EP2893163A2 - Appareil et procédé de fonctionnement d'un injecteur pour un appareil de post-traitement de gaz d'échappement - Google Patents

Appareil et procédé de fonctionnement d'un injecteur pour un appareil de post-traitement de gaz d'échappement

Info

Publication number
EP2893163A2
EP2893163A2 EP12881703.8A EP12881703A EP2893163A2 EP 2893163 A2 EP2893163 A2 EP 2893163A2 EP 12881703 A EP12881703 A EP 12881703A EP 2893163 A2 EP2893163 A2 EP 2893163A2
Authority
EP
European Patent Office
Prior art keywords
exhaust gas
temperature
nozzle
injector
flow
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP12881703.8A
Other languages
German (de)
English (en)
Other versions
EP2893163A4 (fr
Inventor
Philip Meier
Walter JACQUES
Qunlong DONG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mack Trucks Inc
Original Assignee
Mack Trucks Inc
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
Application filed by Mack Trucks Inc filed Critical Mack Trucks Inc
Publication of EP2893163A2 publication Critical patent/EP2893163A2/fr
Publication of EP2893163A4 publication Critical patent/EP2893163A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N11/00—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity
    • F01N11/002—Monitoring or diagnostic devices for exhaust-gas treatment apparatus, e.g. for catalytic activity the diagnostic devices measuring or estimating temperature or pressure in, or downstream of the exhaust apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/2006—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating
    • F01N3/2033—Periodically heating or cooling catalytic reactors, e.g. at cold starting or overheating using a fuel burner or introducing fuel into exhaust duct
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
    • F01N3/206—Adding periodically or continuously substances to exhaust gases for promoting purification, e.g. catalytic material in liquid form, NOx reducing agents
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N9/00—Electrical control of exhaust gas treating apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/03—Adding substances to exhaust gases the substance being hydrocarbons, e.g. engine fuel
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/08—Adding substances to exhaust gases with prior mixing of the substances with a gas, e.g. air
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1453—Sprayers or atomisers; Arrangement thereof in the exhaust apparatus
    • F01N2610/146—Control thereof, e.g. control of injectors or injection valves
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/14—Arrangements for the supply of substances, e.g. conduits
    • F01N2610/1493—Purging the reducing agent out of the conduits or nozzle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2900/00—Details of electrical control or of the monitoring of the exhaust gas treating apparatus
    • F01N2900/06—Parameters used for exhaust control or diagnosing
    • F01N2900/14—Parameters used for exhaust control or diagnosing said parameters being related to the exhaust gas
    • F01N2900/1404—Exhaust gas temperature
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/40—Engine management systems

