WO2015118728A1 - 二酸化炭素回収装置及び二酸化炭素回収方法 - Google Patents
二酸化炭素回収装置及び二酸化炭素回収方法 Download PDFInfo
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Definitions
- the present invention relates to a carbon dioxide recovery device and a recovery method using a carbon dioxide capturing material.
- a gas adsorption separation technique in order to adsorb and separate a specific component in the gas, first, the specific component is first adsorbed on the adsorbent of the adsorption tower containing the adsorbent, and then a certain amount of the specific component is adsorbed.
- a technique for regenerating an adsorbent by desorbing a specific component by heating and aeration of the adsorbing tower is known.
- Regenerating gas such as water vapor that can be easily gas-liquid separated at normal temperature and pressure is desirable as the gas to flow in order to prevent the gas purity of the recovered specific component from decreasing.
- the carbon dioxide capturing material temperature is lower than the water vapor temperature, there is a problem that water vapor condenses on the surface of the carbon dioxide capturing material due to the circulation of water vapor.
- Patent Document 1 discloses a carbon dioxide recovery system that recovers a high concentration of carbon dioxide from a carbon dioxide-containing gas so that when the carbon dioxide is recovered from the carbon dioxide scavenger, it is easily separated from the carbon dioxide by cooling.
- a carrier gas such as water vapor, methanol, ethanol or the like having a boiling point of about 100 ⁇ 50 ° C.
- the heating temperature is not higher than 200 ° C., but also high concentration
- a vacuum pump is provided in a flow path for recovering carbon dioxide to depressurize the container within a pressure difference of 15 atm.
- Patent Document 2 discloses a technique that eliminates the need for depressurization in desorption by blowing with a purge gas having a low CO 2 partial pressure in the desorption step of CO 2 separation and recovery. This document also describes that the water vapor pressure is higher than atmospheric pressure (for example, 105 kPa).
- An object of the present invention is to reduce the amount of regeneration gas supplied into the carbon dioxide recovery tower in the regeneration process of the carbon dioxide capturing material, increase energy efficiency, and shorten the time spent in the regeneration process.
- the carbon dioxide recovery device of the present invention includes a carbon dioxide absorption tower that contains a carbon dioxide capture material, a heating unit that heats the carbon dioxide capture material, and a flow path for introducing a carbon dioxide-containing gas into the carbon dioxide absorption tower. , A flow path for introducing the regeneration gas into the carbon dioxide absorption tower, and a flow path for recovering the mixed gas containing the gas desorbed from the carbon dioxide capture material. Preheating is performed, and then a regeneration gas is introduced into the carbon dioxide absorption tower, and carbon dioxide is recovered from the carbon dioxide capturing material.
- the present invention it is possible to reduce the amount of the regeneration gas supplied into the carbon dioxide recovery tower in the regeneration process of the carbon dioxide capturing material, increase the energy efficiency, and shorten the time spent in the regeneration process.
- FIG. 1A and 1B show a carbon dioxide absorption tower of a carbon dioxide recovery device.
- FIG. 1A is an overall configuration diagram showing a state of a valve in a process of preheating in order to regenerate a carbon dioxide capturing material in a carbon dioxide recovery device.
- FIG. 1B is an overall configuration diagram showing a state of a valve in a process of regenerating a carbon dioxide capturing material by introducing a regeneration gas after the heating process of FIG. 1A.
- a carbon dioxide capturing material 101 is accommodated inside the carbon dioxide absorption tower 100.
- the carbon dioxide absorption tower 100 is connected to a carbon dioxide-containing gas flow path 102, a carbon dioxide removal gas recovery flow path 103, and a mixed gas recovery flow path 105. Each of these is provided with a valve so that the flow of gas can be controlled.
- the carbon dioxide absorption tower 100 is connected to a regeneration gas flow path 104 provided with a regeneration gas flow rate adjusting unit 109.
- the carbon dioxide absorption tower 100 is provided with heat medium flow paths 107 and 108 so that the carbon dioxide capturing material 101 can be heated.
- the opening / closing valve 106 When capturing carbon dioxide, the opening / closing valve 106 is opened, the carbon dioxide-containing gas is introduced into the carbon dioxide absorption tower 100 from the carbon dioxide-containing gas flow path 102, and the carbon dioxide-containing gas 101 contains the carbon dioxide-containing gas. Selectively captures carbon dioxide.
