EP2866843A1 - Filtre et procédé d'ultrafiltration - Google Patents

Filtre et procédé d'ultrafiltration

Info

Publication number
EP2866843A1
EP2866843A1 EP13732508.0A EP13732508A EP2866843A1 EP 2866843 A1 EP2866843 A1 EP 2866843A1 EP 13732508 A EP13732508 A EP 13732508A EP 2866843 A1 EP2866843 A1 EP 2866843A1
Authority
EP
European Patent Office
Prior art keywords
filter
ultrafiltration
water
membranes
water dispenser
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13732508.0A
Other languages
German (de)
English (en)
Inventor
Jürgen JOHANN
Monique Bissen
Bernd Bauer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BWT Holding GmbH
Original Assignee
BWT AG
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
Priority claimed from DE201210105720 external-priority patent/DE102012105720A1/de
Application filed by BWT AG filed Critical BWT AG
Publication of EP2866843A1 publication Critical patent/EP2866843A1/fr
Withdrawn legal-status Critical Current

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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/022—Filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/18—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/024—Hollow fibre modules with a single potted end
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • B01D63/024—Hollow fibre modules with a single potted end
    • B01D63/0241—Hollow fibre modules with a single potted end being U-shaped
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/003—Processes for the treatment of water whereby the filtration technique is of importance using household-type filters for producing potable water, e.g. pitchers, bottles, faucet mounted devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2623—Ion-Exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2626—Absorption or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/26—Further operations combined with membrane separation processes
    • B01D2311/2649—Filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2319/00—Membrane assemblies within one housing
    • B01D2319/06—Use of membranes of different materials or properties within one module
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/38—Hydrophobic membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/48—Antimicrobial properties
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C02F1/505—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment by oligodynamic treatment
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/04—Location of water treatment or water treatment device as part of a pitcher or jug