Definitions

  • the invention is directed to exhaust gas aftertreatment apparatuses for internal combustion engines and methods for their operation. More particularly, the invention is directed to an apparatus and method for preventing coke fouling of an aftertreatment injector nozzle of an aftertreatment system.
  • Exhaust gas aftertreatment apparatuses in automotive vehicles are used to convert or remove targeted substances from the exhaust gas.
  • Aftertreatment devices include, for example, diesel oxidation catalysts (DOC), which can remove particulate matter and oxidize carbon monoxide and uncombusted hydrocarbons in the exhaust gas, diesel particulate filters (DPF), which remove particulate matter from the exhaust gas, and selective catalytic reduction (SCR) systems, that inject an ammonia-based reductant in the presence of a catalyst to convert oxides of nitrogen (NOx) to nitrogen gas and water.
  • DOC diesel oxidation catalysts
  • DPF diesel particulate filters
  • SCR selective catalytic reduction
  • Certain aftertreatment devices operate only at or above a threshold temperature, for example, the SCR devices.
  • Other devices, such as the DPF require the regular removal of collected particulate matter from the filter body.
  • One such process, known as regeneration occurs by oxidation of the collected particulate matter, which requires the filter body to be at an elevated temperature, typically above 600° C.
  • aftertreatment components may be at or near ambient temperature, which is typically too low for operation of those devices.
  • automotive exhaust, and diesel engine exhaust in particular, is not consistently at temperatures high enough for operation of certain exhaust aftertreatment systems on the vehicle, in particular, regeneration of DPFs.
  • some device or method for increasing the temperature of the exhaust gas when necessary is provided.
  • Exhaust heating methods and devices include engine management for control of exhaust gas temperature, resistive heating coils placed in the exhaust, and burners.
  • One such device is a system for injecting hydrocarbon, typically diesel fuel, into the exhaust gas, including an injector with a nozzle positioned to inject fuel into the exhaust gas flow.
  • a problem with hydrocarbon injectors is fouling of the injector nozzle from decomposed liquid hydrocarbon, particulate matter, and other residue collecting on the nozzle, called "coking".
  • an exhaust gas aftertreatment apparatus having a hydrocarbon injector includes an injector nozzle coated with a catalytic material.
  • the catalytic coating allows hydrocarbon that collects on the nozzle to oxidize at a temperature lower than non-catalyzed oxidation.
  • An apparatus further includes a device for providing and controlling an air flow through the injector responsive to the exhaust gas temperature.
  • a method of the invention for operating the injector has three states: (1) fuel injection for heating the aftertreatment devices, (2) after fuel injection, air flow through the nozzle to purge residual fuel and/or cool the nozzle to prevent carbon deposits when exhaust gas temperature is low, and (3) no (or low) air flow to allow passive heating of the nozzle by the exhaust for oxidation of any accumulated carbon when exhaust temperature is high enough to support
  • the method may include an additional air purge to remove ash.
  • a method of operating an injector for an exhaust gas aftertreatment apparatus to avoid coke deposits, the injector nozzle having a catalyst coating includes the steps of injecting a hydrocarbon fluid into an exhaust gas flow over a selected duration, causing air to flow through the injector nozzle when an exhaust gas temperature is below a threshold temperature, and, substantially stopping the flow of air through the injector nozzle when the exhaust gas temperature is above the threshold temperature.
  • the method includes the steps of monitoring a condition of the aftertreatment apparatus, monitoring an exhaust gas temperature, and, responsive to the condition of the aftertreatment apparatus and responsive to the exhaust gas temperature, controlling the injection of hydrocarbon in the exhaust gas flow.
  • air flow is preferably pulsed, the air flow parameters, volume, frequency, and duration, being controlled responsive to exhaust gas temperature.
  • Figure 1 is a schematic drawing of an internal combustion engine and exhaust system having an aftertreatment system in accord with an exemplary embodiment of the invention
  • Figure 2 is a simplified drawing of an exemplary aftertreatment injector
  • FIG. 3 is a flow diagram of a method according to the invention. Detailed Description of the Invention
  • FIG. 1 illustrates an apparatus including an internal combustion engine 10 with an exhaust gas aftertreatment system 12 according to the invention.
  • the engine 10 is connected to an exhaust gas conduit 14 that receives exhaust gas from the engine.
  • Exhaust gas is carried by the conduit to an aftertreatment system 16, which may include a Diesel Oxidation Catalyst (DOC), a Diesel Particulate Filter (DPF), and a device for treating Nitrogen Oxides, such as a selective catalytic reaction device (SCR) or Lean NOx Catalyst (LNC).
  • SCR selective catalytic reaction device
  • LNC Lean NOx Catalyst
  • the DPF filters the exhaust gas and collects soot and other particulate matter, which must be removed at intervals or the DPF becomes clogged.
  • One common method for removing particulate matter is to raise the temperature of the DPF filter body to a temperature sufficient to oxidize the particulate matter.
  • the temperature of the DPF filter body can be increased in various ways, as is known in the art.
  • One way is to add hydrocarbon (or fuel) to the exhaust gas, which is oxidized, releasing heat energy.
  • An injector 20 connected to a source of hydrocarbon 22 is shown in Figure 1 for such a purpose.
  • the injector 20 includes a nozzle 24 to introduce hydrocarbon into the exhaust gas flow.
  • the injector 20 in the illustrated embodiment is also connected to an air source 26.
  • a controller 28 is programmed to control the flow of hydrocarbon and air through the injector 20, as will be described in more detail below.
  • Temperature sensors 30, 34 are positioned at the entry and exit, respectively, of the aftertreatment device 16 to monitor the temperature of the exhaust gas as it enters and exits the device.
  • temperature sensors may be arranged upstream of the DOC, downstream of the DOC and upstream of the DPF, and downstream of the DPF.