- the gas from which carbon dioxide has been removed is discharged from the carbon dioxide removal gas recovery channel 103.
- the carbon dioxide concentration of the gas in the carbon dioxide removal gas recovery channel 103 reaches a set value, or when a certain time has elapsed after the carbon dioxide containing gas is circulated, the carbon dioxide containing gas channel 102 and the carbon dioxide removal gas
- the collection channel 103 is closed.
- FIG. 1A shows the open / close state of the valve in the process of heating in order to regenerate the carbon dioxide capturing material.
- the mixed gas recovery flow path 105 is opened and the heat medium flow path 107 disposed inside the carbon dioxide absorption tower 100.
- the carbon dioxide capturing material 101 is heated by the heat medium passage 108 disposed outside the carbon dioxide absorption tower 100. Carbon dioxide desorbed from the carbon dioxide capturing material 101 by this heating is recovered from the mixed gas recovery flow path 105.
- the heat medium flow path 108 arranged outside the carbon dioxide absorption tower 100 may be arranged outside the carbon dioxide absorption tower 100, or may be arranged inside the wall of the carbon dioxide absorption tower 100, for example. good.
- the heat medium passages 107 and 108 are collectively referred to as “heating units”.
- the regeneration gas flow rate adjustment unit 109 adjusts the flow rate.
- the working gas is fed into the carbon dioxide absorption tower 100 from the regeneration gas flow path 104.
- the carbon dioxide capturing material 101 is preheated by the heating unit (preheating step), and then a regeneration gas (water vapor) is introduced into the carbon dioxide absorption tower 100 (regeneration gas supply step). Collect carbon dioxide.
- a regeneration gas water vapor
- These switching controls may be performed manually by an operator, or may be performed by issuing an electrical or mechanical command based on data detected by an attached control unit.
- the flow rate of the regeneration gas is preferably 0.5 m / second or more in terms of the linear velocity in the carbon dioxide absorption tower 100. Further, from the viewpoint of pressure loss, it is more preferable that the value is 0.5 m / second or more and 2.5 m / second or less.
- the particle size of the carbon dioxide capture material is 2.5 cm
- the porosity is 0.4
- the viscosity is 2.8 ⁇ 10 ⁇ 4
- the height of the carbon dioxide capture material packed bed is 10 m.
- the linear velocity of the regeneration gas is 2.5 m / sec
- the pressure loss is 52 kPa, which exceeds 50 kPa, which is considered as an allowable pressure loss. Therefore, it was determined that the linear velocity of the regeneration gas is preferably 2.5 m / second or less.
- valves of the heat medium passages 107 and 108 may or may not be closed.
- FIG. 1B shows an open / close state of the valve when the circulation of the regeneration gas is started while the circulation of the heat medium is kept open.
- the carbon dioxide partial pressure around the carbon dioxide capturing material 101 can be reduced, the desorption of carbon dioxide from the carbon dioxide capturing material 101 is promoted, and the carbon dioxide capturing material 101
- the regeneration rate can be improved.
- the conditions for switching from heating to regeneration gas circulation may be determined based on the temperature measuring means installed in the carbon dioxide absorption tower 100, and the time to reach the set temperature may be estimated empirically or by calculation. , It may be switched at that time, or when the flow rate (concentration) of the outlet gas (carbon dioxide) desorbed from the carbon dioxide capturing material is measured and the flow rate falls below the set amount (concentration) Control may be performed to switch. That is, when the concentration of carbon dioxide contained in the mixed gas becomes equal to or lower than a predetermined value, the control may be performed so that the introduction of the regeneration gas is stopped.
- the regeneration gas introduction may be controlled to stop.
- the concentration of the regeneration gas may be detected by measuring its dew point.
- the supply may be controlled to stop when the regeneration gas is supplied for a predetermined time. That is, the supply time of the regeneration gas may be set in advance.
- the regeneration gas used here may be any gas other than carbon dioxide, but is preferably a gas that easily condenses.
