US20150107499A1 - Method of Torrefacation of a Biomass Comprising the Step of Cooling the Torrefaction - Google Patents

Method of Torrefacation of a Biomass Comprising the Step of Cooling the Torrefaction Download PDF

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Publication number
US20150107499A1
US20150107499A1 US14/117,998 US201214117998A US2015107499A1 US 20150107499 A1 US20150107499 A1 US 20150107499A1 US 201214117998 A US201214117998 A US 201214117998A US 2015107499 A1 US2015107499 A1 US 2015107499A1
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Prior art keywords
torrefaction
zone
heating
cooling
biomass
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Abandoned
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US14/117,998
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English (en)
Inventor
Ingemar Olofsson
Martin Nordwaeger
Anders Nordin
Katrina Aberg
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Bioendev AB
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Bioendev AB
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Assigned to BIOENDEV AB reassignment BIOENDEV AB ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ABERG, KATARINA HAKANSSON, NORDIN, ANDERS, NORDWAEGER, Martin, OLOFSSON, INGEMAR
Publication of US20150107499A1 publication Critical patent/US20150107499A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C10L5/447—Carbonized vegetable substances, e.g. charcoal, or produced by hydrothermal carbonization of biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • C10L5/44—Solid fuels essentially based on materials of non-mineral origin on vegetable substances
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B21/00—Heating of coke ovens with combustible gases
    • C10B21/10—Regulating and controlling the combustion
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B39/00—Cooling or quenching coke
    • C10B39/04—Wet quenching
    • C10B39/06—Wet quenching in the oven
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/02—Multi-step carbonising or coking processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B7/00—Coke ovens with mechanical conveying means for the raw material inside the oven
    • C10B7/10—Coke ovens with mechanical conveying means for the raw material inside the oven with conveyor-screws
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/083—Torrefaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
    • F23G5/20—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having rotating or oscillating drums
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B17/00—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement
    • F26B17/18—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotating helical blades or other rotary conveyors which may be heated moving materials in stationary chambers, e.g. troughs
    • F26B17/20—Machines or apparatus for drying materials in loose, plastic, or fluidised form, e.g. granules, staple fibres, with progressive movement with movement performed by rotating helical blades or other rotary conveyors which may be heated moving materials in stationary chambers, e.g. troughs the axis of rotation being horizontal or slightly inclined
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B11/00—Machines or apparatus for drying solid materials or objects with movement which is non-progressive
    • F26B11/02—Machines or apparatus for drying solid materials or objects with movement which is non-progressive in moving drums or other mainly-closed receptacles
    • F26B11/04—Machines or apparatus for drying solid materials or objects with movement which is non-progressive in moving drums or other mainly-closed receptacles rotating about a horizontal or slightly-inclined axis
    • F26B11/0463—Machines or apparatus for drying solid materials or objects with movement which is non-progressive in moving drums or other mainly-closed receptacles rotating about a horizontal or slightly-inclined axis having internal elements, e.g. which are being moved or rotated by means other than the rotating drum wall
    • F26B11/0477—Machines or apparatus for drying solid materials or objects with movement which is non-progressive in moving drums or other mainly-closed receptacles rotating about a horizontal or slightly-inclined axis having internal elements, e.g. which are being moved or rotated by means other than the rotating drum wall for mixing, stirring or conveying the materials to be dried, e.g. mounted to the wall, rotating with the drum
    • F26B11/0486—Machines or apparatus for drying solid materials or objects with movement which is non-progressive in moving drums or other mainly-closed receptacles rotating about a horizontal or slightly-inclined axis having internal elements, e.g. which are being moved or rotated by means other than the rotating drum wall for mixing, stirring or conveying the materials to be dried, e.g. mounted to the wall, rotating with the drum the elements being held stationary, e.g. internal scraper blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B2200/00—Drying processes and machines for solid materials characterised by the specific requirements of the drying good
    • F26B2200/02—Biomass, e.g. waste vegetative matter, straw
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to the field of torrefaction of biomass.
  • it relates to a method and an arrangement for precise control of torrefaction temperature, which is crucial for accurate control of the quality and properties of the torrefied material.
  • the torrefaction stage is characterised by decomposition of hemicellulose at temperatures from 220° C.-230° C., and at higher torrefaction temperatures cellulose and lignin also starts to decompose and release volatiles; cellulose decomposes at a temperature of 305-375° C. and lignin gradually decomposes over a temperature range of 250-500° C.;
  • the requirements for quality and properties of the torrefied products differ considerably depending of the intended use of the product.
  • the inventors have realized that it is crucial to be able to precisely control the torrefaction temperature in order to generate a torrefied product with the desired characteristics.
  • the present invention is based on the insight that exothermal, temperature-increasing reactions, takes place during the torrefaction process and that the amount of generated energy differs considerably between different types of lignocellulosic materials.
  • the inventors have discovered that the torrefaction of woody biomass from eucalyptus generates considerably more energy by exothermal reactions than the torrefaction of woody biomass from spruce.
  • FIG. 1 shows a torrefaction arrangement comprising a torrefaction zone wherein the torrefaction zone comprises means for cooling.
  • FIG. 2 shows a typical temperature variation in the torrefaction arrangement shown in FIG. 1 . Note that the cooling zone is not shown in FIG. 1 .
  • FIG. 3 shows a typical temperature variation in the torrefaction arrangement disclosed in FIG. 1 . Note that the cooling zone is not shown in FIG. 1 .
  • a thermal pre-treatment method that takes place in a virtually inert (oxygen free) atmosphere at a temperature above 220° C. but below 600° C. and which produces a torrefied biomass and combustible gases.
  • a torrefaction stage parts of the biomass, in particular hemicellulose, decompose and give off different types of organic volatiles.
  • the actual torrefaction stage is preceded by a drying stage wherein free water retained in the biomass is removed and by a heating stage wherein the biomass is heated to the desired torrefaction temperature.
