WO2012014213A1 - Method for production of cellulose nano crystals from cellulose-containing waste materials - Google Patents
Method for production of cellulose nano crystals from cellulose-containing waste materials Download PDFInfo
- Publication number
- WO2012014213A1 WO2012014213A1 PCT/IL2011/000613 IL2011000613W WO2012014213A1 WO 2012014213 A1 WO2012014213 A1 WO 2012014213A1 IL 2011000613 W IL2011000613 W IL 2011000613W WO 2012014213 A1 WO2012014213 A1 WO 2012014213A1
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- Prior art keywords
- cellulose
- process according
- sludge
- acid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/08—Fractionation of cellulose, e.g. separation of cellulose crystallites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C11/00—Regeneration of pulp liquors or effluent waste waters
- D21C11/0085—Introduction of auxiliary substances into the regenerating system in order to improve the performance of certain steps of the latter, the presence of these substances being confined to the regeneration cycle
Definitions
- Solid paper-mill waste residues amounting to thousands of tons per annum are usually disposed of in landfill sites creating a worldwide environmental problem.
- the use of recycled paper and its waste by-products increases the environmental implications of the paper manufacturing process. Removing the ink, clay, coatings and contaminants from waste paper in order to recover reusable cellulose fibers to produce recycled paper creates deinking sludge which in turn creates disposal problems.
- other non-cellulose by products obtained in the process of producing paper such as coatings, adhesives, dyes and fillers like calcium carbonate and clay wind up in the sludge creating an environmental problem and reducing the yield of cellulose production from paper mill waste.
- wastes are very diverse in composition and consist of different types of sludge. In general, the paper sludge contains very high levels of dry solids because it is rich in fibers and therefore dewaters quite easily. All paper and wood waste (pulp, paper sludge, paper white and waste water) is a mixture of cellulose fibers (40-60% of dry solids), printing inks and mineral components (40-60% dry solids: kaolin, talc and calcium carbonate). The sludge from process water clarification is generated in the fiber recovery process from white waters and in the physical wastewater treatment process. It consists of mostly fines and fillers (both around 50%) depending on the recovered paper being processed [1,2]. A more extensive review on waste water characteristics is given by Pokhrel and Viraraghavan [3].
- landfills are eliminated as final destinations for wastes, and incineration with energy recovery is becoming the main waste recovery method.
- Other options such as pyrolysis, gasification, land spreading, composting and reuse as building material are being applied, although research and economic assessment is still needed for optimization of the processes [1].
- the second obstacle is the high amounts of acid required for the process.
- NCC Nano Crystalline Cellulose
- NCC tensile strength
- the inventors of the present invention have developed a process for using paper mill waste as a source for nano-cellulose whiskers, also known as Nano Crystalline Cellulose (NCC).
- NCC Nano Crystalline Cellulose
- the process disclosed herein provides a cost and energy effective means for producing NCC and other valuable components that are recovered in the process, as will be disclosed hereinbelow.
- the present invention provides a process for treating a cellulose containing sludge, such as a cellulose sludge from paper production plants, to recover (separate) therefrom pure cellulose (namely a cellulose containing less than 10% impurities, such as CaC0 3 , calcium carbonate).
- a cellulose containing sludge such as a cellulose sludge from paper production plants
- pure cellulose namely a cellulose containing less than 10% impurities, such as CaC0 3 , calcium carbonate.
- Such cellulose is a suitable source for, e.g., producing NCC.
- the present invention provides a process for recovering pure cellulose from a cellulose-containing sludge, e.g., paper sludge cellulose source, the process comprising treating the sludge cellulose source under conditions permitting dissolution of non-cellulose material and suspension of the cellulose.
- the cellulose which is collected may be further treated to produce NCC.
- the pure cellulose recovered from a cellulose-containing sludge, or waste is cellulose containing no more than 10% of impurities.
- the impurities may be any non- cellulose material which is present in the original sludge or waste material (the so-called "sludge cellulose source") or any such impurity which is generated in the recovery process.
- the type and/or concentration of impurities may vary.
- the main impurity may be calcium carbonate (CaC0 3 ) or any other calcium salt or calcium ions.
