WO2010096521A2 - Systèmes de purification et d'amélioration de l'eau - Google Patents

Systèmes de purification et d'amélioration de l'eau Download PDF

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Publication number
WO2010096521A2
WO2010096521A2 PCT/US2010/024531 US2010024531W WO2010096521A2 WO 2010096521 A2 WO2010096521 A2 WO 2010096521A2 US 2010024531 W US2010024531 W US 2010024531W WO 2010096521 A2 WO2010096521 A2 WO 2010096521A2
Authority
WO
WIPO (PCT)
Prior art keywords
water
purification system
water purification
saturated
media
Prior art date
Application number
PCT/US2010/024531
Other languages
English (en)
Other versions
WO2010096521A3 (fr
Inventor
Eugene A. Fitzgerald
Ya-Hong Xie
Thomas Langdo
Richard Renjilian
Brian T. Foley
Carl V. Thompson
Original Assignee
The Water Initiative
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 to EP10744279.0A priority Critical patent/EP2398572A4/fr
Priority to AU2010216068A priority patent/AU2010216068B2/en
Priority to BRPI1008398A priority patent/BRPI1008398A2/pt
Priority to CA2753144A priority patent/CA2753144A1/fr
Application filed by The Water Initiative filed Critical The Water Initiative
Priority to MX2011008730A priority patent/MX2011008730A/es
Priority to JP2011551206A priority patent/JP2012518530A/ja
Priority to RU2011138381/05A priority patent/RU2528989C2/ru
Priority to CN201080008752.2A priority patent/CN102438719B/zh
Publication of WO2010096521A2 publication Critical patent/WO2010096521A2/fr
Publication of WO2010096521A3 publication Critical patent/WO2010096521A3/fr
Priority to IL214707A priority patent/IL214707A0/en
Priority to ZA2011/06077A priority patent/ZA201106077B/en
Priority to US13/137,507 priority patent/US9206058B2/en
Priority to US14/335,478 priority patent/US20150166382A1/en
Priority to US14/635,694 priority patent/US20160023144A1/en

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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/004—Processes for the treatment of water whereby the filtration technique is of importance using large scale industrial sized filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D35/00—Filtering devices having features not specifically covered by groups B01D24/00 - B01D33/00, or for applications not specifically covered by groups B01D24/00 - B01D33/00; Auxiliary devices for filtration; Filter housing constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D27/00—Cartridge filters of the throw-away type
    • B01D27/14—Cartridge filters of the throw-away type having more than one filtering element
    • B01D27/146—Cartridge filters of the throw-away type having more than one filtering element connected in series
    • 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
    • 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
    • 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
    • C02F1/008—Control or steering systems not provided for elsewhere in subclass C02F
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • 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
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/685—Devices for dosing the additives
    • C02F1/688—Devices in which the water progressively dissolves a solid compound
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/152—Water filtration