  • a specific region of a compartment in a torrefaction arrangement located upstream of a torrefaction zone in relation to a biomass inlet of a torrefaction arrangement, comprising means for specifically regulating the temperature in said specific region and wherein the temperature of a biomass is increased to a temperature near the desired torrefaction temperature prior to torrefaction.
  • a specific region of a compartment in a torrefaction arrangement located downstream of a heating zone in relation to a biomass inlet of a torrefaction arrangement, comprising means for specifically regulating the temperature in said specific region and wherein the temperature of a previously heated biomass is kept virtually constant at the desired torrefaction temperature for a desired torrefaction time wherein a desired torrefaction temperature is in a range between 220° C. to 600° C.
  • a specific region of a compartment in a torrefaction arrangement located upstream of a heating zone in relation to a biomass inlet of a torrefaction arrangement, comprising means for regulating the temperature in said specific region and wherein a biomass is dried to a water content below 10% prior to heating.
  • a specific region in a torrefaction arrangement located downstream of a torrefaction zone in relation to a biomass inlet of a torrefaction arrangement, comprising means for regulating the temperature in said specific region and wherein the biomass is cooled to a temperature below 220° C. preferably below 100° C.
  • a specific region in a torrefaction arrangement located immediately upstream of a heating zone and immediately downstream of a torrefaction zone in relation to a biomass inlet of said torrefaction arrangement.
  • the helicoidal transport device can be fixed to a central shaft or to the inner casing of a compartment, such as a drum, surrounding the transport screw.
  • the material temperature of the biomass during the torrefaction stage should be kept virtually constant such as that the maximum temperature and the minimum temperature of the biomass in a torrefaction zone deviates with at most 50° C., preferably with at most 40° C., preferably with at most 30° C. preferably with at most 20° C., preferably with at most 10° C. preferably with at most 5° C. and more preferably with at most 2° C.
  • an additional heating can take place in the torrefaction zone.
  • the temperature Prior to this short additional heating the temperature can be more than 50° C. below the desired torrefaction temperature, for example 60° C. or 65° C. or 70° C. or 75° C. or even 80° C. below the desired torrefaction temperature.
  • the temperature of the biomass entering a first heating zone is between 90° C. and 130° C.
  • the temperature of the biomass leaving a heating zone deviates from the torrefaction temperature with at most 80° C., such as 75° C., such as 70° C., such as 60° C., such as 65° C., such as 60° C., such as 55° C., preferably at most 50° C., preferably with at most 40° C., preferably with at most 30° C., preferably with at most 20° C., preferably with at most 15° C., preferably with at most 10° C. and more preferably with at most 5° C.
  • the preferred torrefaction temperature according to the present invention is in the range between 220° C. to 600° C., such as 220-500° C., such as 220-450° C., such as 220-400° C., such as 230-600° C., such as 230-500° C., such as 230-450° C., such as 230-400° C., preferably 240-500° C., preferably 240-400° C., preferably 240-350° C. most preferably 270-350° C.
  • the preferred torrefaction time according to the present invention is in the range between 1 and 60 minutes preferably between 1 and 30 minutes, preferably 2-25 minutes and more preferably 2-20 minutes.
  • the torrefaction time normally refers to the residence time of the dried and heated biomass in a torrefaction zone.
  • the cooling is performed during the second half of the torrefaction time or in the downstream half of the torrefaction zone.
  • Such an embodiment may be preferred as the heat from the exothermal reactions may accumulate over the torrefacation reaction leading to an increased need for cooling during the later stage of the torrefaction reaction.
  • the material is dried in a drying zone before the material enters the heating zone and preferably the water content in the biomass is lower than 10%, preferably lower than 7%, preferably lower than 5%, preferably lower than 4% preferably lower than 3%, preferably lower than 2%, more preferably lower than 1% when the biomass enters the heating zone.
  • the torrefied material is cooled in a cooling zone after the material have been torrefied in the torrefaction zone.
  • the material is heated in the heating zone using the means for heating in the heating zone and the temperature in the torrefaction zone is regulated using heat generated from the exothermic energy generated from the biomass during the torrefaction process and cooling supplied from the means for cooling in the torrefaction zone.
  • External heating can also be supplied in the torrefaction zone to control the torrefaction temperature via the means for heating in the torrefaction zone.
  • no external heating is used in the torrefaction zone.
  • the biomass is represented by lignocellulosic biomass.
  • FIG. 2 shows typical temperatures of the biomass in the different zones in the torrefaction arrangement disclosed in FIG. 1 :
  • Zone 1 represents the drying zone ( 3 )
  • zone 2 represents the heating zone ( 6 )
  • zone 3 represents the first torrefaction zone ( 9 )
  • zone 4 represents the second torrefaction zone ( 12 ).
  • the drying zone ( 3 ) the biomass is dried, typically to a water content of 2-10% (w/w) and the temperature is elevated to about 100° C.
  • the heating zone ( 6 ) the material is post-dried to about 0% moisture (w/w) and the temperature of the material is elevated to close to the desired torrefaction temperature which in this example is 350° C.
  • the temperature is kept virtually constant at the desired torrefaction temperature for a time corresponding to the desired torrefaction time. Cooling of the torrefaction reaction in the torrefaction zones counteracts a temperature increase derived from the exothermic torrefaction reactions and thereby facilitates the constant temperature in the torrefaction zones.
  • the second torrefaction zone have special means for cooling the torrefaction reaction ( 18 ) but the torrefaction reaction can also be cooled using cooling media which is introduced to the torrefaction zones via the torrefaction zone cooling media inlet ( 11 , 13 ) Thereafter the temperature is decreased below 100° C. in a cooling zone.
  • FIG. 3 shows typical times and temperatures of the biomass in the different zones in the torrefaction arrangement disclosed in FIG. 1 .
  • the torrefaction temperature is 350° C. and the torrefaction time is 20 minutes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Processing Of Solid Wastes (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
US14/117,998 2011-05-18 2012-05-16 Method of Torrefacation of a Biomass Comprising the Step of Cooling the Torrefaction Abandoned US20150107499A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE1150465-1 2011-05-18
SE1150465A SE535466C2 (sv) 2011-05-18 2011-05-18 Torrefieringsmetod innefattande att torrefieringsreaktionen kyls för att åtminstone delvis motverka en temperaturhöjning
PCT/SE2012/050525 WO2012158110A1 (en) 2011-05-18 2012-05-16 Method of torrefaction of a biomass comprising the step of cooling the torrefaction reaction

