Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/04—Raw material of mineral origin to be used; Pretreatment thereof
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/105—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with a mixture of organic and inorganic binders
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/06—Methods of shaping, e.g. pelletizing or briquetting
  • C10L5/10—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders
  • C10L5/14—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders
  • C10L5/143—Methods of shaping, e.g. pelletizing or briquetting with the aid of binders, e.g. pretreated binders with organic binders with lignin-containing products
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L5/00—Solid fuels
  • C10L5/02—Solid fuels such as briquettes consisting mainly of carbonaceous materials of mineral or non-mineral origin
  • C10L5/34—Other details of the shaped fuels, e.g. briquettes
  • C10L5/36—Shape
  • C10L5/363—Pellets or granulates
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L5/442—Wood or forestry waste
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L5/445—Agricultural waste, e.g. corn crops, grass clippings, nut shells or oil pressing residues
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/08—Drying or removing water
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
  • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
  • C10L2290/148—Injection, e.g. in a reactor or a fuel stream during fuel production of steam
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/30—Pressing, compressing or compacting
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/32—Molding or moulds
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
  • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
  • C10L2290/545—Washing, scrubbing, stripping, scavenging for separating fractions, components or impurities during preparation or upgrading of a fuel
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
• • 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

• Various embodiments disclosed herein are generally directed to a method of producing lignocellulosic fiber masses suitable, among other things for the manufacture of fuel pellets, in particular, from feedstocks that, because of high contents of substances, are regarded as deleterious to good combustion performance such as alkali metals and chlorides.
• Each of these methods produce a fuel pellet having the bulk of compounds of alkali metals, chlorine and sulfur present in the feed. Furthermore, their resistance to water is variable; white pellets must be stored under cover, while black pellets need to be stored under conditions that minimize leaching. Therefore, a need exists to produce a fuel pellet and other lignocellulosic products having reduced hemicellulose, alkali metal and chlorine contents.
• the present disclosure is directed toward a method of producing such a fuel pellet and/or other lignocellulosic product.
• the methods described herein can be used to manufacture fuel pellets and other materials by steam treatment of biomass such as wood chips, bagasse, straw and energy crops that may be difficult to process without steam treatment and that may contain unacceptably high levels of compounds of alkali metals, chlorine and sulfur, for use as fuel pellets, with the additional possibility of avoiding an energy-demanding and often difficult drying step before steam treatment.
• biomass such as wood chips, bagasse, straw and energy crops that may be difficult to process without steam treatment and that may contain unacceptably high levels of compounds of alkali metals, chlorine and sulfur, for use as fuel pellets, with the additional possibility of avoiding an energy-demanding and often difficult drying step before steam treatment.
• These pellets can be stored under wet conditions for long periods of time with minimal loss of energy content and durability. They have higher energy contents and somewhat higher bulk densities than pellets made from the same feed by state-of-the-art methods and can be produced at lower temperatures, thus reducing the cost of plant needed to make them.
• the steam treated materials made in accordance with the methods consist of two fractions: a water phase and a solid phase.
• the water phase will contain water soluble materials, primarily carbohydrates and minerals, primarily alkali metals and chlorides, plus some alkaline earth metals and sulfates.
• This product is eminently suitable, as a component in animal feed as a feedstock for fermentation or chemical processing.
• the solid fraction can, as described above, be used to manufacture fuel pellets, but it can also be converted to fibrous materials for cartons and coarse paper or, with the addition of vegetable oil and, optionally, an acidic catalyst, as a component in wooden boards and mouldings.
• One particularly advantageous application for the methods of this invention is the addition of an oil before or after steam treatment (or both) enabling the dried residue to be used as a thermoplastic compound. This is possible because the residue contains fewer substances such as reducing sugars that can react with and crosslink the lignin.
• Lignocellulose-based products with low contents of hemicellulose, chlorine, sulfur, and alkali and alkaline earth metals are, in at least one embodiment, made by steam-treating an undried biomass, and washing the steam treated material to remove water soluble materials and, optionally, drying the residue.