Definitions

  • the present invention relates to a low-cost potable water purification system and a sensor to alert the user when the water is no longer safe to drink.
  • This low-cost water purification system incorporates additional functionality that enables beneficial impurities and molecules to be added to the water.
  • Water purification systems can be comprised of many different components using various mechanisms for removing impurities from water.
  • One class of prior water purification systems is commonly referred to as 'point-of-use' (POU) water purification systems.
  • POU systems are composed of components that remove water impurities on a relatively small scale, e.g. a table-top or dwelling-oriented system as opposed to a large central facility, iike a municipal water treatment facility.
  • POU systems in genera! have been constructed for high-end marketplaces, i.e., markets where higher costs in POU systems can be tolerated. POU systems have not effectively penetrated large but lower-end marketplaces due to the lack of inventive design in low-cost environments.
  • a typical POU system may have a p re-filter to remove sediment, followed by mechanisms that ensure pathogen and sometimes inorganic material removal.
  • Most POU systems use a time-based system where, after a certain amount of time has passed, a light turns on (or some other indicator) which signals that it is time to change the filter. This relatively low cost sensor is not adequate, if the water purification system is deployed in different environments, the required length of time between filter changes to avoid contamination can vary greatly, thus possibly exposing individuals to contaminated water,
  • the main method of determining water composition is to periodically take samples of the water and ship these samples to a laboratory where relatively large equipment is used to analyze the water composition. This information supplies feedback to the user or service personnel of what is in the water.
  • field-kits which can test for particular contaminates, e.g. chlorine.
  • neither of these standardized test methods is either universal enough or compatible with a POU water system.
  • neither of these test methods is consumer friendly.
  • the present invention seeks to satisfy this need.
  • a water purification system comprising at ieast two filtration media sized with respect to each other to allow a first contaminate to be saturated first with a delay before a second contaminate is saturated.
  • a method of purifying water comprising passing water through a system comprising at least two filtration media sized with respect to each other to allow a first contaminate in the water to be saturated first with a delay before a second contaminate is saturated.
  • An important aspect of the present system is to employ the user of the system as the end-point detector of pathogens or other dangerous elements. This aspect of the system aliows for the ultimate in low-cost water purification and water safety.
  • the present inventive system employs the user as a detector through the user's sight or taste. A mechanism in the water purification system releases a color element when the water filter has reached or is beginning to reach the end of its life. Additionally the system also has the ability to release a different taste in the water which also can alert the user that the filter has reached its end of life.
  • these detection mechanisms are introduced in a iow-cost manner, the same mechanisms can be utilized to impart desired molecules or compounds into purified water, thus creating healthy beverages and/or therapeutic drinks.
  • Figure 1 is a schematic of a first embodiment of the present invention showing a iow-cost arsenic purification system
  • Figure 2 iilustrates how taste removal media breaks through first and the water will possess an undesirable musty or earthy taste for some time period of defay before the water begins to be contaminated with arsenic;
  • Figure 3 illustrates how time release capsules can release taste substances at a constant rate which is absorbed by a downstream media and saturates the media at the right time;
  • Figure 4 illustrates how time release capsules are engineered into abrupt-release form which are located in this case at the end of the purification system;
  • Figure 5 illustrates time-release capsules designed to inject an even dose of flavor over time;
  • Figure 6 illustrates a time-release capsule designed so that the outer shell dissolves at a rate such that the flavor is released as abruptly as possible when the arsenic media is about to expire;
  • Figure 1 is a schematic of a first embodiment of the present invention of a low-cost arsenic purification system.
  • the system 2 comprises a reservoir 4 for containing water to be purified connected via a valve 8 to a filter region 10 having a series of remediation medias 12,14,16. Water passing through the filter region 10 exits through nozzle 18 via valve 20 into receiving vessel 22.
  • the prefilter 12 is designed to eliminate large particles and sediment from the water.
  • the pre-fiiter 12 is followed by a series filter medias which are designed to remove targeted atoms, molecules, or compounds from the water and/or may be employed to impart either a color or taste change to the water when the media are saturated with contaminates and the media is no longer purifying the water (i.e. the invention indicates that the water will soon be unsafe), in the particular embodiment illustrated in Figure 1 , the prefilter media 12 is followed by a taste removal media 14, and an arsenic removal media 16,
  • Beneficial compounds can be, for example, vitamins, amino acids, minerals, and/or herbal extracts. Some examples include vitamin A, vitamin C, vitamin D, and vitamin E, vitamin K, vitamin Be, vitamin B ⁇ 2 , thiamin, riboflavin, niacin, foiic acid, biotin, pantothenic acid, calcium, iron, phosphorus, iodine, magnesium, zinc, selenium, copper, manganese, chromium, molybdenum, potassium, boron, nickel, silicon, tin, vanadium, lutein, and lycopene.
  • vitamins amino acids, minerals, and/or herbal extracts.
  • Some examples include vitamin A, vitamin C, vitamin D, and vitamin E, vitamin K, vitamin Be, vitamin B ⁇ 2 , thiamin, riboflavin, niacin, foiic acid, biotin, pantothenic acid, calcium, iron, phosphorus, iodine, magnesium, zinc, selenium, copper, manganese,
  • the system of the invention is primarily designed for treatment of water which has been disinfected with chlorine.
  • one of the remediation medias 14 may be designed to remove undesirable tastes, and the other 16 may be chosen to remove arsenic,
  • EBCT empty bed contact time
  • the purification system may include additional filter stages after the remediation medias described above (not shown).
  • a filter to remove media fines such as a fiber wound filter
  • a filter to remove microbial contaminants may be implemented after the remediation media stages.
  • Common causes of water taste problems are algal metabolites such as geosmin, or 2 metnylisoborneol (MIB) which impart musty or earthy tastes to the water. (See for example, chapter 26 in Adsorption by Carbon, edited by Bottani and Tascon).
  • MIB 2 metnylisoborneol
  • the medias may be intermixed, alternating, or stacked.
  • activated carbon also referred to as activated charcoal