- the recovery process of the invention it is not necessary to remove all impurities as the purity of the cellulose which is recovered is sufficient for the further manipulation of the cellulose material, e.g., for the production of NCC. More of the impurities may be recovered or removed (discarded), depending, e.g., on the final intended application.
- the pure cellulose is 90% pure. In other embodiments, the cellulose is 91% pure. In further embodiments, the cellulose is 92% pure. Still, in some embodiments, the cellulose is 93% pure and further in other embodiments, the pure cellulose is 94% pure.
- the cellulose purity is between 95 and 99%.
- the cellulose is 95% pure.
- the cellulose is 96% pure.
- the cellulose is 97% pure.
- the cellulose is 98% pure.
- the cellulose recovered is 99% pure.
- the cellulose purity is between 93 and 97% pure.
- sludge cellulose source refers to any cellulose- containing sludge or waste material from which separation of the cellulose is required or intended. Such sludge cellulose source may contain between 5% and about 60% of cellulose (based on the total amount of solid matter).
- the sludge cellulose source is paper mill sludge.
- paper sludge cellulose source known also as “paper mill waste” or “paper mill sludge” refers to discharges from paper mills containing cellulose left-over that remains after paper and pulp are prepared.
- the paper sludge cellulose source typically comprises very high levels (40-60%) of dry solids, i.e., cellulose fibers and non-cellulose materials.
- the non-cellulose materials typically comprise (40-60%) a variety of solid and non-solid materials including printing inks and mineral components, such as kaolin, talc and calcium carbonate.
- the cellulose source employed by a process of the invention typically comprises between about 10% and about 40% by weight carbonaceous matter and between about 5% and about 30% by weight mineral matter (such as clay and calcium carbonate). This source may be further characterized by a high C/N ratio of about 50 to 200.
- the sludge cellulose source may also contain a variety of solid materials, including wood barks, plastics, metals and others, depending on the composition of raw materials delivered to the production plant, e.g., paper production plant. These solid contaminants may be removed by a variety of mechanical separation techniques.
- the paper sludge cellulose source dry material contains between about 40% to about 60%, by weight, calcium carbonate and between about 40% to about 60%, by weight, of cellulose fibers.
- the paper sludge cellulose source dry material contains about 50%, by weight, calcium carbonate and about 50% by weight of cellulose fibers.
- the process allows the removal of between about 80% and about 99% by weight of calcium carbonate from the cellulose source. In other embodiments, between about 93% and 97% of calcium carbonate is removed. In further embodiments, about 95% of calcium carbonate is removed from the cellulose source.
- the sludge cellulose source is homogenized prior to affecting the conditions permitting dissolution of a non- cellulose material and suspension of the cellulose. Subsequent to homogenizing the paper sludge cellulose source, it is treated with a dilute acid to cause acidification of the non-cellulose materials (e.g., CaC0 3 ) and dissolution thereof in the aqueous medium, without substantially altering (affecting) the cellulose morphology, namely without substantially altering the molecular structure, domain distribution, domain arrangement, or domain constitution of amorphous and/or crystalline domains defining the cellulose material.
- a dilute acid to cause acidification of the non-cellulose materials (e.g., CaC0 3 ) and dissolution thereof in the aqueous medium, without substantially altering (affecting) the cellulose morphology, namely without substantially altering the molecular structure, domain distribution, domain arrangement, or domain constitution of amorphous and/or crystalline domains defining the cellulose material.
- the acidification is achievable by treating the sludge with a dilute acid having a concentration of between 0.1M and 1M acid.
- the acid concentration is between 0.1M and 0.8M.
- the acid concentration is between 0.1M and 0.6M.
- the acid concentration is between 0.3M and 0.8M.
- the acid concentration is between 0.3M and 0.6M.
- the acid concentration is between 0.4M and 0.6M.
- the acid concentration is between 0.1M and 0.3M.
- the acid may be an organic or inorganic acid, which does not form water- insoluble salts with calcium carbonate.
- Non-limiting examples of such acids include HC1, HBr, H 3 P0 4 , and HN0 3 , and natural acids such as citric acid, maleic acid, tartaric acid and others.
