EP0813501A1 - Procede et dispositif de traitement electrochimique de l'eau, en vue de son adoucissement - Google Patents
Procede et dispositif de traitement electrochimique de l'eau, en vue de son adoucissementInfo
- Publication number
- EP0813501A1 EP0813501A1 EP96906805A EP96906805A EP0813501A1 EP 0813501 A1 EP0813501 A1 EP 0813501A1 EP 96906805 A EP96906805 A EP 96906805A EP 96906805 A EP96906805 A EP 96906805A EP 0813501 A1 EP0813501 A1 EP 0813501A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- water
- calcium carbonate
- value
- treated
- 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- Withdrawn
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
- C02F1/4602—Treatment of water, waste water, or sewage by electrochemical methods for prevention or elimination of deposits
-
- 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
Definitions
- the present invention relates to a process for the electrochemical treatment of water, with a view to softening it, as well as to a device for implementing this process.
- the present invention aims to remedy these drawbacks by proposing a method and an apparatus making it possible, under particularly economical and reliable conditions, to obtain controlled, total or partial softening of water.
- the subject of the present invention is therefore a process for the electrochemical treatment of water with a view to reducing its hydrotiter, in which an electrolysis of the water to be treated is carried out between an anode and a cathode, respectively connected to the terminals positive and negative of a current generator, each consisting of at least one electrode, characterized in that it comprises the stages consisting in constituting at the cathode a thin and porous coating formed at least in part of calcium carbonate, producing simultaneously an electrolysis of water and the formation of a gas flow, through the porosities of the cathode, so that the crystals constituted at least in part of calcium carbonate which are formed on said coating during 1 ' electrolysis are detached from it under the action of said gas flow.
- the hydrotimetric degree of the treated water can be checked, in particular automatically, by measuring the value of a given parameter thereof and by modifying the value of the intensity of the electric current flowing through the liquid to be treated as a function of the value of said parameter.
- the present invention also relates to an electrochemical water treatment device with a view to reducing its hydrotimetric titer, consisting of an electrolytic cell comprising an anode and a cathode respectively connected to the positive and negative terminals of a generator.
- current each consisting of at least one - electrode, characterized in that the cathode comprises a coating consisting, at least in part, of adhesive and porous calcium carbonate, and means for, through the porosities of this cathode, propel a gas flow, so as to take off and precipitate the deposits which form on said coating, and in particular the deposits of calcium carbonate.
- the cathode consists of a porous metal, in particular a sintered metal, covered with a thin and porous layer of calcium carbonate.
- the gas jet can consist of hydrogen, the latter being obtained in particular by bringing the potential of the cathode to a given sufficient value.
- this device comprises means capable of measuring the value of a given parameter of the treated water and means capable of modifying the value of the intensity of the electric current flowing through the electrolytic cell as a function of the value of said parameter.
- Figure 1 is an electrical diagram of a water treatment device according to the invention.
- Figure 2 is a perspective drawing of a water treatment device according to the invention.
- Figure 3 is a longitudinal sectional view of an alternative embodiment of a cathode according to the invention.
- Figure 4 is a diagram of an embodiment for constituting a cathode covered with a thin and porous coating of calcium carbonate.
- Figure 5 is a schematic view of an embodiment of the invention.
- FIG. 6 is a sectional view of a water treatment device according to the invention along the line VI-VI of FIG. 7.
- Figure 7 is a sectional view of the device shown in Figure 6 along line VII-VII thereof.
- the device according to the invention represented in FIG. 1 essentially consists of a current generator 1 which supplies a power potentiometer 3 which delivers between its terminals A and B a current of intensity adjustable when these are respectively connected to an anode 5 and to a cathode 7 of an electrolytic tank 8 containing the water 10 which it is desired to lower the hydrotimetric titer.
- the terminals A and B of the potentiometer 3 are connected to the two ends of a divider bridge, consisting of two resistors, namely a fixed resistor 9 and an adjustable resistor 11, of which a midpoint C allows an adjustable reference voltage to be taken which is supplied to an electronic voltage comparator 13.
- the latter is connected to an adjustable voltage generator 15, the positive terminal of which is connected to the ground and the negative terminal of which is connected to the cathode 7, so that it makes it possible to apply to it an adjustable negative voltage.
- the electrolytic tank 8 is for example made up of a tank of insulating material of parallelepipedal shape which comprises at its base a water inlet pipe to be treated 22, and at its upper part, a evacuation pipe for the treated water 24.
- the cathode 7 consists of eight stainless steel plates 7a, preferably of the food type such as that of reference 316L, which are kept parallel to one another by nine bars 5a, with the interposition of insulating rings 6, so that these bars constitute the anodes 5.
