimiento para la electro-incineracion de materia organica contenida en soluciones acuosas y equipo que aplica este proceso.

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5186973A (en) * 1990-09-13 1993-02-16 Diamonex, Incorporated HFCVD method for producing thick, adherent and coherent polycrystalline diamonds films
US6306270B1 (en) * 1999-02-25 2001-10-23 Csem Centre Suisse D'electronique Et De Microtechnique Sa Electrolytic cell with bipolar electrode including diamond
EP1411143B1 (fr) * 2002-10-14 2007-07-18 Adamant Technologies SA Procédé de fabrication de pieces tubulaires avec revêtement interne de diamant
JP2004358452A (ja) * 2003-06-04 2004-12-24 Ebara Corp 電解処理装置
KR20060046358A (ko) * 2004-06-01 2006-05-17 인하대학교 산학협력단 붕소 도핑 다이아몬드 전극을 이용한 전기화학적 폐수처리방법
BRPI0502246A (pt) * 2005-05-31 2007-01-23 Unicamp processo eletroquìmico de oxidação de compostos orgánicos utilizando um reator composto de um anodo de diamante
BRPI0600897A (pt) * 2006-03-16 2007-11-20 Unicamp processo de fabricação de eletrodos de diamante dopado para eletroquìmica
MXPA06014912A (es) * 2006-12-18 2008-10-08 Univ Autonoma Metropolitana Procedimiento para la electro-incineracion de materia organica contenida en soluciones acuosas y equipo que aplica este proceso.

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013007816A3 (fr) * 2011-07-14 2013-06-20 United Initiators Gmbh & Co. Kg Cellule électrolytique non divisée et son utilisation
CN103827354A (zh) * 2011-07-14 2014-05-28 联合引发剂有限责任两合公司 不分开的电解槽及其用途
US9556527B2 (en) 2011-07-14 2017-01-31 United Initiators Gmbh & Co. Kg Undivided electrolytic cell and use of the same
WO2014009536A1 (fr) * 2012-07-13 2014-01-16 United Initiators Gmbh & Co. Kg Cellule électrolytique dépourvue de séparateur et son utilisation
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
WO2014019991A1 (fr) * 2012-07-30 2014-02-06 Elta Cellule d'electrolyse et chaine de detection avec ladite cellule et cellule de detection electrochimique de metaux lourds
GB2544267A (en) * 2015-11-04 2017-05-17 Charles Llewelyn Thomas Robert Waste water treatment
US10604428B2 (en) 2015-11-04 2020-03-31 Robert Charles Llewelyn Thomas Waste water treatment
GB2544267B (en) * 2015-11-04 2021-03-24 Charles Llewelyn Thomas Robert Waste water treatment
WO2018100357A1 (fr) * 2016-11-29 2018-06-07 Roseland Holdings Limited Électrode et cellule électrochimique comprenant celle-ci
WO2018100359A1 (fr) * 2016-11-29 2018-06-07 Roseland Holdings Limited Électrode et cellule électrochimique la comprenant
US11390957B2 (en) 2016-11-29 2022-07-19 Oxi-Tech Solutions Limited Electrode and electrochemical cell comprising the same

Also Published As

Publication number Publication date
BRPI0905277A2 (pt) 2011-07-19
BRPI0905277B1 (pt) 2019-11-26

Similar Documents

Publication Publication Date Title
WO2011066632A1 (fr) Cellule électrochimique cylindrique avec anode coaxiale de diamant dopé obtenue par procédé de dépôt de films de diamant sur des substrats cylindriques mécaniquement résistants en vue d'une application dans des procédés de purification de solutions aqueuses
US7285194B2 (en) Conductive diamond electrode and process for producing the same
US5900127A (en) Electrode for electrolysis and electrolytic cell using the electrode
Tröster et al. Electrochemical advanced oxidation process for water treatment using DiaChem® electrodes
KR101340239B1 (ko) 오존 생성 장치
US6375827B1 (en) Electrochemical treating method and apparatus
JP5368340B2 (ja) 二酸化炭素の電解還元装置
EP3067324B1 (fr) Procédé pour la préparation d'électrodes de diamant nanocristallin dopé au bore
JPH09268395A (ja) 電解用電極及び該電極を使用する電解槽
Wang et al. Flow-through electrochemical removal of benzotriazole by electroactive ceramic membrane
Jiang et al. Simultaneous hydrogen production and electrochemical oxidation of organics using boron-doped diamond electrodes
Haenni et al. Industrial applications of diamond electrodes
Zhang et al. Co-degradation of ammonia nitrogen and 4-chlorophenol in a photoelectrochemical system by a tandem reaction of chlorine and hydroxyl radicals
Brosler et al. In-house vs. commercial boron-doped diamond electrodes for electrochemical degradation of water pollutants: A critical review
Vasconcelos et al. Recent advances on modified reticulated vitreous carbon for water and wastewater treatment–A mini-review
TWI467058B (zh) 硫酸電解槽及使用硫酸電解槽之硫酸循環型清洗系統
Chen et al. Fabrication of a SnO2–Sb electrode with TiO2 nanotube array as the middle layer for efficient electrochemical oxidation of amaranth dye
Fryda et al. Applications of DIACHEM® electrodes in electrolytic water treatment
CN109809532A (zh) 一种超低功耗的污水处理电化学反应器
JP2007070701A (ja) 固体高分子電解質型オゾン生成装置
Ma et al. Electrochemical oxidation of reactive brilliant orange X-GN dye on boron-doped diamond anode
Pushkarev et al. Electrochemical generation of ozone in a system with a solid polymer electrolyte
JP2010270364A (ja) オゾン生成方法及びオゾン生成装置
BR122019019848B1 (pt) Processo de deposiqao de material diamantifero para obtenqao de anodo de diamante dopado e anodo de diamante dopado obtido pelo processo
Liu et al. Study on the wastewater disinfection at the boron-doped diamond film electrode

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10834109

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10834109

Country of ref document: EP

Kind code of ref document: A1