- the acid is HC1. In further embodiments, the acid is HC1 at a concentration of between 0.4M and 0.6M. In further embodiments, the acid is HC1 at a concentration of between 0.1M and 0.3M.
- the treatment of the paper sludge cellulose source under acidic conditions may be carried out at room temperature or at a higher temperature.
- acidic treatment is carried out at a temperature below 100°C.
- the acidic treatment is carried out at a temperature between 40° and 100°C.
- the acidic treatment is carried out at a temperature between 40° and 80°C.
- the acidic treatment is carried out at a temperature between 40° and 70°C.
- the acidic treatment is carried out at a temperature between 40° and 60°C.
- the acidic treatment is carried out at a temperature between 50° and 60°C.
- the paper sludge cellulose source is treated with HC1 at a temperature between 40°C and 80°C.
- the process of the invention comprises:
- a sludge cellulose source such as paper sludge cellulose source, as defined herein;
- the liquid phase (supernatant) is removed and a fresh volume of acid is introduced to wash the solid phase containing cellulose.
- This step may be repeated 2 or more times. In some embodiments, the step is repeated at least 3 times and at most 10 times.
- the process of the invention comprises:
- a sludge cellulose source such as paper sludge cellulose source, as defined herein;
- step b) repeating step b) at least twice;
- the acid is added at a ratio of acid per gram of cellulose source of about 10-15 ml acid for each gram of a cellulose source.
- the cellulose material separated from the acidic liquid phase may be collected dry, e.g., following filtration or centrifugation, and may be re-suspended prior to use, or may be collected as aqueous suspension and used as such.
- the process further comprises using the pure cellulose for preparing NCC.
- the process of the invention comprises:
- step d) dispersing the product obtained in step c) to obtain NCC (cellulose whiskers).
- cellulose e.g. natural plant cellulose
- morphology may vary depending on its synthesis and source.
- cellulose fibers there are regions with high arrangement and molecular order of the cellulose chains that are tightly linked together by hydrogen bonding. The high arrangement results in high crystallinity. These areas are surrounded by areas where there is less arrangement and the cellulose chains are looser [8].
- the physical properties of cellulose, as well as their chemical behavior and reactivity are strongly influenced by the arrangement of the cellulose molecules (morphology) with respect to each other and to the fiber axis, as well.
- cellulose amorphous domains refers to regions in a cellulose material where there is less arrangement of cellulose fibers and the cellulose chains are looser.
- cellulose crystalline domains refers, in the context of the present invention to regions in a cellulose material characterized by high arrangement and molecular order of the cellulose chains that are tightly linked together by hydrogen bonding. The high arrangement results in high crystallinity.
- the acid treatment is generally carried out under conditions of acid concentration, duration and temperature that allow preferential degradation of the amorphous domain of the cellulose.
- such preferential or selective treatment is achieved when an aqueous acid solution is used at a concentration between about 20% and about 60% acid.
- the acid concentration is between 20% and 50%, or between 40% and 60%, or between 50% and 60%.
- the concentration of the acid is between about 20% and about 50%.
- the concentration of the acid is between about 30% and about 50%.
- the concentration of the acid is between about 40% and about 50%.
- the concentration of the acid is about 50%.
- the high acid concentration used to degrade the amorphous domains and thereby alter the morphology of the cellulose is much higher than the acid concentration used to dissolve the impurities in the recovery steps of cellulose from the sludge or waste, as disclosed hereinabove.
- the higher acid concentration permits also the dissolution (or decomposition) of additional impurities in the liquid medium and separation of highly pure NCC fibers.
- the acid used to degrade the cellulose amorphous domains may be selected from a variety of acids, including organic and inorganic acids.
- acids including organic and inorganic acids.
- the acid is derived from one or more inorganic compound such as sulfuric acid, HC1, HBr and nitric acid.
- the cellulose when the cellulose is treated by acid (e.g. 50% H 2 S0 4 ) said treatment may be carried out in water, preferably at a temperature of below 60°C, for a time period of time sufficient to destroy the amorphous domains.
- acid e.g. 50% H 2 S0 4
- said treatment may be carried out in water, preferably at a temperature of below 60°C, for a time period of time sufficient to destroy the amorphous domains.