- a gas that easily condenses For example, water vapor, a gas having a boiling point of about 100 ⁇ 50 ° C. at 1 atm, alcohols such as methanol and ethanol, ketones such as acetone, and the like. From the viewpoint of safety and the like, water vapor is particularly desirable. This is because the recovered mixed gas of regeneration gas and carbon dioxide can be separated and recovered by cooling.
- Examples of the carbon dioxide capturing material 101 include high specific surface area materials including silica, alumina, titania, zirconia, ceria, zeolite, polymer material, activated carbon, MOF (Molecular Organic Framework), ZIF (Zeolytic Immediate Framework), and the like. Alternatively, a material containing an oxide or carbonate of alkali metal and alkaline earth metal may be used. Further, the shape of the carbon dioxide capturing material 101 may be such that the minimum unit of the constituent material is granular, a granular aggregate, or a composite thereof. Further, when the carbon dioxide capturing material 101 is formed as a member, it preferably has a shape having air permeability so as to reduce pressure loss.
- the carbon dioxide capturing material 101 may be formed as a porous body or a honeycomb. You may make it. Further, the carbon dioxide capturing material 101 may have a bulk shape, a plate shape, or the like. As the carbon dioxide capturing material 101, an oxide containing Ce (ceria enhanced by adding other elements) is particularly desirable.
- oxides containing Ce include oxides containing Al in addition to Ce.
- the element with the largest content is Ce
- the content of Al is preferably 0.01 mol% or more and 40 mol% or less.
- the content of Ce in the oxide containing Ce is desirably 40 mol% or more.
- the oxide containing Ce further contains 0.01 mol% or more of at least one element selected from the group consisting of Fe, Cu, V, and Mo.
- the oxide containing Ce preferably further contains 0.01 to 50 mol% of La, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu in total.
- FIG. 2 shows a schematic configuration of the test apparatus used in Comparative Example 1 and Examples 1 to 3 below.
- the test apparatus shown in the figure includes a reaction tube 110 provided with a heater 122, a steam generator 114, a bubbling pot 115 provided in a constant temperature bath 116, and a steam recovery water tank 118 provided in a cooling water tank 117. .
- the reaction tube 110 is filled with a carbon dioxide capturing material 111.
- the steam generator 114 and the bubbling pot 115 are connected to the reaction tube 110 via pipes 112 and 113, respectively.
- the amount of water vapor generated by the water vapor generator 114 can be collected and measured via the vapor amount measurement channel 123.
- the carbon dioxide concentration meter 119 and the flow meter 120 can measure the carbon dioxide concentration and the flow rate.
- Comparative Example 1 As Comparative Example 1, a test for regeneration by supplying saturated steam at 100 ° C. to a carbon dioxide trapping material that has reached a trapping equilibrium (adsorption equilibrium) at 50 ° C. and a partial pressure of carbon dioxide of 13 kPa will be described.
- HS high specific surface area ceria
- 16 cm 3 of carbon dioxide trapping material molded into a granular shape of 0.5 to 1.0 mm was prepared and filled in a reaction tube having a cross-sectional area of 0.9 cm 2 , and the following tests were performed.
- the carbon dioxide capturing material 111 is cleaned by flowing nitrogen at a flow rate of 400 cc / min and a heater temperature of 300 ° C. for 2 hours.
- the carbon dioxide containing gas added with water vapor is passed through the bubbling pot 115 in the thermostatic chamber 116 in which the carbon dioxide containing gas is set to 50 ° C. Then, it is made to flow through the reaction tube 110 and is brought into contact with the carbon dioxide capturing material 111.
- the temperature of the heater 122 is set to 50 ° C.
- the reaction tube outlet gas passes through a steam recovery water tank 118 cooled in a cooling water tank 117 set at 10 ° C., and after removing the steam, the carbon dioxide concentration meter 119 measures the carbon dioxide concentration.
- the piping valve 121 connected to the flow meter 120 is closed.
- the flow rate of the steam generated by the steam generator 114 is 898 cc / min as a result of measurement through the steam amount measurement channel 123, and 0.2 m / sec when converted into the linear velocity in the reaction tube 110. It was.
- the capturing step was terminated and the flow of the carbon dioxide-containing gas was stopped.
- the regeneration process started at the end of the capture process.
