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WO2012013221A1 - Appareil de traitement de l'eau et méthode de fabrication de celui-ci - Google Patents

Appareil de traitement de l'eau et méthode de fabrication de celui-ci Download PDF

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Publication number
WO2012013221A1
WO2012013221A1 PCT/EP2010/060899 EP2010060899W WO2012013221A1 WO 2012013221 A1 WO2012013221 A1 WO 2012013221A1 EP 2010060899 W EP2010060899 W EP 2010060899W WO 2012013221 A1 WO2012013221 A1 WO 2012013221A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
electrode
coating
substrate
water
Prior art date
Application number
PCT/EP2010/060899
Other languages
English (en)
Inventor
Rudolf Gensler
Ai Cheng Lee
Original Assignee
Siemens Aktiengesellschaft
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 Siemens Aktiengesellschaft filed Critical Siemens Aktiengesellschaft
Priority to PCT/EP2010/060899 priority Critical patent/WO2012013221A1/fr
Publication of WO2012013221A1 publication Critical patent/WO2012013221A1/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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene
    • 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

Definitions

  • the present invention relates to an apparatus for water treatment, in particular, for electrochemical treatment of water .
  • Electrochemical treatment of water for example, waste water, involves removal of ions or ionizable species from water in an electrochemical cell, such as an electrodialysis (ED) cell or an electrodeionization (EDI) cell.
  • ED electrodialysis
  • EDI electrodeionization
  • the standard material for anodes used in ED and EDI systems include titanium (Ti) coated with platinum (Pt) or metal dioxides based on ruthe ⁇ nium (Ru) and iridium (Ir) .
  • the object of the present invention is to provide a means for water treatment that is cost effective and energy efficient.
  • the above object is achieved by the apparatus according to claim 1 and the method according to claim 8.
  • the underlying idea of the present invention is to improve the energy efficiency and cost-effectiveness of a water treatment apparatus by using a graphene based electrode therein.
  • Graphene is the building block for graphite-like carbon materials of every other dimensionality. It is a one- atom thick sheet of carbon atoms arranged in a honeycomb, hexagonal lattice. The electrons moving around carbon atoms interact with the periodic potential of the honeycomb lattice of graphene, which gives rise to new quasi-particles that have lost their mass, or 'rest mass' (i.e. mass-less Dirac fermions) . That means that graphene never stops conducting. It was also found that electrons in graphene travel far faster than electrons in other semiconductors.
  • Graphene is a low cost material compared to the precious metals such as Pt, Ti, Ru and Ir and is substantially more electrically conduc- tive than these precious metals.
  • the use of a graphene as an electrode material in a water treatment apparatus is shown minimize the operating cost of the apparatus by providing very high current densities at significantly lower energy consumptions and reducing leakage current.
  • said at least one electrode is made of graphene particles dispersed in a composite bulk material. This makes it possible to manufacture the electrode in a sin ⁇ gle step, for example, by casting or injection molding.
  • said at least one electrode com ⁇ prises a substrate and a graphene based coating applied on a surface of the substrate.
  • a graphene coating can be applied on an existing electrode, which now becomes the substrate, to increase energy efficiency of an existing water treatment apparatus.
  • said graphene based coating is ap ⁇ plied around multiple surfaces of the substrate so as to form a continuous layer of said coating.
  • the substrate can be made of an electrically non- conductive material or an inexpensive material.
  • said coating comprises graphene particles dispersed in a liquid based binder material.
  • the coating can thus be applied using any known liquid coating process such as spray coating, dip coating, spin coating, flow coating and doctor blading, among others.
  • said binder material comprises a polymer, or a sol-gel binder, or ceramic particles.
  • said coating is cured in vacuum.
  • FIG 1 is a schematic diagram of a water treatment apparatus
  • FIG 2 shows an electrode having graphene particles dispersed in a composite bulk material, according to one embodiment of the present invention
  • FIG 3 shows an electrode having a graphene based coating ap- plied on a surface of a substrate, according another embodi ⁇ ment of the present invention.
  • FIG 4 shows an electrode having a graphene based coating ap ⁇ plied continuously around the substrate, according yet an- other embodiment of the present invention.
  • the present invention provides a energy efficient and cost effective water treatment apparatus having an electrochemical cell for removing ions or ionizable species from waste water.
  • Embodiments of the present invention are advantageous for several types of electrochemical cells for water treatment, such as, electrodialysis cells, electrodeionization (EDI) cells, capacitive deionization (CapDI) cells, electro ad ⁇ vanced oxidation process (EAOP) cells, electrochorination cells and electro-disinfection cells.
  • the electrodialysis cell 2 illustrated herein is a multi-chamber cell comprising depletion chambers 12 and concentration chambers 13 arranged in alternate order.
  • the chambers 12 and 13 are defined by spaced apart ion ex ⁇ change membranes 14 and 15, i.e., membranes that are selec ⁇ tively permeable to either positively or negatively charged ions.
  • the membranes are arranged such that positive ion se ⁇ lective membranes 14 are interspaced by 15 negative ion se- lective membranes.
  • the electrochemical cell 2 further in ⁇ cludes a pair of electrodes, namely an anode 3 disposed in an anode chamber 16 and a cathode 4 disposed in a cathode cham ⁇ ber 17.
  • the anode chamber 16 and cathode chamber 17 are lo ⁇ cated at opposite ends of the electrochemical cell 2.
  • Anolyte and catholyte solutions 18 and 19 respectively are conducted continuously through the anode chamber 16 and cathode chamber 17 respectively during the operation of the cell 2.
  • the solu ⁇ tion 11 through which ions are to be extracted which is waste water in this example, is made to occupy the volume of the depletion 12 chambers while the solution 20 in which ions are to be collected are made to occupy the volume of the con ⁇ centration chambers 13.