  • one or more of granular ferric hydroxide, activated alumina, granular ferric oxide, titanium oxide, zirconium oxide, or another metal oxide or mixture of metal oxides may be selected as the arsenic removal media 16.
  • the design of the system of the invention is very low cost for two principal reasons.
  • the system is targeted at the two primary problems arising with the water, namely the toxic arsenic concentration and the undesirable taste.
  • the method of end-point-detection is either time, or more importantly, taste.
  • the system is able to employ user taste as an end-point detection mechanism by sizing the taste-removai media and the arsenic-removal media such that the taste-removal media is saturated before the arsenic-removal media is saturated.
  • the taste removal media breaks through first, and the water wili possess an undesirable musty or earthy taste for some time period of delay before the water begins to be contaminated with arsenic.
  • the local water is measured to determine the level of taste imparting compounds such as geosmin or MIB and the level of arsenic in the water.
  • the taste and arsenic removal media is tested to determine how long it will take a volume of media to be saturated with geosmin and/or MIB or arsenic.
  • volumes of the media in the system can b chosen to achieve the effect shown in Fig. 2.
  • a two component POU filter can be constructed with activated carbon for taste improvement and granular ferric oxide (GFO) for arsenic removal.
  • GFO granular ferric oxide
  • the relevant parameters are the media adsorption capacities for target contaminants, typically listed in mg contaminant adsorbed per gram of media.
  • the adsorption capacity of MlB on activated carbon is in the range of 1 to 3 mg/g, depending on activated carbon structure (carbon containing source material, pore size distribution, and surface area), and water chemistry. (See for example, Chapter 26 in Adsorption by Carbon, edited by Bottani and Tascon, p.683, (2008)).
  • the adsorption capacity of arsenic (V) on GFO is in the range of 0.5 to 1 mg/g depending on water chemistry. (Reference, Adsorption Treatment Technologies for Arsenic Removal ,AWWA publishing, Chapter 6, (2005)).
  • a suitable activated carbon can be obtained from Caigon Carbon Corporation
  • the overall media masses must be chosen appropriately for the intended water flowrate and filter lifetime. If the concentration of geosmin or MIB is not large enough, the saturation is not abrupt enough, or another suitable taste imparting compound is not present in the water, the method described above cannot be used as an end-point-detection sensor.
  • the invention has a similar design as shown in Fig.1 since the geosmin or IvIIB taste removal media is replaced with a media that removes the intentionally introduced taste compound.
  • the taste substance or compound may be added within the POU system by employing time-release capsules,
  • Figure 3 shows a system similar to that shown in Figure 1 except that a region 24 is provided downstream of the taste removal media 14 containing capsules adding constant rate release of taste substances.
  • These time release capsules can either release taste substances at a constant rate which is absorbed by a downstream media and saturates the media at the right time (as seen in Fig. 3), or the capsules may be engineered into abrupt- release form 26 which are located in this case at the end of the purification system as the last stage (see Fig. 4).
  • the time- release capsules are designed to inject an even dose of flavor over time.
  • this is designed so that the outer shell dissolves at a rate such that the flavor is released as abruptly as possible when the arsenic media is about to expire.
  • the inventive time-release capsules used in the water purification system of the invention can also be used to release color either in addition to or instead of taste.
  • both methods described above for flavor release can be used for color release
  • the constant-rate- release time capsule can be used to release a color that is absorbed by one of the media in a filter system, and the saturation is planned such that the coior compound achieves saturation in the media just before a purification media becomes saturated with an undesirable atom, molecule, or compound(s) which is being removed.
  • the water will change color when it is time to replace the purification media.
  • a time delay is designed into this system as well, so that even though the water changes color, the water is still safe for some delay time.
  • the deiay is designed by understanding the saturation rate of the color compound concentration released by the time- release capsule as welf as the saturation of the undesirable atom, molecule, or compound that is being removed.
  • An abrupt-time-release time capsule can be used as well to impart color in the water to indicate that it is time to replace the purification media,
  • the outer shell of the time release capsule dissolves at a rate such that color is released abruptly just before the purification media is saturated with the atom, molecule, or compound that it is removing from the water.
  • the time-release capsules described herein are also useful in adding desirable atoms, molecules, or compounds to the water.
  • the constant-rate time capsules described previously are desirable for this beneficial release.
  • the capsules are loaded into a media, or separately, located at the last stage of the water purification system (so that other media do not remove the desired beneficial atoms, moiecuies, or compounds). Flavors can be released by these capsu ⁇ es, as well as therapeutic substances such as vitamins.
  • a key aspect of the invention is the recognition that local water conditions must be carefully assessed in order to choose the most appropriate, lowest cost media for optimum arsenic POU removal with sufficient longevity to produce potable water in amounts suitable for a household. For example, in one particular location, testing determined that the chlorine content, arsenic valence, and pH would need to be primarily considered when choosing the most appropriate arsenic removal media. Likewise, the ratios of the media in the filtration system would have to be adjusted based on the water characteristics and desired (ongevity and quality of the water post-filtration.
  • Chlorine neutralization requires activated carbon (AC), while arsenic removal requires a metal oxide media such as GFO,
  • GFO media was chosen because it exhibits superior As(V) removal at the elevated pHs present in the local water supply compared to other metal oxide medias such as activated alumina.
  • the media ratios can be adjusted without undue experimentation once the iocal water characteristics have been assessed.
  • the medias formed two distinct layers, and water flowed through the AC prior to the GFO.
  • Figures 7 and 8 show arsenic removal results of the combination AC/GFO filter on ChapaSa water over the lifetime of the filter. Arsenic is maintained below the 0.01 mg/L limit during the test. In addition, chlorine was not detected in the treated water, resulting in pleasing taste to local residents.
  • POU filter size, and designed operational lifetime the ratios of GFO to AC may be adjusted as required.