- the nine bars 5a are joined together and at an anode terminal 14 by a conductor 12, and the eight plates 7a are joined together and at a cathode terminal 17 by a bar 16.
- the surface of the plates 7a forming the cathode 7 is carefully polished, either mechanically or preferably by electrolytic polishing.
- the ratio of the total surface ⁇ 5 of the plates 7a forming the cathode 7 to the total surface S_ of the bars 5a forming the anode 5 is of the order of 10 to 20, so that at the anode the surface density of the current or 10 to 20 times greater than it is at cathode 7.
- the cathode plates 7a are spaced from each other by about 2 cm.
- the material constituting the anode 5 is such that the oxidation reaction of the water takes place there without excessive overvoltage. Furthermore, this material must be stable over very long periods. Use will therefore preferably be made of titanium and preferably of titanium coated with platinum, iridium or ruthenium. Under these conditions, the operation of the present device is carried out as described below.
- a thin and porous layer, called a primary layer, of calcium carbonate is formed on the plates 7a constituting the cathode 7.
- a first electrolysis of the water is carried out in which the voltage generator 15 is adjusted so that it applies a negative voltage to the cathode 7, such that the only electrochemical reaction at the cathode is the reduction of oxygen. dissolved, so that a thin and adherent layer of calcium carbonate is then deposited on the cathode according to the reaction: 4 Ca ++ + 4 HC03 " + 02 + 4th Ca CO3 + 2H 2 0
- the resistance of the electrolytic cell gradually increases, so that the intensity of the electrolysis current decreases, as does the potential difference at terminals A and C of the voltage comparator 13, to reach a predetermined threshold value, which has been fixed beforehand by means of the adjustable resistor 11, of the divider bridge.
- This value is preferably such that it corresponds to a drop in the intensity of the current in the electrolytic cell of 20%.
- the comparator 13 controls the voltage generator 15 which applies to the cathode 7 a negative voltage with respect to the mass, which is fixed at a determined value, to cause the cathode to reduce the water, which results in a evolution of hydrogen according to the well known reaction:
- the porous layer of calcium carbonate plays the role of nucleation center and generates thereon the formation of germs which serve as a support for the birth of crystals of calcium carbonate during electrolysis, these crystals being torn from the cathode by the stream of hydrogen, so that they then precipitate in the liquid 10 and fall to the bottom of the tank 8, where it suffices to recover them.
- the calcium carbonate crystals being torn from the cathode 7 as they are formed, the thickness of the primary layer of calcium carbonate remains constant over time and the electrolysis can be prolonged as long as necessary.
- a negative potential is applied to the cathode sufficient for the surface current density at the cathode to be greater than 2A / m ⁇ .
- the surface density of the current at the cathode will be between 2A / m.2 and 8A / m.2.
- porous cathodes can be used, and in particular cathodes made of sintered metal. These cathodes are in a first step covered with a porous layer of calcium carbonate. They are, as shown in FIG. 3, constituted by a sintered metal cylinder 7 ′ comprising a central and longitudinal cavity 18 which is in communication, via a pipe 20, with means for supplying gas under pressure. The gas is released through the cathode 7 ′, so that it entrains the calcium carbonate crystals formed thereon during electrolysis.
- the voltage generator 15 is no longer used, since it is no longer necessary to cause the cathode to reduce the water in order to obtain a release of hydrogen.
- the process according to the invention generating carbon dioxide at the anode, the treated water gradually acidifies as the treatment progresses. The decrease in pH thus makes it possible to control, as explained below, the process of decarbonation of water.
- the decarbonated water thus produced insofar as one does not wish to use its aggressive character (as explained below) with respect to Ca CO 3 , will therefore have to undergo a treatment intended to remove the carbon.
- Known methods of mixing, whirling, runoff, etc. may be used for this.
- the device consists of a sintered metal support, intended to constitute the cathode, having the shape of a bell 21.
- This bell 21 is immersed in a tank 23 supplied with carbonated water by a lower pipe 25.
- the tank 23 has an upper pipe 26 which acts as an overflow.
- An electrical resistor 28 is disposed inside the bell 21, and a pipe 30 communicates the interior of the latter with the interior of the tank 23.
- Electric resistance is supplied with electric current 28 so as to bring the water contained to the boil in the tank 23.
- a deposit of calcium carbonate is formed on the walls of the bell 21, and in particular on the external walls of the latter.
- the vapor bubbles formed in the bell 21 pass through its walls of sintered metal to escape outside by passing through the thin coating of calcium carbonate formed, which creates pores therein.