  • the ions are transferred, depending on their polarity, through the ion selective membranes 14 and 15, under the influence of an electrical potential applied to the electrodes 3 and 4 between which an electric current passes in series across the membranes 14 and 15 and compart ⁇ ments 12 and 13 defined between them.
  • one of the elec- trodes which, in this example, is the anode 3, is made of a material comprising graphene .
  • graphene is the building block for graphite-like carbon materials of every other dimensionality. It is a one-atom thick sheet of carbon atoms arranged in a honeycomb, hexagonal lattice. The electrons moving around carbon atoms interact with the peri ⁇ odic potential of the honeycomb lattice of graphene, which gives rise to new quasi-particles that have lost their mass, or 'rest mass' (i.e. mass-less Dirac fermions) . That means that graphene never stops conducting.
  • Graphene is a low cost material compared to the precious met ⁇ als such as Pt, Ti, Ru and Ir. Pure and un-doped graphene can carry and sustain an ultra-high current densities of about 10 8 A/cm 2 , which is two orders of magnitude greater than cop ⁇ per, and has an electrical resistivity of about 1.0x10-6 Q.cm at room temperature. Graphene is 35 % more electrically con ⁇ ductive than the most electrically conductive metal known to date, i.e.
  • the silver is 79 - 97 % more conductive than the precious metals (Pt, Ti, Ru and Ir) used for electrodes in ED or EDI application.
  • Pt, Ti, Ru and Ir precious metals
  • This feature enables the reduction of the leakage current (IR drop) due to the internal resis ⁇ tance of electrode materials, and the delivery of current density required by the ED or EDI systems at a lower energy consumption.
  • IR drop leakage current
  • graphene electrodes provide cost- effectiveness and high energy efficiency, thereby making electrochemical water treatment systems competitive on both the capital and operating costs basis.
  • the graphene based electrode 3 may be formed out of graphene particles 5 dispersed in a bulk com ⁇ posite material 6.
  • the composite material 6 may include, for example a polymer composite, a ceramic composite or even a metallic composite.
  • the graphene particles 6 may include, ex ⁇ ample nano graphene platelets (NGP) , which exhibit electrical properties comparable to carbon nano-tubes (CNT) but are more readily available at much lower costs.
  • NGP nano graphene platelets
  • the platelet shape offers NGP edges that are easier to modify chemically for enhanced dispersion in polymers.
  • particles 5 may include exfoliated nano graphite platelets (xNGP) that include small stacks of graphene that are 1 to 15 nanometers thick, with diameters ranging from sub-micrometers to 100 mi- crometers . Exfoliated nano graphite platelets may be obtained by heat expansion of intercalated graphite.
  • the particles 5 are dispersed to be present in an amount so that composite material 5 is electrically conductive.
  • the electrode 3 may be formed in a single step by casting or injection molding of the graphene based composite material into a suitable shape, such as a plate, a sheet, a foil or a mesh.
  • a graphene based electrode 3 may be formed by applying a graphene based coating 9 on a surface of a substrate 7.
  • the coating 9 is applied on one surface 8a of the sub ⁇ strate 7.
  • the coating 9 on the surface 8a is exposed to the electrochemical reaction during operation of the appa- ratus 1, while the surface 8b is coupled to an electrical contact 10 connected to a power supply.
  • the substrate 7 may be made of any metals, such as stainless steel, titanium, niobium, tantalum, vanadium and their alloys, as well as conductive ceramics, conductive plastics, conductive carbona- ceous materials.
  • the coating 9 is applied on mul ⁇ tiple surfaces 8a, 8b, 8c, and 8d to form a continuous layer of coating 9, having a one side exposed to the electrochemical reaction and an opposite side connected to an electrical contact 10.
  • the substrate 7 need not necessarily be made an electrically conductive ma- terial as long as it is dimensionally & chemically & electro- chemically stable for the target application.
  • the substrate 7 in both embodiments may be made in any suitable shape, such as a plate, a sheet, a mesh, a foil etc.
  • the coating layer 9 may comprise graphene-based materials or composites or paints.
  • the coating 9 is made of a mixture containing graphene powder and a liquid based binder component.
  • the binder compo ⁇ nent may include materials such as a chemically resistant polymer resin such as epoxy resin and silicone resin, with solvent (s) and processing additives.
  • a sol-gel binder may also be used instead of a polymer binder.
  • a binder composed of ceramic particles, including electrically conductive ce ⁇ ramic particles, is also a possible embodiment of this inven- tion.
  • the processes of making the graphene based coating 9 on the substrate 7 may include any liquid coating technique, for ex ⁇ ample spray coating, dip coating, spin coating, flow coating, doctor blading, etc.
  • the coating 9 is cured at temperatures and for curing times most appropriate for the respective coating formulations, typically between room temperature and 1000 °C and for 10 minutes - 2 days. For temperatures higher than 400 °C, curing is realized in vacuum to prevent oxida- tion of the graphene.
  • graphene based elec ⁇ trode in a water treatment apparatus in accordance with em ⁇ bodiments of the present invention.
  • graphene exhibits high chemical stability in acidic and alkaline me ⁇ dium, therefore capable of serving as electrode materials with excellent corrosion and oxidation resistance.
  • graphene electrodes have a wide operating potential window (> 3.5 V) comparable to that of boron-doped diamond (BDD) elec ⁇ trodes, but available at much lower costs compared to BDD.
  • BDD boron-doped diamond
  • Graphene electrodes may hence prove to be alternatives to BDD electrodes [e.g.
  • Electrodes in elec- trochemical advanced oxidation process (EAOP) for water treatment processes.
  • EAOP elec- trochemical advanced oxidation process
  • Graphene based electrodes proposed herein may hence have several target application areas in wa ⁇ ter treatment, including electrodes for ED, EDI, CapDI, EAOP, electrochlorination and electro-disinfection systems.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