Definitions

  • the invention relates to a method and a filter for ultrafiltration.
  • the invention relates to a filter for water treatment, which ausgasende
  • Filter media such as activated carbon or
  • the invention relates to both gravity-driven and pressure-operated water filters.
  • Sterilize as bacteria usually can not pass such a filter. This will be sterile
  • capillary membranes are known as filter medium for ultrafiltration, in which the wall of the capillary forms the membrane.
  • filters for ultrafiltration are therefore also suitable for sterilizing or disinfecting drinking water. It has been shown, however, that the drinking water used frequently contains gases, for example carbon dioxide or carbon dioxide, or air as a result of outgassing media, which lead to bubble formation in the filter and this
  • filters for ultrafiltration are not consistent for gas bubbles. Rather, it has become established in practice that gas bubbles are used to check a filter for ultrafiltration on its functionality. In the so-called bubble-point test, it is checked whether the filter medium
  • Ion exchangers which hydrogen ions against alkali or alkaline earth ions, it comes as a result of gas formation to a blockage of the ultrafilter.
  • Known gravity-driven water balance filters typically include an ion exchange resin. It is also known to add activated carbon to the filter medium. It is also known to use a fleece to remove suspended matter. With these approaches, however, bacteria in drinking water can not be safely removed.
  • Hot drinks usually contain ion exchangers which exchange hydrogen ions and activated carbon.
  • activated carbon and formed during the ion exchange of carbon dioxide or carbon dioxide can be used according to the prior art, no ultrafilter after the water filters, since the ultrafilters block as a result of the gases.
  • the filter material chemical substances can be added with disinfecting effect.
  • this can have negative effects on the water.
  • in a gravity-driven filter usually does not come to a continuous release of the disinfectant, so that a sufficient effect is not always guaranteed over the entire life of the filter material. It is further known that water dispensers with a
  • Storage tank which are often designed for dispensing cooled and / or uncooled water, bring with it the danger that germs multiply in the water.
  • germs may form in particular in the vicinity of the outlet of the water dispenser, which naturally can not be reached by the heated water but are flushed out when the water dispenser is actuated.
  • the invention has the object, a device or a method for
  • the invention further relates to a
  • the invention relates to a filter for ultrafiltration, ie a filter by means of which in particular
  • the filter for ultrafiltration comprises a membrane packet which according to the invention comprises partially hydrophobic membranes.
  • Hydrophobic membranes are understood to mean membranes whose surface at least partially does not wet with water when the filter is used as intended.
  • Polyhalogenolefin in particular polytetraflouretylene (PTFE) can be used.
  • PTFE polytetraflouretylene
  • the remaining membranes of the membrane package that is, the non-hydrophobic membranes formed in the context of the invention are wetted with water when used as intended.
  • a polyethersulfone can be used for these membranes. Also conceivable is the use of
  • Polyethersulfone allows the formation of a filter for ultrafiltration, which is usually suitable for a gravity-driven operation.
  • the invention is based on the finding that the hydrophobic membranes are not wetted with the medium to be filtered, but that gas bubbles rise in or along the hydrophobic membranes and can leave the filter.
  • the membrane packet to less than 50%, preferably less than 25%, more preferably less than 50% hydrophobic membranes, in this sense, the number of membranes is understood.
  • the membranes of the membrane package are in a preferred embodiment of the invention as Kapillarmembranen
  • the open end of the membranes forms the permeate side, i.
  • the membranes are arranged in a sleeve and bent over, so that the open ends of the membranes form the outlet of the filter.
  • the water to be filtered thus runs from the outside into the
  • the capillary membranes are preferably in the form of a bundle, the capillary membranes at least partially abutting one another.
  • the fibers may be disordered or such
  • the bundle is preferably folded, the ends of the capillary membranes being arranged on the permeate side.
  • the capillary membranes preferably have a mean pore size of from 0.005 to 0.1 ⁇ m, preferably from 0.01 to 0.5 ⁇ m and more preferably from 0.015 to 0.025 ⁇ m.
  • the capillary membranes preferably have an average diameter (outer diameter) of between 0.5 and 2 mm.
  • the invention further relates to a process for the ultrafiltration of liquids, in particular of
  • Drinking water wherein the liquid passes through a membrane pack of capillary membranes, which are partially hydrophobic, so that in the liquid gas present at least partially through the hydrophobic
  • Capillary membranes is discharged.
  • a filter for ultrafiltration as described above is used.
  • the inventive method is particularly suitable for a gravity-powered operation.
  • the invention further relates to a
  • Gravity powered water balance filter This comprises a filter for ultrafiltration, in particular a filter for ultrafiltration as described above.
  • the gravity-driven water balance filter usually includes a filter medium, which a
  • Ion exchange material comprises.
  • an ion exchange resin is used.
  • gravity-driven water balance filters are used primarily for softening the water.
  • pollutants, especially heavy metals can be removed.
  • By additionally providing a filter for ultrafiltration it is also possible without the use of chemicals to remove bacteria almost completely and in a very simple manner from the water to be treated.
  • Ultrafiltration is arranged below the ion exchanger.
  • the ultrafiltration filter is another component of the water balance filter
  • Ion exchange resin separable formed.
  • Ion exchange material of the filter for ultrafiltration which usually has a longer life, separated and reused.
  • the filter for ultrafiltration on the permeate side comprises a biocidal contact material.
  • a biocidal contact material Under a biocidal
  • Contact material is understood to mean materials which have a bactericidal and / or fungicidal action on contact with water.