- the regeneration process includes a preheating process and a subsequent regeneration gas supply process.
- the heater 122 was heated to 200 ° C., the flow path to the carbon dioxide concentration meter 119 was closed, and the piping valve 121 connected to the flow meter 120 was opened instead.
- the carbon dioxide desorption amount when the heater 122 was heated to 200 ° C. was calculated from the integrated flow rate calculated using the flow meter 120.
- the amount of carbon dioxide desorbed in the preheating step was about 500 mmol / L.
- saturated steam (regeneration gas) at 100 ° C. and 0.1 MPa generated by the steam generator 114 is supplied to the reaction tube 110 via the pipe 113 (steam channel). did.
- the output of the heater 122 was kept at 200 ° C. to prevent water vapor from condensing.
- the flow rate integrated value was calculated from the flow meter 120, and the change with time in the accumulated desorption amount of carbon dioxide when water vapor was flowed was obtained.
- Example 1 the same capture process and desorption process test as in Comparative Example 1 were performed. However, since the output of the steam generator was changed, the flow rate of the generated steam was measured via the steam flow channel, and as a result, it was 2781 cc / min, which was 0.5 m / sec when converted to the linear velocity in the reaction tube. It was. The flow rate integrated value was determined from the flow rate measurement and recording means 120, and the change with time of the accumulated desorption amount of carbon dioxide when steam was circulated was obtained.
- Example 2 the same capture process and desorption process test as in Comparative Example 1 were performed. However, since the output of the steam generator was changed, the flow rate of the generated steam was measured via the steam flow channel, and as a result, it was 7021 cc / min, and 1.3 m / sec when converted to the linear velocity in the reaction tube. It was. The flow rate integrated value was determined from the flow rate measurement and recording means 120, and the change with time of the accumulated desorption amount of carbon dioxide when steam was circulated was obtained.
- Example 3 the same capture process and desorption process test as in Comparative Example 1 were performed. However, since the output of the steam generator was changed, the flow rate of the generated steam was measured through the steam flow channel, and as a result, it was 10691 cc / min, and 2.0 m / sec when converted to the linear velocity in the reaction tube. It was. The flow rate integrated value was determined from the flow rate measurement and recording means 120, and the change with time of the accumulated desorption amount of carbon dioxide when steam was circulated was obtained.
- FIG. 3 shows the integrated value of the CO 2 desorption amount when 0.5 minutes, 1 minute, 1.5 minutes, 2 minutes, and 2.5 minutes have elapsed.
- the horizontal axis shows the vapor linear velocity of Comparative Example 1 and Examples 1 to 3.
- FIG. 4 shows the time required from the start of the circulation of water vapor until the entire amount of CO 2 is desorbed.
- FIG. 3 shows that the desorption amount and desorption rate of CO 2 increase as the water vapor linear velocity increases.
- Example 1 As compared with Comparative Example 1, the time required until the entire amount of CO 2 is desorbed can be shortened to about 1/2 of about 6 minutes.
- Example 2 As compared with Comparative Example 1, the time required until the entire amount of CO 2 is desorbed can be shortened to about 1/4 of about 3 minutes.
- Example 3 As compared with Comparative Example 1, the time required until the entire amount of CO 2 is desorbed can be shortened to about 1/4 of about 3 minutes.
- 100 carbon dioxide absorption tower, 101: carbon dioxide capturing material, 102: carbon dioxide containing gas flow path, 103: carbon dioxide removal gas recovery flow path, 104: regeneration gas flow path, 105: mixed gas recovery flow path, 106 : Open / close valve, 107, 108: Heat medium flow path, 109: Regeneration gas flow rate adjusting unit, 110: Reaction tube, 111: Carbon dioxide trapping material, 112, 113: Piping, 114: Steam generator, 115: For bubbling Pot: 116: constant temperature bath, 117: cooling water bath, 118: steam recovery water bath, 119: carbon dioxide concentration meter, 120: flow meter, 121: valve, 122: heater, 123: steam amount measurement channel.