  • pressure sensors 32, 36 are provided at the aftertreatment device 16 entry and exit, respectively, to monitor a pressure change of the exhaust gas across the DPF. The difference between entry and exit exhaust gas pressure is useful to determine the soot loading of the DPF.
  • the injector 20 is upstream of the aftertreatment device 16, it is exposed to exhaust gas carrying particulate matter.
  • the injector nozzle 24 and the hydrocarbon liquid at and exiting the nozzle 24 of the injector are exposed to the heat of the exhaust. This can result in coking of the nozzle as hydrocarbon liquid and particulate matter deposits form on the nozzle.
  • Maintaining the nozzle at a relative low temperature can help avoid, although not eliminate, coking.
  • Coke deposits may be removed by heating the nozzle to a sufficiently high temperature to oxidize the carbon, and devices for heating nozzles are known. However, these add expense and complexity to the injector system.
  • an injector nozzle 24 is provided with a coating of a catalytic material that allows coke deposits to oxidize at a relatively low temperature.
  • Suitable catalytic materials include precious metal catalysts such as platinum and palladium.
  • an injector nozzle 24 includes a nozzle body 40 having a flow channel 42 for a liquid fuel.
  • the flow channel 42 ends in a tip 44, which may include fluid distribution devices to control flow volume or induce swirl or spray angle, for example.
  • the injector 20 may be any suitable fluid injector, and may include an injector body 50 having an interior passage 52 for the injected fluid, a needle 54 movable in the passage 52 operable by a spring 56 and an actuator device (not shown) to control the flow into the nozzle channel 42 and to the tip 44.
  • a catalytic coating is preferably applied to surfaces exposed to exhaust gas heat and the fuel injected by the nozzle 24.
  • Such surfaces include the exterior surface 46 of the nozzle body 24, the tip 44, and a surface 48 defining the flow channel 42.
  • FIG 3 is a diagram of a method according to the invention for preventing coke fouling of an injector.
  • the aftertreatment (AT) device is monitored for operational condition (S100) by monitoring a pressure differential between incoming and outgoing exhaust gas and/or by monitoring a temperature of the device.
  • a temperature of the exhaust gas entering the AT device is also monitored (S102).
  • the method determines if the exhaust gas is above a temperature threshold at which the exhaust gas can heat the catalyst coated nozzle to a temperature sufficient for oxidization of deposited carbon (S104). Using a precious metal as a catalyst, heating the nozzle to about 240°C or higher will promote oxidation.
  • the method of the invention is not performed entirely sequentially; the steps of monitoring the AT device, monitoring the exhaust gas temperature, and determining if the exhaust gas temperature is above the threshold are performed continually or in a repeating sequence as the rest of the method is performed.
  • Step S106 stops air flow through the injector or substantially stops air flow to provide a minimal amount of air flow, for example, to prevent ingress of exhaust gas into the nozzle, but not effectively cool the nozzle.
  • the lack of air flow or low amount of air flow allows the nozzle to heat to the temperature sufficient for oxidizing any carbon deposits.
  • a timer may be started to measure an interval during which the nozzle is heated and oxidation occurs.
  • the air flow will remain off or at a minimum as long as the exhaust gas temperature is above the threshold as determined in Step S104.
  • Step S108 When the heating/oxidizing time interval has elapsed (Step S108) or the exhaust gas temperature falls below the threshold temperature, the method increases air flow through the nozzle (S110), to provide cooling to inhibit coking.
  • Step S104 if the exhaust gas temperature is below the threshold temperature, the condition of the AT device is evaluated to determine if it is necessary to increase the exhaust gas temperature (Step S112).
  • a DPF device may require a regeneration procedure to remove collected particulate matter.
  • the method causes air to flow through the nozzle (Step S114). Air flow will help cool the nozzle to prevent or inhibit coking fouling.
  • hydrocarbon is injected through the injector (Step S116) while the exhaust gas temperature is monitored. An amount of hydrocarbon and a frequency of injections are controlled to the exhaust gas temperature to heat the DPF device to a target temperature and maintain that temperature for a time interval sufficient for regenerating the DPF. Alternatively, the DPF may be heated until the exhaust gas pressure differential between the entry and exit drops below a threshold.
  • Step S114 When the regeneration process is completed, the hydrocarbon injection is stopped and air is caused to flow through the nozzle (Step S114).
  • the flow of air after hydrocarbon injection will help purge the nozzle of residual hydrocarbon and the continued flow of air helps cool the nozzle to help inhibit or prevent coke fouling.
  • air flows continuously through the nozzle to maintain nozzle temperatures as low as possible to slow carbon deposition.
  • air flow through the nozzle is completely or substantially completely shut off to avoid cooling the nozzle and allow oxidation of any coking.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de fonctionnement d'un injecteur de système de post-traitement d'échappement pour empêcher le calaminage. Ce procédé comprend les étapes d'injection de carburant pour chauffer les dispositifs de post-traitement, en l'absence d'injection de carburant, d'écoulement d'air pour purger et refroidir la buse pour empêcher des dépôts de carbone lorsque la température de gaz d'échappement est basse, et sensiblement arrêter l'écoulement d'air pour permettre un chauffage passif de la buse par l'échappement pour une oxydation de tout carbone accumulé lorsque la température d'échappement est suffisamment élevée pour permettre l'oxydation. De préférence, la buse a un revêtement de matière catalytique pour réduire la température nécessaire pour une oxydation de la matière de calaminage.
EP12881703.8A 2012-07-26 2012-07-26 Appareil et procédé de fonctionnement d'un injecteur pour un appareil de post-traitement de gaz d'échappement Withdrawn EP2893163A4 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2012/048277 WO2014018036A2 (fr) 2012-07-26 2012-07-26 Appareil et procédé de fonctionnement d'un injecteur pour un appareil de post-traitement de gaz d'échappement