- the acid is a recycled acid, obtained after the acidification of the cellulose amorphous regions (e.g., acid which about between 85% and 99% thereof is recovered and further used to treat subsequent batches of cellulose).
- the use of recycled acid in the destruction of the amorphous cellulose is an advantage of the method of the present invention since it recovers valuable components found in the paper waste including the cellulose whiskers.
- the mineral acid is recycled by the recovery procedure described by Eyal and Baniel [5,6], incorporated herein by reference.
- the mineral acid is extracted by organic acid/hydrophobic amine which is then converted to mineral acid and reused in the acidification chamber.
- the mineral acid may be extracted and may then be recovered by backwashing of the extract phase with water concentrations approaching those in the original solutions.
- the extractant comprises a strong organic acid and amine (both being water insoluble in their free acid or salt form) dissolved in a carrier solvent. The exact amine and organic acid are tested for their ability to form an extracting couple and their molar ratio is adjusted. For a detailed description of the process see US patent 4,291,007, incorporated herein by reference.
- the recovered mineral acid is reused in the acidification step.
- the preferential degradation of cellulose amorphous domains is achievable by enzymatic treatment.
- the cellulose amorphous domains are degraded using cellulase, an enzyme that catalyzes the hydrolysis of cellulose, under concentrations, duration and temperature that degrade only the cellulose amorphous domain and not the crystalline domain, as disclosed hereinabove.
- the concentration of cellulase used to degrade the cellulose amorphous domains is between 1 mili Unit to 1000 Units
- the reaction temperature ranges from between about 4°C to about 60°C
- the duration of the enzymatic reaction ranges from a few minutes (e.g., 2 minutes) to several hours (e.g., 5 hours).
- the NCC are washed for several cycles in water and the remaining cellulose is separated (e.g., by centrifugation or nano-filtration).
- the NCC are washed for several cycles in water the remaining cellulose is separated (e.g. by centrifugation or nano-filtration), dialyzed against water and sonicated and/or mechanically dispersed to produce dispersed NCC.
- the invention also provides a process for the preparation of NCC from cellulose sludge (waste) source, the process comprising:
- step d) optionally dispersing the product obtained in step c) to obtain NCC.
- the NCC obtained by this or any other process of the invention is in the form of fibers, 100-500 nm in length, and 10-20 nm in width.
- the pure cellulose is obtainable by a process according to the present invention.
- the process step a) may be carried out under acidic conditions.
- the process step b) may be carried out under acidic or enzymatic conditions.
- the process steps a) and b) are each carried under acidic conditions, wherein the acidic conditions employed in step a) are different from the conditions employed in step b).
- the sludge (waste) cellulose source may be used as a source for additional materials present in the sludge.
- the process of the invention comprises may comprise one or more process steps to separate such additional materials/compounds as sugar, Kaolin, Gypsum and CaCl 2 .
- sugar may be obtained by complete hydrolysis of the amorphous cellulose and other glucans that are present in the raw cellulose material; Kaolin may be recovered by sedimentation; Gypsum may be obtained by treating the reaction medium with sulfuric acid and CaCl 2 may be obtained by using hydrochloric acid.
- the hydrolyzed sugars may be fermented to produce bioethanol; for example water insoluble clay, such as kaolin, may be recovered by sedimentation; and calcium carbonate in the presence of acid releases C0 2 gas.
- the use of sulfuric acid brings about the formation of gypsum that may be recovered and utilized for construction (finish of walls and ceilings), as a fertilizer and soil conditioner etc.
- the usage of HC1 results in the formation of CaCl 2 that may be used as brine for refrigeration plants, ice and dust control on roads, and in concrete.
- the present invention provides a novel process for isolating pure cellulose from an environmentally contaminating source, which cellulose may be used in a great variety of applications including the production of NCC.
- NCC may be used for many material applications, such as foams, films for paper reinforcement and packaging, medical applications (e.g., tissue engineering), food thickening and lubricants.
- Example 1 Recovery of Pure Cellulose from paper sludge cellulose source
- the material was optionally homogenized by Ultrathorax homogenizer
- the cycle is repeated 3 times.