L'invention concerne un appareil (1) de traitement de l'eau comprenant une cellule électrochimique (2) comportant au moins une paire d'électrodes (3, 4) permettant d'appliquer une différence de potentiel électrique à un volume d'eau (11) entre elles afin d'éliminer les ions ou les espèces ionisables contenues dans ladite eau (11). Selon la présente invention, au moins une (3) dite électrode est constituée d'un matériau contenant du graphène.
PCT/EP2010/060899 2010-07-27 2010-07-27 Appareil de traitement de l'eau et méthode de fabrication de celui-ci WO2012013221A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/060899 WO2012013221A1 (fr) 2010-07-27 2010-07-27 Appareil de traitement de l'eau et méthode de fabrication de celui-ci

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2010/060899 WO2012013221A1 (fr) 2010-07-27 2010-07-27 Appareil de traitement de l'eau et méthode de fabrication de celui-ci

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WO2012013221A1 true WO2012013221A1 (fr) 2012-02-02

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103058334A (zh) * 2013-01-17 2013-04-24 山东大学 一种石墨烯薄膜电极电化学处理印染废水的方法
CN103910415A (zh) * 2014-04-29 2014-07-09 山东大学 一种处理高浓度有机废水的三维石墨烯纳米材料电化学反应器
CN103922443A (zh) * 2014-04-29 2014-07-16 山东大学 一种三维石墨烯纳米材料电化学处理高浓度有机废水的方法
WO2016056994A1 (fr) * 2014-10-10 2016-04-14 Joyce River Hi-Tech Pte Ltd Appareil permettant de réaliser une électro-réaction de fenton pour la décomposition de composés chimiques organiques
WO2017014695A1 (fr) * 2015-07-20 2017-01-26 National University Of Singapore Dispositif et méthode pour procédé électro-fenton utilisant une électrode en carbone et son application pour éliminer les polluants organiques
CN108341467A (zh) * 2018-03-09 2018-07-31 陕西科技大学 一种Ag/GO/Ti电极与制备方法及其在去除水中硝酸盐中的应用
WO2022008621A1 (fr) * 2020-07-08 2022-01-13 Profit Gregoire Dispositif de traitement d'un liquide
CN114074981A (zh) * 2020-08-12 2022-02-22 云米互联科技(广东)有限公司 电去离子净水装置和家用净水装置
GB2623155A (en) * 2022-08-03 2024-04-10 Politechnika Lodzka A sieve electrode for separating ions