- the process is interrupted and a cathode covered with a thin and porous layer of calcium carbonate is thus available.
- the pipe 30 makes it possible to take off water that has already been treated, therefore deprived in part of its calcium carbonate, in order to produce the vapor bubbles, which minimizes the amount of calcium carbonate formed inside the bell 21.
- each anode and each cathode can be made up of any number of elements.
- this calcium carbonate layer When the porous calcium carbonate layer is formed on a sintered metal, and more generally on a porous metal, this calcium carbonate layer can be used as a filtration membrane, either in the case where it is performed by thermal effect or by electrolysis. It is easy to regularly interrupt the release of gas through the layer of calcium carbonate to use the pores of this layer as a passage for the water to be filtered. A simple system to prevent clogging of pores consists of alternating the filtration and gas evolution operations.
- the present invention makes it possible to control, in particular automatically, the level of decarbonation of water.
- a physico-chemical parameter of the water is continuously measured during the electrolysis and, as soon as it reaches a predetermined value representative of the decarbonation state of the water, action is taken. on the process.
- the intervention on the electrolysis process can also be progressive, and it is thus possible, as the pH of the treated water decreases, gradually decrease the electrolysis current to cut it completely when 'a given floor value is reached.
- FIG. 5 thus represents a device according to the invention comprising a sensor 36 which is arranged on a pipe 38 downstream of an electrolytic cell 40 and which is connected to an analysis block 42.
- the latter compares the parameter measured by the sensor 36, in particular the pH, the conductivity, etc., at a set value recorded in the analysis block 42. This is in relation with an interface 44 capable of acting on the intensity of the current flowing through the electrolytic cell 40 in order to correct it as a function of the measurement carried out by the sensor 36.
- One of the parameters which is particularly suitable for controlling the hydrotimetric titer of water is the pH, on the one hand due to its close correlation with it and on the other hand to the ease of its measurement.
- the process and the device according to the invention make it possible, together with the crystallization of calcium carbonate, to ensure the precipitation of other salts, in particular iron, sodium, manganese salts, etc., the all of these reactions which can lead to a partial purification of water or more exactly to a more complete demineralization thereof.
- the present invention is thus advantageous for the treatment of brackish or ferruginous water.
- the present invention can also be implemented in a lamellar settling device.
- a device of this type consisting of a closed tank 50 having at its upper part an inlet pipe for the water to be treated 52.
- the interior of the tank 50 is delimited in two chambers, namely an inlet chamber 54 of small volume and a treatment chamber 58, by a transverse partition 56 which extends from the upper part of the tank 50 to a distance from the bottom thereof , so as to allow communication from the inlet chamber 54 with the treatment chamber 58.
- the interior of the treatment chamber 58 comprises a series of twelve transverse plates 59 inclined with respect to the vertical and which are held at their lower part by longitudinal beams 60 and at their upper part by longitudinal beams 62.
- the upper part of the inclined plates is in communication with a device too full 64 connected to a discharge pipe for treated water 66.
- the plates 59 are made of a metal, and in particular of stainless steel, and are joined together by a longitudinal rod 68 so that they constitute as many electrodes forming the cathode 7 of the device according to the invention.
- Metallic wires 70 are stretched between each of the lower 60 and upper 62 beams, between the plates 59. All the wires 70 of the same beam are joined together by a longitudinal wire 72, the various longitudinal wires 72 being interconnected by a transverse wire 74, so that the various wires 70 constitute as many electrodes forming the anode 5 of the device.
- the various wires 70 forming the anode 5 will be made of iridized titanium.
- Such a device is particularly advantageous in that it combines the normal effect of a decanter with that of the treatment of water according to the invention.
- This device is also particularly effective in that it combines a large surface of electrodes and a large volume of degassing.
- the decarbonation yield is increased by removing part of the hardness of the water to be treated by passing it through a fluidized bed consisting of the crystals formed mainly by the calcium carbonate extracted from the water during treatment. Such a passage can also be carried out from already treated water.
- all the parts of the cathode can be made using vitreous carbon or silver, which makes it possible to reduce any excess dissolved oxygen in the water during its passage through the treatment cell. .
- the demineralized water thus obtained for the purpose of temporarily or periodically descaling installations, in particular installations using boilers.