• the lignocellulose-based products are made by steam treating a biomass, which may contain up to 60% by weight of moisture prior to steam treatment, defibrillating and washing the steam treated material to remove water soluble materials and, optionally, drying the residue.
• a vessel containing the biomass is evacuated before the introduction of steam, such that the total free oxygen content of the gas in the vessel into which the steam is injected is less than 10 volume % and preferably not more than 3 volume %.
• the lignocellulose-based products from biomass treated by injecting dry saturated or unsaturated steam at a temperature of at least 300°F at a pressure of at least 52 psig and preferably between 120 and 280 psig into a reactor containing the biomass and maintaining the chosen pressure for between 1 and 30 minutes, the lower the steam pressure, the longer the residence time.
• the lignocellulose-based products from biomass treated by injecting dry saturated or unsaturated steam have a temperature of at least 150°C at a pressure of at least 60 psig and between 120 and 240psig into a reactor containing the biomass and maintaining the chosen pressure for between 3 and 30 minutes, the lower the steam pressure, the longer the residence time.
• up to 8% on biomass dry weight of an organic substance capable of functioning as a swelling agent or solvent for lignin during steam treatment and having a boiling point greater than 100°C such as a fatty acid, a triglyceride, glycerol or a glycol is included in the biomass prior to the introduction of steam .
• up to 5% on biomass dry weight of an acidic catalyst such as nitric acid or acetic acid having a boiling point of less than 200°C may be added after evacuation of the vessel and prior to the introduction of steam .
• hydrophobic lignocellulose-based products including fuel pellets with low chlorine and alkali metal contents, made from steam processed materials as described herein are then water-washed, in at least one embodiment, in a counter-current process and the residue dried to less than 10% moisture by weight and in other embodiments, less than 5% moisture by weight, adding to it between 3% and 20% and between 5% and 8% by weight of an oil and then subjecting the whole to compression, for example, in a conventional molding or extrusion process.
• hydrophobic lignocellulose-based products including fuel pellets with low chlorine, hemicellulose and alkali metal contents, made from steam processed materials as described herein are then subjected to dewatering and optionally water-washed, in at least one embodiment, in a counter-current process and the residue dried to less than 10% moisture by weight and in other embodiments, less than 5% moisture by weight, then adding sufficient of one of the above-mentioned lignin swelling agents or solvents to bring the total content of the said agent to at least 2% and preferably between 2 and 8% by weight and then subjecting the whole to compression, for example, in a conventional molding, pelletizing or extrusion process.
• the oil can be added to the dewatered filter cake prior to the final drying step, or immediately prior to the subsequent conversion process or to the biomass itself before steam treatment.
• Thermoplastic molding and extrusion compounds made as described herein may contain at least 3% and not more than 25% by weight of an oil containing at least 20% unsaturates and having a boiling point of at least 150°C at atmospheric pressure.
• the wheat straw or wheat straw pellets are transferred to the reactor without drying .
• the whole is evacuated to -0.85 bar and allowed to stand for 2 minutes. Dry saturated steam having a temperature of 200°C is introduced and the whole allowed to stand for 7 minutes once a pressure of 14.5 bar is reached and maintained.
• the filter cake is dried to a moisture content of more than 2% and less than 15% by weight and, in one embodiment between 4% and 8% by weight either before or after the addition of oil, such that the total amount of oil contained in the filter cake immediately prior to it being converted to pellets is not less than 2% on dry matter and the whole pelletized in a mill such that the surface temperature of the pellets is >95°C and preferably between 105°C and 125°C.
• These pellets have the following properties:
• Example 3 Fuel pellets made with a brittle additive
• At least 3 weight % on dry matter of an oil and at least 10% finely ground bituminous coal are added to the filter cake and the whole thoroughly mixed.
• the whole is then transferred to a pellet mill and pelletized through a pellet die such that the surface temperature of the pellets as they exit the die is not less than 90°C and preferably between 105°C and 120°C.