Publications (2)

Publication Number Publication Date
EP2893163A2 true EP2893163A2 (fr) 2015-07-15
EP2893163A4 EP2893163A4 (fr) 2016-06-08

Family

ID=49997940

Family Applications (1)

Application Number Title Priority Date Filing Date
EP12881703.8A Withdrawn EP2893163A4 (fr) 2012-07-26 2012-07-26 Appareil et procédé de fonctionnement d'un injecteur pour un appareil de post-traitement de gaz d'échappement

Country Status (8)

Country Link
US (1) US20150192050A1 (fr)
EP (1) EP2893163A4 (fr)
JP (1) JP5909028B2 (fr)
CN (1) CN104541030A (fr)
BR (1) BR112015001717A2 (fr)
CA (1) CA2879562A1 (fr)
RU (1) RU2604405C2 (fr)
WO (1) WO2014018036A2 (fr)

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JP6563890B2 (ja) * 2016-12-27 2019-08-21 株式会社Ｓｏｋｅｎ 内燃機関の排気浄化装置
CN108240250B (zh) 2016-12-27 2020-11-24 丰田自动车株式会社 内燃机的排气净化装置
CN109209569B (zh) * 2017-07-07 2022-01-25 卡明斯公司 柴油机热管理控制策略
CN107387206A (zh) * 2017-08-17 2017-11-24 无锡威孚高科技集团股份有限公司 一种用于dpf再生系统的燃油喷嘴
EP3894674A4 (fr) * 2018-12-14 2022-09-07 Cummins Filtration IP, Inc. Module de dosage de carburant diesel pour la régénération de filtres à particules diesel avec purge continue
US11885251B2 (en) * 2022-05-25 2024-01-30 Tenneco Automotive Operating Company Inc. Selective catalytic reduction catalyst pre-heating burner assembly and method of controlling burner emissions

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Also Published As

Publication number Publication date
WO2014018036A3 (fr) 2014-05-01
RU2015106316A (ru) 2016-09-20
CA2879562A1 (fr) 2014-01-30
RU2604405C2 (ru) 2016-12-10
CN104541030A (zh) 2015-04-22
WO2014018036A2 (fr) 2014-01-30
JP2015526634A (ja) 2015-09-10
JP5909028B2 (ja) 2016-04-26
EP2893163A4 (fr) 2016-06-08
US20150192050A1 (en) 2015-07-09
BR112015001717A2 (pt) 2017-07-04

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