- the suspension was transferred to a 60°C water bath and incubated while shaking for 30 min.
- step (5) The product obtained from step (5) was transferred to a 3,500 Da cutoff dialysis bag and dialyzed against DDW over night. The water was changed at least 4 times. The final pH of the solution was around 6.
- the whiskers solution was sonicated in an ice bath until the solution became optically clear. A final honey-like viscosity was achieved after the suspension has cooled (usually takes a few hours).
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Abstract
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Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2011284253A AU2011284253B2 (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
BR112013002163A BR112013002163B8 (en) | 2010-07-29 | 2011-07-28 | method for producing cellulose nanocrystals from cellulose-containing waste materials |
ES11752351T ES2729656T3 (en) | 2010-07-29 | 2011-07-28 | Production process of cellulose nanocrystals from waste materials containing cellulose |
US13/812,875 US9464142B2 (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste material |
EP11752351.4A EP2598535B1 (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
KR1020137005486A KR101864907B1 (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
CA2806815A CA2806815C (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
CN201180046255.6A CN103124744B (en) | 2010-07-29 | 2011-07-28 | For prepare the method for cellulose nanocrystal from the waste material of containing cellulose |
IL224461A IL224461B (en) | 2010-07-29 | 2013-01-29 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
ZA2013/00856A ZA201300856B (en) | 2010-07-29 | 2013-02-01 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
Applications Claiming Priority (2)
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US36868010P | 2010-07-29 | 2010-07-29 | |
US61/368,680 | 2010-07-29 |
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WO2012014213A1 true WO2012014213A1 (en) | 2012-02-02 |
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PCT/IL2011/000613 WO2012014213A1 (en) | 2010-07-29 | 2011-07-28 | Method for production of cellulose nano crystals from cellulose-containing waste materials |
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US (1) | US9464142B2 (en) |
EP (1) | EP2598535B1 (en) |
KR (1) | KR101864907B1 (en) |
CN (1) | CN103124744B (en) |
AU (1) | AU2011284253B2 (en) |
BR (1) | BR112013002163B8 (en) |
CA (1) | CA2806815C (en) |
ES (1) | ES2729656T3 (en) |
IL (1) | IL224461B (en) |
WO (1) | WO2012014213A1 (en) |
ZA (1) | ZA201300856B (en) |
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WO2015145442A2 (en) | 2014-03-27 | 2015-10-01 | Melodea Ltd. | Nanocrystaline cellulose as absorbent and encapsulation material |
WO2015177795A1 (en) | 2014-05-20 | 2015-11-26 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Nano crystalline cellulose in construction applications |
KR20160042033A (en) * | 2013-08-08 | 2016-04-18 | 에코랍 유에스에이 인코퍼레이티드 | Use of nanocrystaline cellulose and polymer grafted nanocrystaline cellulose for increasing retention in papermaking process |
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2011
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US10294383B2 (en) | 2012-03-06 | 2019-05-21 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Coating layers of a nanocomposite comprising a nano-cellulose material and nanoparticles |
EP3372635A1 (en) | 2012-03-06 | 2018-09-12 | Yissum Research Development Company of The Hebrew University of Jerusalem Ltd. | Light spectrum tunable nanocomposites |
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AU2011284253B2 (en) | 2014-06-05 |
EP2598535B1 (en) | 2019-03-06 |
AU2011284253A1 (en) | 2013-02-21 |
ES2729656T3 (en) | 2019-11-05 |
CA2806815A1 (en) | 2012-02-02 |
KR20130091339A (en) | 2013-08-16 |
BR112013002163B1 (en) | 2020-06-09 |
CN103124744B (en) | 2016-05-04 |
ZA201300856B (en) | 2014-01-29 |
KR101864907B1 (en) | 2018-07-04 |
US20130131332A1 (en) | 2013-05-23 |
BR112013002163B8 (en) | 2020-11-24 |
IL224461B (en) | 2018-06-28 |
US9464142B2 (en) | 2016-10-11 |
CA2806815C (en) | 2018-09-04 |
EP2598535A1 (en) | 2013-06-05 |
CN103124744A (en) | 2013-05-29 |
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