• State-of-the-art steam-treated biomass used in the manufacture of so-called black pellets has the property of beginning to crosslink or thermosetting once subjected to the temperatures and pressures that typify pelletizing, whether in an extruder or a pellet mill. This is also the case when pellets containing vegetable oils are made from this type of biomass.
• microchips 100 parts by weight of fresh, birch-wood "microchips" (in at least one embodiment, the chips having at least 30% moisture content by weight) .
• the moisture content of the steam treated material is adjusted to at least 50% by weight and preferably between 60 and 70% by weight and compressed to remove as much moisture as possible, e.g., in a filter or screw press.
• the resulting solid material can be dried to the desired moisture content at once or the above process repeated as necessary before the final material is dried as required.
• the steam treated biomass is removed from the reactor vessel and transferred to a slurrying tank where the continuous phase can be the final filtrate from the washing process.
• the whole is transferred to a counter-current washing system, e.g., a series of filter presses.
• the excess liquor from the first wash stage is removed for further treatment and the washing process continued counter-currently such that the residue in the final filtration step is washed with clean water.
• the final filter cake is removed and dried as required.
• the miscanthus is transferred to the reactor without drying.
• the whole is evacuated to -0.85 bar and allowed to stand for 2 minutes. Dry saturated steam having a temperature of 200°C is introduced and the whole allowed to stand for 7 minutes once a pressure of 14.5 bar is reached and maintained.
• the mixture of oil and filter cake is pelletized in a mill through a die with a compression ratio of 6, so that the surface temperature of the pellets is ⁇ 95°C and preferably between 105°C and 125°C.
• Chlorine content (as chloride) : ⁇ 0.03%
• the mixture of oil and filter cake is processed in a pelletizing extruder such that the surface temperature of the pellets is >95°C and preferably between 105°C and 125°C.
• Chlorine content (as chloride) : ⁇ 0.03%
• Example 7 Fuel pellets made with a brittle additive
• the miscanthus is transferred to the reactor without drying.
• the whole is evacuated to -0.85 bar and allowed to stand for 2 minutes. Dry saturated steam having a temperature of 200°C is introduced and the whole allowed to stand for 7 minutes once a pressure of 14.5 bar is reached and maintained.
• the steam treated biomass is removed from the reactor vessel and transferred to a slurrying tank where the continuous phase is the final filtrate from the washing process.
• the whole is transferred to a counter- current washing system, e.g., a series of filter presses.
• the excess liquor from the first wash stage is removed for further treatment and the washing process continued counter-currently such that the residue in the final filtration step is washed with clean water.
• the final filter cake is removed and dried to 5% moisture content by weight.
• the whole is then transferred to a pellet mill and pelletized through a pellet die having a compression ratio of 5, making sure that the surface temperature of the pellets thus made is not less than 95°C and preferably between 105°C and 120°C.
• Chlorine content (as chloride) : ⁇ 0.03%

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Geology (AREA)
• Agronomy & Crop Science (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Biodiversity & Conservation Biology (AREA)
• Ecology (AREA)
• Forests & Forestry (AREA)
• Wood Science & Technology (AREA)
• Solid Fuels And Fuel-Associated Substances (AREA)

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• 2014
  • 2014-02-10 CA CA2900646A patent/CA2900646A1/en not_active Abandoned
  • 2014-02-10 US US14/177,056 patent/US20140223811A1/en not_active Abandoned
  • 2014-02-10 EP EP14749241.7A patent/EP2954034A4/de not_active Withdrawn
  • 2014-02-10 BR BR112015018965A patent/BR112015018965A2/pt not_active IP Right Cessation
  • 2014-02-10 JP JP2015557183A patent/JP2016506993A/ja active Pending
  • 2014-02-10 WO PCT/US2014/015640 patent/WO2014124399A1/en not_active Ceased
• 2015
  • 2015-08-07 PH PH12015501747A patent/PH12015501747A1/en unknown

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