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Abstract
Description
(2)二酸化炭素捕捉材に捕捉した二酸化炭素を加熱によって脱離させた後、再生用ガスを流通させることで二酸化炭素吸収塔内の二酸化炭素を追い出して、再度捕捉工程で二酸化炭素捕捉材を使用可能にする二酸化炭素捕捉材の「再生工程」
(3)加熱された二酸化炭素捕捉材を、二酸化炭素含有ガスと同じかそれよりやや高い温度にまで冷却する「冷却工程」
また、少なくとも三基の二酸化炭素吸収塔100を設置し、三基の二酸化炭素吸収塔100にそれぞれ三つの工程を割り振ることで、二酸化炭素含有ガスから連続的に二酸化炭素を回収することが可能となる。
(式中の単位はmol%である。)
Ceを含む酸化物は、さらに、La、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb及びLuを合計で0.01~50mol%含むことが望ましい。
比較例1として、50℃、二酸化炭素分圧13kPaで捕捉平衡(吸着平衡)に達した二酸化炭素捕捉材に100℃の飽和水蒸気を供給することで、再生する試験について記載する。
Claims (14)
- 二酸化炭素捕捉材を収納した二酸化炭素吸収塔と、前記二酸化炭素捕捉材を加熱する加熱部と、前記二酸化炭素吸収塔に二酸化炭素含有ガスを導入するための流路と、前記二酸化炭素吸収塔に再生用ガスを導入するための流路と、前記二酸化炭素捕捉材から脱離したガスを含む混合ガスを回収するための流路とを備え、前記加熱部により前記二酸化炭素捕捉材の予熱を行い、その後、前記二酸化炭素吸収塔に前記再生用ガスを導入し、前記二酸化炭素捕捉材から二酸化炭素を回収することを特徴とする二酸化炭素回収装置。
- 前記再生用ガスの供給時間をあらかじめ設定しておくことを特徴とする請求項1記載の二酸化炭素回収装置。
- 前記混合ガスに含まれる二酸化炭素の濃度が所定値以下となった場合に前記再生用ガスの導入を停止することを特徴とする請求項1記載の二酸化炭素回収装置。
- 前記混合ガスに含まれる前記再生用ガスの濃度が所定値以上となった場合に前記再生用ガスの導入を停止することを特徴とする請求項1記載の二酸化炭素回収装置。
- 前記再生用ガスの前記二酸化炭素吸収塔内における線速度を0.5m/秒以上2.5m/秒以下とすることを特徴とする請求項1~4のいずれかに記載の二酸化炭素回収装置。
- 前記再生用ガスは、水蒸気であることを特徴とする請求項1~5のいずれかに記載の二酸化炭素回収装置。
- 前記二酸化炭素捕捉材は、Ceを含む酸化物であることを特徴とする請求項1~6のいずれかに記載の二酸化炭素回収装置。
- 二酸化炭素捕捉材を収納した二酸化炭素吸収塔と、前記二酸化炭素捕捉材を加熱する加熱部と、前記二酸化炭素吸収塔に二酸化炭素含有ガスを導入するための流路と、前記二酸化炭素吸収塔に再生用ガスを導入するための流路と、前記二酸化炭素捕捉材から脱離したガスを含む混合ガスを回収するための流路とを備えた二酸化炭素回収装置を用いた二酸化炭素回収方法であって、前記加熱部により前記二酸化炭素捕捉材の予熱を行う予熱工程と、その後、前記二酸化炭素吸収塔に前記再生用ガスを導入し前記二酸化炭素捕捉材から二酸化炭素を回収する再生用ガス供給工程と、を含むことを特徴とする二酸化炭素回収方法。
- 前記再生用ガスの供給時間をあらかじめ設定しておくことを特徴とする請求項8記載の二酸化炭素回収方法。
- 前記混合ガスに含まれる二酸化炭素の濃度が所定値以下となった場合に前記再生用ガスの導入を停止することを特徴とする請求項8記載の二酸化炭素回収方法。
- 前記混合ガスに含まれる前記再生用ガスの濃度が所定値以上となった場合に前記再生用ガスの導入を停止することを特徴とする請求項8記載の二酸化炭素回収方法。
- 前記再生用ガスの前記二酸化炭素吸収塔内における線速度を0.5m/秒以上2.5m/秒以下とすることを特徴とする請求項8~11のいずれかに記載の二酸化炭素回収方法。
- 前記再生用ガスは、水蒸気であることを特徴とする請求項8~12のいずれかに記載の二酸化炭素回収方法。
- 前記二酸化炭素捕捉材は、Ceを含む酸化物であることを特徴とする請求項8~13のいずれかに記載の二酸化炭素回収方法。
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CN201480046979.4A CN105473207B (zh) | 2014-02-10 | 2014-10-15 | 二氧化碳回收装置及二氧化碳回收方法 |
CA2922664A CA2922664C (en) | 2014-02-10 | 2014-10-15 | Carbon dioxide recovery apparatus, and carbon dioxide recovery method |