  • silver for example formed as a silver network, comes into consideration.
  • Spout is prevented from germs, algae or fungi after removal of germs through the membrane pack form.
  • connection of a silver mesh, which on the permeate side forms the last layer of the filter leads in a simple manner to the desired
  • the invention further relates to a water dispenser.
  • the water dispenser usually includes one
  • Water reservoir and an actuator for dispensing drinking water which can be dispensed, for example, as a sweetened cold drink.
  • the water dispenser may have a device for cooling the water to be dispensed. Furthermore, the water dispenser usually includes one
  • Stand can be set up so in particular in the commercial sector so that customers can remove water.
  • the water filter comprises a filter for ultrafiltration, which is preferably designed as an outlet of the water dispenser.
  • the filter is designed as a spout, the water runs directly from the filter into the container of the user.
  • the use of the water filter as the last component in the waterway ensures that even germs that form on or in the outlet can not be dispensed.
  • the outlet is surrounded by a contact protection.
  • a wall is provided which extends from above at least up to the height of the outlet, so that the outlet against
  • the water dispenser comprises a filter, as described above, ie a filter for
  • the water has a carbonic acid content of more than 50 mg / l, preferably more than 200 mg / l of carbon dioxide.
  • the invention further relates to a filter cartridge for drinking water.
  • this embodiment of the invention is designed as a pressure-operated filter cartridge, which is used for example in the inflow of a device for beverage preparation, in particular a coffee machine.
  • Such filter cartridges are
  • filter cartridges commonly referred to as filter cartridges and usually have a housing which comprises an inlet and a drain.
  • Ion exchange material in particular filled with a weakly acidic cation exchange resin.
  • the filter cartridge comprises a filter for ultrafiltration, on which preferably the outlet side, ie immediately before the expiration, is arranged.
  • the filter for ultrafiltration is preferably as
  • Membrane package formed, in particular with one or more features described above.
  • a filter for ultrafiltration as described above is used, in which a membrane packet comprises hydrophobic membranes.
  • hydrophobic membranes ensures that the filter cartridge is not blocked by gas bubbles.
  • gas bubbles may be present in particular after connection of the water filter and be so large that they are not in operation but may permanently block the filter cartridge.
  • Fig. 1 shows a schematic view of a filter for ultrafiltration 1.
  • the filter for ultrafiltration 1 comprises a membrane packet 2, which in a sleeve 4, preferably made of
  • Plastic is formed, is arranged.
  • the membranes of the membrane packet 2 are formed as a bundle of capillary membranes 3, which is folded once.
  • Capillary membranes 3 has.
  • the sleeve 4 comprises fastening means 6, which
  • FIG. 2 shows a schematic view of the end face, that is to say the outlet of the ultrafiltration filter 1.
  • the capillaries 3b are designed to be hydrophobic, whereas the capillaries 3b are hydrophobic
  • Capillary membranes 3a are so hydrophilic that they can absorb the water when used as intended. In operation, gas can now pass through the hydrophobic
  • the water to be filtered passes through the open ends of the capillary membranes 3a.
  • the filter for ultrafiltration can not be blocked by gas bubbles.
  • Fig. 3 shows a schematic view of a
  • the gravity-driven water balance filter 7 comprises a jug for receiving the filtered water.
  • the water balance filter 7 comprises a funnel 9, is poured into the water to be treated.
  • Filter cartridge 10 is detachably connected.
  • the ultrafiltration filter 1 removes bacteria. When necessary replacement of the filter cartridge 2, the filter can be removed for ultrafiltration and
  • the water dispenser 11 comprises a water container 12, which is inserted into a housing 13. On the housing, an actuating means 14 is arranged, on which the user can press. Then flows through the spout 15 water in the cup 16 of the user, which can be arranged in a standing surface of the housing 13.
  • the outlet 15 is designed as a filter for ultrafiltration 1.
  • the filtered water thus runs directly out of the ultrafiltration filter 1.
  • a shock protection 17 is arranged in the form of a circumferential wall, by means of which it is prevented that the user unintentionally attacks the outlet 15 and contaminates it with bacteria.
  • Fig. 5 and Fig. 6 is a variant of a filter for ultrafiltration 1 will be explained in more detail how it can be used in particular for the water dispenser described above.
  • the ultrafiltration filter 1 comprises a silver mesh 19 as biocides
  • Membrane packet 2 is arranged.
  • the silver mesh 19 prevents germs, algae or fungi from forming in the adhering water. Between the silver mesh 19 and the membrane packet 2, an intermediate layer 18 may be provided, which
  • FIG. 7 shows a filter cartridge 20, which comprises a filter for ultrafiltration 1.
  • the filter cartridge 20 is as in a supply line
  • the usable filter cartridge and includes an inlet 22 and a drain 23. About the inlet 22, the water to be treated runs into the housing 21 of
  • Filter cartridge 20 and leaves the housing 21 through the drain 23.
  • the path of the water is marked with arrows.
  • Such a filter cartridge 20 is commonly referred to as a filter cartridge.
  • activated carbon 24 germs are to be killed.
  • the water reverses the flow and passes through a fine filter 26 in a riser 27 to be led to the outlet 23.
  • ion exchange material 25 comprises the
  • the ion-exchange material 25 does not pass through the water to be treated, but reaches the outlet 23 without an ion exchange taking place. In this way, the hardness of the water can be adjusted in a simple way in which softened water mixes with non-softened water.
  • a filter for ultrafiltration 1 is now arranged before the outlet 23.
  • This has a slightly larger diameter than the riser 27 and partially comprises hydrophobic membranes through which gas bubbles, which are present due to gases dissolved in the water and / or after the connection of the filter cartridge 20
  • Ultrafiltration are provided to ensure that it is not blocked by dissolved gases in the water.