- Timing systems can thus be used which allow the boiler to operate normally during the day and which, at night, control bypass means making it possible to circulate in the pipes of the boiler and its accessories the water previously treated. This significantly reduces the scaling of the circuits of this boiler, by periodic dilution of the scale formed.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9502819 | 1995-03-10 | ||
FR9502819A FR2731420B1 (fr) | 1995-03-10 | 1995-03-10 | Procede et dispositif de traitement de l'eau en vue de son adoucissement par voie electrochimique |
PCT/FR1996/000369 WO1996028389A1 (fr) | 1995-03-10 | 1996-03-08 | Procede et dispositif de traitement electrochimique de l'eau, en vue de son adoucissement |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0813501A1 true EP0813501A1 (fr) | 1997-12-29 |
Family
ID=9476933
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96906805A Withdrawn EP0813501A1 (fr) | 1995-03-10 | 1996-03-08 | Procede et dispositif de traitement electrochimique de l'eau, en vue de son adoucissement |
Country Status (9)
Country | Link |
---|---|
US (1) | US5897765A (fr) |
EP (1) | EP0813501A1 (fr) |
JP (1) | JPH11501568A (fr) |
CN (1) | CN1181746A (fr) |
AU (1) | AU707432B2 (fr) |
CA (1) | CA2215488A1 (fr) |
FR (1) | FR2731420B1 (fr) |
RU (1) | RU2164219C2 (fr) |
WO (1) | WO1996028389A1 (fr) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7758742B2 (en) | 1998-02-27 | 2010-07-20 | Scott Wade Powell | Method and apparatus for separation of water from petroleum products in an electrocoagulation process |
US8048279B2 (en) | 1998-02-27 | 2011-11-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
US7211185B2 (en) | 1998-02-27 | 2007-05-01 | Scott Wade Powell | Method and apparatus for electrocoagulation of liquids |
IL137892A (en) | 1998-02-27 | 2004-06-20 | Scott Wade Powell | METHOD AND DEVICE FOR ELECTROCOGULATION OF LIQUIDS |
US6284293B1 (en) * | 2000-04-12 | 2001-09-04 | Jeffery J. Crandall | Method for generating oxygenated water |
AU2002952743A0 (en) * | 2002-11-19 | 2002-12-05 | Waterpower Systems Pty Ltd | Electrocoagulation system |
FR2875227B1 (fr) * | 2004-09-16 | 2006-12-01 | Saint Gobain Seva | Procede et dispositif de traitement d'un fluide |
EP1817261A1 (fr) * | 2004-09-16 | 2007-08-15 | Saint-Gobain Seva | Procede et dispositif de traitement d'un fluide par electrolyse. |
CN101193822B (zh) * | 2005-06-08 | 2013-06-12 | 棚氏处理有限公司 | 液体的pH调节方法以及pH调节装置 |
US20090134029A1 (en) * | 2005-09-27 | 2009-05-28 | Tanah Process Ltd. | Ion Concentration Regulation Method and Ion Concentration Regulation Apparatus |
US7998225B2 (en) | 2007-02-22 | 2011-08-16 | Powell Scott W | Methods of purifying biodiesel fuels |
US20090032446A1 (en) * | 2007-08-01 | 2009-02-05 | Triwatech, L.L.C. | Mobile station and methods for diagnosing and modeling site specific effluent treatment facility requirements |
US7699988B2 (en) * | 2007-08-02 | 2010-04-20 | Ecosphere Technologies, Inc. | Enhanced water treatment for reclamation of waste fluids and increased efficiency treatment of potable waters |
WO2009032455A1 (fr) * | 2007-08-02 | 2009-03-12 | Ecosphere Technologies, Inc. | Traitement des eaux amélioré dans le recyclage de fluides résiduaires et traitement à rendement accru des eaux potables |
US8906242B2 (en) * | 2007-08-02 | 2014-12-09 | Ecosphere Technologies, Inc. | Transportable reactor tank |
US8999154B2 (en) | 2007-08-02 | 2015-04-07 | Ecosphere Technologies, Inc. | Apparatus for treating Lake Okeechobee water |
US9266752B2 (en) | 2007-08-02 | 2016-02-23 | Ecosphere Technologies, Inc. | Apparatus for treating fluids |
US8721898B2 (en) * | 2007-08-02 | 2014-05-13 | Ecosphere Technologies, Inc. | Reactor tank |
US20100224495A1 (en) * | 2007-08-02 | 2010-09-09 | Mcguire Dennis | Real-time processing of water for hydraulic fracture treatments using a transportable frac tank |