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  • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Treatment By Sorption (AREA)
  • Filtering Materials (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention porte sur un système de purification de l'eau comprenant au moins deux matériaux filtrants, dimensionnés l'un par rapport à l'autre pour permettre à un premier produit polluant d'être saturé en premier avec un retard, avant qu'un second produit polluant ne soit saturé.
PCT/US2010/024531 2009-02-20 2010-02-18 Systèmes de purification et d'amélioration de l'eau WO2010096521A2 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
JP2011551206A JP2012518530A (ja) 2009-02-20 2010-02-18 水質浄化および水質向上のシステム
BRPI1008398A BRPI1008398A2 (pt) 2009-02-20 2010-02-18 sistemas de realce e de purificação de água
CA2753144A CA2753144A1 (fr) 2009-02-20 2010-02-18 Systemes de purification et d'amelioration de l'eau
CN201080008752.2A CN102438719B (zh) 2009-02-20 2010-02-18 水净化加强系统
MX2011008730A MX2011008730A (es) 2009-02-20 2010-02-18 Sistemas de purificacion de agua y mejoramiento.
AU2010216068A AU2010216068B2 (en) 2009-02-20 2010-02-18 Water purification and enhancement systems
RU2011138381/05A RU2528989C2 (ru) 2009-02-20 2010-02-18 Устройства для очистки и улучшения воды
EP10744279.0A EP2398572A4 (fr) 2009-02-20 2010-02-18 Systèmes de purification et d'amélioration de l'eau
IL214707A IL214707A0 (en) 2009-02-20 2011-08-17 Water purification and enhancement systems
ZA2011/06077A ZA201106077B (en) 2009-02-20 2011-08-18 Water purification and enhancement systems
US13/137,507 US9206058B2 (en) 2009-02-20 2011-08-22 Water purification and enhancement systems
US14/335,478 US20150166382A1 (en) 2009-02-20 2014-07-18 Water purification and enhancement systems
US14/635,694 US20160023144A1 (en) 2009-02-20 2015-03-02 Water purification and enhancement systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15407009P 2009-02-20 2009-02-20
US61/154,070 2009-02-20