Landscapes

  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Epidemiology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Sorption (AREA)

Abstract

L'invention concerne un filtre d'ultrafiltration doté d'un ensemble de membranes comprenant des membranes en partie hydrophobes.
EP13732508.0A 2012-06-28 2013-06-28 Filtre et procédé d'ultrafiltration Withdrawn EP2866843A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE201210105720 DE102012105720A1 (de) 2012-06-28 2012-06-28 Filter und Verfahren zur Ultrafiltration
DE102012109267 2012-09-28
PCT/EP2013/063636 WO2014001506A1 (fr) 2012-06-28 2013-06-28 Filtre et procédé d'ultrafiltration

Publications (1)

Publication Number Publication Date
EP2866843A1 true EP2866843A1 (fr) 2015-05-06

Family

ID=48703530

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13732508.0A Withdrawn EP2866843A1 (fr) 2012-06-28 2013-06-28 Filtre et procédé d'ultrafiltration

Country Status (3)

Country Link
US (1) US20150298995A1 (fr)
EP (1) EP2866843A1 (fr)
WO (1) WO2014001506A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6715575B2 (ja) * 2015-06-18 2020-07-01 住友化学株式会社 二酸化炭素分離方法及び二酸化炭素分離装置
RU2019108810A (ru) 2016-01-22 2019-05-14 Бакстер Интернэшнл Инк. Способ и машина для производства мешков для стерильного раствора продукта
PL3405161T3 (pl) 2016-01-22 2020-07-13 Baxter International Inc Woreczek do wyrobu w postaci roztworu sterylnego
US10688441B2 (en) 2017-04-19 2020-06-23 Mann+Hummel Gmbh Integrated ultrafiltration membrane and ion-exchange filtration system
NL2018750B1 (nl) * 2017-04-20 2018-11-05 Sterwater Int B V Inrichting en werkwijze voor het zuiveren van leidingwater
DE102020129850A1 (de) 2020-11-12 2022-05-12 Bwt Holding Gmbh Wasserinstallationssystem sowie Verfahren zur Aufbereitung von Trinkwasser

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US5443739A (en) * 1992-09-17 1995-08-22 J. Vogel Premium Water Company Water purification and dispenser with uncontaminated mineral addition
JP3468568B2 (ja) * 1993-03-31 2003-11-17 川田 武豊 携帯用液体浄化器
JP4157378B2 (ja) * 2000-12-25 2008-10-01 三菱レイヨン株式会社 ピッチャー型浄水器用浄水カートリッジ及びピッチャー型浄水器
JP4863425B2 (ja) * 2003-01-31 2012-01-25 三菱レイヨン株式会社 浄水カートリッジ及び浄水器
JP4838714B2 (ja) * 2004-05-18 2011-12-14 三菱レイヨン株式会社 浄水器
JP4512455B2 (ja) * 2004-09-06 2010-07-28 三菱レイヨン株式会社 自重濾過型浄水器及び浄水カートリッジ
US20090008318A1 (en) * 2006-12-04 2009-01-08 Prismedical Corporation Modular Water Purification and Delivery System

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See also references of WO2014001506A1 *

Also Published As

Publication number Publication date
US20150298995A1 (en) 2015-10-22
WO2014001506A1 (fr) 2014-01-03

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