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* Cited by examiner, † Cited by third party
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US20070158618A1 (en) * 2006-01-11 2007-07-12 Lulu Song Highly conductive nano-scaled graphene plate nanocomposites and products
US20090092747A1 (en) * 2007-10-04 2009-04-09 Aruna Zhamu Process for producing nano-scaled graphene platelet nanocomposite electrodes for supercapacitors
US20090314652A1 (en) * 2008-03-19 2009-12-24 Buschmann Wayne E Production of Peroxycarboxylic Acids
EP2180539A1 (fr) * 2008-10-21 2010-04-28 Commissariat à l'Energie Atomique Nouveaux matériaux et leur utilisation dans l'évolution électrocatalytique ou la capture de H2
WO2010115904A1 (fr) * 2009-04-06 2010-10-14 Sa Envitech S.R.L. Électrodes à base de graphène pour des réactions électrochimiques et procédé d'électro-oxydation pour l'élimination de contaminants à partir de liquides à l'aide desdites électrodes
EP2315342A1 (fr) * 2009-10-23 2011-04-27 Voltea B.V. Appareil pour l'élimination d'ions, convertisseur de puissance bidirectionnel et procédé de fonctionnement pour l'élimination d'ions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070158618A1 (en) * 2006-01-11 2007-07-12 Lulu Song Highly conductive nano-scaled graphene plate nanocomposites and products
US20090092747A1 (en) * 2007-10-04 2009-04-09 Aruna Zhamu Process for producing nano-scaled graphene platelet nanocomposite electrodes for supercapacitors
US20090314652A1 (en) * 2008-03-19 2009-12-24 Buschmann Wayne E Production of Peroxycarboxylic Acids
EP2180539A1 (fr) * 2008-10-21 2010-04-28 Commissariat à l'Energie Atomique Nouveaux matériaux et leur utilisation dans l'évolution électrocatalytique ou la capture de H2
WO2010115904A1 (fr) * 2009-04-06 2010-10-14 Sa Envitech S.R.L. Électrodes à base de graphène pour des réactions électrochimiques et procédé d'électro-oxydation pour l'élimination de contaminants à partir de liquides à l'aide desdites électrodes
EP2315342A1 (fr) * 2009-10-23 2011-04-27 Voltea B.V. Appareil pour l'élimination d'ions, convertisseur de puissance bidirectionnel et procédé de fonctionnement pour l'élimination d'ions

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103058334A (zh) * 2013-01-17 2013-04-24 山东大学 一种石墨烯薄膜电极电化学处理印染废水的方法
CN103910415A (zh) * 2014-04-29 2014-07-09 山东大学 一种处理高浓度有机废水的三维石墨烯纳米材料电化学反应器
CN103922443A (zh) * 2014-04-29 2014-07-16 山东大学 一种三维石墨烯纳米材料电化学处理高浓度有机废水的方法
CN106660837A (zh) * 2014-10-10 2017-05-10 久瑞高科技私人有限公司 用于进行电芬顿反应以分解有机化合物的装置
WO2016056994A1 (fr) * 2014-10-10 2016-04-14 Joyce River Hi-Tech Pte Ltd Appareil permettant de réaliser une électro-réaction de fenton pour la décomposition de composés chimiques organiques
CN107848845A (zh) * 2015-07-20 2018-03-27 新加坡国立大学 用于使用碳电极的电芬顿方法的装置和方法及其用于去除有机污染物的应用
WO2017014695A1 (fr) * 2015-07-20 2017-01-26 National University Of Singapore Dispositif et méthode pour procédé électro-fenton utilisant une électrode en carbone et son application pour éliminer les polluants organiques
CN108341467A (zh) * 2018-03-09 2018-07-31 陕西科技大学 一种Ag/GO/Ti电极与制备方法及其在去除水中硝酸盐中的应用
WO2022008621A1 (fr) * 2020-07-08 2022-01-13 Profit Gregoire Dispositif de traitement d'un liquide
FR3112340A1 (fr) * 2020-07-08 2022-01-14 Grégoire PROFIT Dispositif de traitement d ’un liquide
CN114074981A (zh) * 2020-08-12 2022-02-22 云米互联科技(广东)有限公司 电去离子净水装置和家用净水装置
CN114074981B (zh) * 2020-08-12 2024-03-19 云米互联科技(广东)有限公司 电去离子净水装置和家用净水装置
GB2623155A (en) * 2022-08-03 2024-04-10 Politechnika Lodzka A sieve electrode for separating ions

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