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/137,507 Continuation-In-Part US9206058B2 (en) 2009-02-20 2011-08-22 Water purification and enhancement systems

Publications (2)

Publication Number Publication Date
WO2010096521A2 true WO2010096521A2 (fr) 2010-08-26
WO2010096521A3 WO2010096521A3 (fr) 2010-12-09

Family

ID=42634434

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2010/024531 WO2010096521A2 (fr) 2009-02-20 2010-02-18 Systèmes de purification et d'amélioration de l'eau

Country Status (13)

Country Link
EP (1) EP2398572A4 (fr)
JP (1) JP2012518530A (fr)
KR (1) KR20110136816A (fr)
CN (2) CN102438719B (fr)
AU (1) AU2010216068B2 (fr)
BR (1) BRPI1008398A2 (fr)
CA (1) CA2753144A1 (fr)
IL (1) IL214707A0 (fr)
MX (1) MX2011008730A (fr)
PE (1) PE20121106A1 (fr)
RU (1) RU2528989C2 (fr)
WO (1) WO2010096521A2 (fr)
ZA (1) ZA201106077B (fr)

Cited By (4)

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WO2013028750A1 (fr) * 2011-08-22 2013-02-28 The Water Initiative, Llc Systèmes de purification et d'amélioration d'eau
WO2013090785A1 (fr) 2011-12-15 2013-06-20 The Water Initiative, Llc Procédé et appareil pour filtration d'eau sur point d'utilisation
US10035131B2 (en) 2011-11-24 2018-07-31 Indian Institute Of Technology Multilayer organic-templated-boehmite-nanoarchitecture for water purification
US10041925B2 (en) 2012-04-17 2018-08-07 Indian Institute Of Technology Detection of quantity of water flow using quantum clusters

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US20160135468A1 (en) * 2013-06-28 2016-05-19 Indian Institute Of Technology A Composition for Enhanced Biocidal Activity and Water Purification Device on the Same

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CN103930378A (zh) * 2011-08-22 2014-07-16 水源公司 水净化加强系统
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IL214707A0 (en) 2011-11-30
JP2012518530A (ja) 2012-08-16
MX2011008730A (es) 2012-01-12
EP2398572A2 (fr) 2011-12-28
CN102438719B (zh) 2015-10-14
AU2010216068A1 (en) 2011-09-22
EP2398572A4 (fr) 2013-05-15
PE20121106A1 (es) 2012-09-07
CN105152376A (zh) 2015-12-16
RU2528989C2 (ru) 2014-09-20
CA2753144A1 (fr) 2010-08-26
RU2011138381A (ru) 2013-03-27
WO2010096521A3 (fr) 2010-12-09
CN102438719A (zh) 2012-05-02
AU2010216068B2 (en) 2016-03-10
BRPI1008398A2 (pt) 2016-11-01
KR20110136816A (ko) 2011-12-21

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