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US20150107499A1 true US20150107499A1 (en) 2015-04-23

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US14/117,998 Abandoned US20150107499A1 (en) 2011-05-18 2012-05-16 Method of Torrefacation of a Biomass Comprising the Step of Cooling the Torrefaction

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US (1) US20150107499A1 (ru)
EP (1) EP2710100A4 (ru)
CN (1) CN103608435B (ru)
BR (1) BR112013029477A2 (ru)
CA (1) CA2834303C (ru)
RU (1) RU2615169C2 (ru)
SE (1) SE535466C2 (ru)
WO (1) WO2012158110A1 (ru)

Cited By (2)

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US20160341423A1 (en) * 2015-05-20 2016-11-24 Geoffrey W.A. Johnson Self Torrefied Pellet Stove
CN113046103A (zh) * 2021-03-17 2021-06-29 湖南耕农富硒农业科技股份有限公司 一种生物质燃料的加工设备及加工方法

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JP5752212B2 (ja) * 2013-11-13 2015-07-22 三菱重工環境・化学エンジニアリング株式会社 外熱式炭化炉
CN103756745B (zh) * 2014-01-03 2015-09-02 张家港天源生物能源科技有限公司 生物质烘焙方法
FI125541B (en) * 2014-04-24 2015-11-30 Torrec Oy Torrefieringsanordning
RU2714648C1 (ru) * 2019-07-16 2020-02-18 Смышляев Сергей Владимирович Реактор для торрефикации древесного сырья
RU2714649C1 (ru) * 2019-07-16 2020-02-18 Смышляев Сергей Владимирович Способ торрефикации древесного сырья

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US20100083530A1 (en) * 2008-10-03 2010-04-08 Wyssmont Co. Inc. System and method for drying and torrefaction
WO2012074374A1 (en) * 2010-12-01 2012-06-07 Biolake B.V. Apparatus and process for the thermal treatment of biomass

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160341423A1 (en) * 2015-05-20 2016-11-24 Geoffrey W.A. Johnson Self Torrefied Pellet Stove
US9927174B2 (en) * 2015-05-20 2018-03-27 Geoffrey W. A. Johnson Self Torrefied Pellet Stove
CN113046103A (zh) * 2021-03-17 2021-06-29 湖南耕农富硒农业科技股份有限公司 一种生物质燃料的加工设备及加工方法

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WO2012158110A1 (en) 2012-11-22
CA2834303C (en) 2019-12-03
RU2013156049A (ru) 2015-06-27
SE1150465A1 (sv) 2012-08-21
CN103608435B (zh) 2016-03-30
SE535466C2 (sv) 2012-08-21
CN103608435A (zh) 2014-02-26
EP2710100A4 (en) 2014-10-08
EP2710100A1 (en) 2014-03-26
CA2834303A1 (en) 2012-11-22
RU2615169C2 (ru) 2017-04-04
BR112013029477A2 (pt) 2020-08-04

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