EP18166309.7A EP3403711A1 (en) | 2014-02-10 | 2014-10-15 | Carbon dioxide capturing material and carbon-dioxide recovery apparatus |
EP14881848.7A EP3106216A4 (en) | 2014-02-10 | 2014-10-15 | Carbon-dioxide recovery apparatus, and carbon-dioxide recovery method |
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JP2015150500A (ja) * | 2014-02-14 | 2015-08-24 | 日立化成株式会社 | 二酸化炭素捕捉材及びこれを用いた二酸化炭素回収装置 |
CN108472571A (zh) * | 2016-01-21 | 2018-08-31 | 日立化成株式会社 | 二氧化碳分离回收装置、使用其的燃烧系统和火力发电系统以及二氧化碳的分离回收方法 |
WO2017199917A1 (ja) * | 2016-05-16 | 2017-11-23 | 日立化成株式会社 | 吸着剤及びその製造方法、二酸化炭素の除去方法、二酸化炭素除去器、並びに、空調装置 |
JP6181835B1 (ja) * | 2016-10-11 | 2017-08-16 | 株式会社西部技研 | ガス回収濃縮装置 |
WO2019147806A1 (en) * | 2018-01-24 | 2019-08-01 | Sri International | Apparatuses and methods involving extraction of heavy rare gases |
JP7123748B2 (ja) * | 2018-10-30 | 2022-08-23 | 公益財団法人地球環境産業技術研究機構 | 二酸化炭素分離回収システム及び方法 |
GB201901445D0 (en) * | 2019-02-01 | 2019-03-27 | Provost Fellows Found Scholars And The Other Members Of Board Of The College Of The Holy And Undivid | Improvements relating to carbon dioxide capture |
KR102033745B1 (ko) * | 2019-06-28 | 2019-10-17 | 한국화학연구원 | 이산화탄소 포집장치 및 포집공정 |
JP7088144B2 (ja) * | 2019-08-23 | 2022-06-21 | トヨタ自動車株式会社 | Co2回収装置を搭載した車両の制御装置 |
CN110921667A (zh) * | 2019-12-27 | 2020-03-27 | 天津健威泽节能环保科技股份有限公司 | 一种水泥熟料生产线捕集纯化二氧化碳的系统及实现方法 |
CN113289452A (zh) * | 2021-06-28 | 2021-08-24 | 北京德润晨环保科技有限公司 | 一种烟道气二氧化碳回收工艺 |
CN114548481B (zh) * | 2021-12-26 | 2022-08-23 | 特斯联科技集团有限公司 | 基于强化学习的电力设备碳中和处理装置 |
JP2023108268A (ja) * | 2022-01-25 | 2023-08-04 | エア・ウォーター株式会社 | Co2回収方法およびco2回収装置 |
CN114307534A (zh) * | 2022-02-09 | 2022-04-12 | 西安热工研究院有限公司 | 一种空气直接捕集二氧化碳试验研究系统及方法 |
WO2023210797A1 (ja) * | 2022-04-28 | 2023-11-02 | 株式会社Atomis | ガスの回収装置及び回収方法 |
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EP3106216A1 (en) | 2016-12-21 |
US20160220943A1 (en) | 2016-08-04 |
JP2015150464A (ja) | 2015-08-24 |
JP6107695B2 (ja) | 2017-04-05 |
CA2922664A1 (en) | 2015-08-13 |
CA2922664C (en) | 2019-01-22 |
CN105473207B (zh) | 2017-09-22 |
EP3403711A1 (en) | 2018-11-21 |
CN105473207A (zh) | 2016-04-06 |
EP3106216A4 (en) | 2017-09-27 |
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