US8529737B2 (en) * | 2008-03-25 | 2013-09-10 | Tanah Process Ltd. | Portable device for regulating hardness of drinking water |
US20110108437A1 (en) * | 2008-06-23 | 2011-05-12 | Tanah Process Ltd. | Disinfection method and disinfection device |
FR2937054B1 (fr) * | 2008-10-13 | 2010-12-10 | Commissariat Energie Atomique | Procede et dispositif de decontamination d'une surface metallique. |
US7981293B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
US7981301B2 (en) | 2008-11-21 | 2011-07-19 | Scott W. Powell | Method and apparatus for treatment of contaminated liquid |
EP2397789B1 (fr) * | 2009-02-16 | 2019-05-08 | Mitsubishi Electric Corporation | Chauffe-eau |
TWI386524B (zh) * | 2009-04-17 | 2013-02-21 | Univ Nat Kaohsiung 1St Univ Sc | 電化學表面處理治具 |
US9447657B2 (en) * | 2010-03-30 | 2016-09-20 | The Lubrizol Corporation | System and method for scale inhibition |
JP4968375B2 (ja) * | 2010-09-30 | 2012-07-04 | ダイキン工業株式会社 | ヒートポンプ式給湯機 |
WO2012051657A1 (fr) * | 2010-10-20 | 2012-04-26 | Poolrite Research Pty Ltd | Procédé de désinfection de l'eau |
US9028689B1 (en) | 2011-10-04 | 2015-05-12 | Global Water Holdings, Llc | Electric arc for aqueous fluid treatment |
RU2476624C1 (ru) * | 2011-12-13 | 2013-02-27 | Николай Петрович Куприков | Способ изготовления титанового электрода |
US10745299B2 (en) | 2013-02-22 | 2020-08-18 | NiBru Traka, Inc. | Struvite formation by precipitation of ammonia in electrocoagulation process |
US10358361B2 (en) | 2013-02-22 | 2019-07-23 | Loren L. Losh | System and method for remediation of wastewater including aerobic and electrocoagulation treatment |
FR3028531B1 (fr) * | 2014-11-14 | 2016-11-25 | Seb Sa | Appareil comportant une anode et une cathode pour faire precipiter le carbonate de calcium |
FR3063494B1 (fr) * | 2017-03-06 | 2022-05-27 | Saur | Procede de valorisation des sous-produits issus de la decarbonatation |
AU2020221906A1 (en) * | 2019-02-11 | 2021-08-05 | ElectroSea, LLC | System for electro-chemically inhibiting biological growth in air treatment units |
JP7330484B2 (ja) * | 2019-03-19 | 2023-08-22 | 株式会社白石中央研究所 | 炭酸カルシウム焼結体及び骨補填材 |
CN111924938B (zh) * | 2020-06-22 | 2021-11-19 | 西安交通大学 | 一种去除卤水中钙离子并回收碳酸钙的电化学方法 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SE429449B (sv) * | 1978-07-18 | 1983-09-05 | Chlorine Eng Corp Ltd | Elektrolyscell for elektrolys av havsvatten |
FR2569394A1 (fr) * | 1984-08-24 | 1986-02-28 | Mercier Dominique | Appareil de traitement de l'eau par flux electronique de basse tension qui permet la neutralisation simultanee d'un ou plusieurs sels dissous dans l'eau |
EP0233225A1 (fr) * | 1985-08-22 | 1987-08-26 | Hans LÜBER | Dispositif d'adoucissement d'eau et son procede d'utilisation |
-
1995
- 1995-03-10 FR FR9502819A patent/FR2731420B1/fr not_active Expired - Fee Related
-
1996
- 1996-03-08 CA CA002215488A patent/CA2215488A1/fr not_active Abandoned
- 1996-03-08 US US08/913,058 patent/US5897765A/en not_active Expired - Fee Related
- 1996-03-08 EP EP96906805A patent/EP0813501A1/fr not_active Withdrawn
- 1996-03-08 CN CN96193299.6A patent/CN1181746A/zh active Pending
- 1996-03-08 AU AU50077/96A patent/AU707432B2/en not_active Ceased
- 1996-03-08 JP JP8527329A patent/JPH11501568A/ja active Pending
- 1996-03-08 RU RU97116728/12A patent/RU2164219C2/ru not_active IP Right Cessation
- 1996-03-08 WO PCT/FR1996/000369 patent/WO1996028389A1/fr not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO9628389A1 * |
Also Published As
Publication number | Publication date |
---|---|
CN1181746A (zh) | 1998-05-13 |
FR2731420B1 (fr) | 1997-06-13 |
CA2215488A1 (fr) | 1996-09-19 |
WO1996028389A1 (fr) | 1996-09-19 |
AU5007796A (en) | 1996-10-02 |
US5897765A (en) | 1999-04-27 |
AU707432B2 (en) | 1999-07-08 |
FR2731420A1 (fr) | 1996-09-13 |
JPH11501568A (ja) | 1999-02-09 |
RU2164219C2 (ru) | 2001-03-20 |
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