WO2014125733A1 - 触媒コンバーター - Google Patents
触媒コンバーター Download PDFInfo
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- WO2014125733A1 WO2014125733A1 PCT/JP2013/084080 JP2013084080W WO2014125733A1 WO 2014125733 A1 WO2014125733 A1 WO 2014125733A1 JP 2013084080 W JP2013084080 W JP 2013084080W WO 2014125733 A1 WO2014125733 A1 WO 2014125733A1
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- catalytic converter
- catalyst layer
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 210000004027 cell Anatomy 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 210000002421 cell wall Anatomy 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 45
- 230000002093 peripheral effect Effects 0.000 claims description 22
- 238000000746 purification Methods 0.000 abstract description 11
- 239000007789 gas Substances 0.000 description 44
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052878 cordierite Inorganic materials 0.000 description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000005485 electric heating Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011206 ternary composite Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- -1 silicon carbide Chemical compound 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/464—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B01J35/19—
-
- B01J35/56—
-
- 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
- F01N3/24—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 constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/903—Multi-zoned catalysts
- B01D2255/9032—Two zones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- B01J35/40—
-
- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
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- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/30—Honeycomb supports characterised by their structural details
- F01N2330/48—Honeycomb supports characterised by their structural details characterised by the number of flow passages, e.g. cell density
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- 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
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/60—Discontinuous, uneven properties of filter material, e.g. different material thickness along the longitudinal direction; Higher filter capacity upstream than downstream in same housing
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
まず、本発明の触媒コンバーターが介在する排ガスの排気系統を概説する。本発明の触媒コンバーターが適用される排ガスの排気系統は、エンジン、触媒コンバーター、三元触媒コンバーター、サブマフラーおよびメインマフラーが配されて相互に系統管で繋がれ、エンジンで生成された排ガスが系統管を介して各部を流通し、排気されるようになっている。次に、以下、触媒コンバーターの実施の形態を説明する。
図1は本発明の触媒コンバーターの実施の形態を説明した模式図であり、図2aは基材の第1の領域(中央領域)のセル壁面を拡大した図であり、図2bは基材の第2の領域(周辺領域)のセル壁面を拡大した図である。また、図3はセル密度一様の基材と中央領域と周辺領域でセル密度が異なる基材の排ガスの流速分布を説明した図である。
本発明者等は、以下で示す実施例1、2と比較例1~6の各触媒コンバーターを試作し、それぞれの触媒コンバーターの排ガスエミッション量と圧損量を測定し、エミッションに関しては比較例1の値に対する他の触媒コンバーターの値の比を求め、圧損に関しては比較例2の値に対する他の触媒コンバーターの値の比を求めてグラフ化した。以下、各触媒コンバーターの基材の仕様や触媒層の仕様と耐久評価試験方法の概要を説明する。
<ハニカム構造体1>
押出成形によってコージェライト製のハニカム構造基材を作製し、中央領域と周辺領域でセル密度を相違させた。ハニカム構造体のサイズは排ガスの流れ方向に直交する円形断面の直径がφ103mmで長手方向の長さLが105mmであり、セル密度が相対的に低い周辺領域のセル密度が400cpsi(62個/cm2)であり、セル密度が相対的に高い中央領域のセル密度が600cpsi(93個/cm2)であり、中央領域と周辺領域の切替ラインがφ70mmの位置であり、セルの格子形状は2つの領域ともに四角形状である。
押出成形によってコージェライト製のハニカム構造基材を作製し、セル密度が均一である。ハニカム構造体のサイズは排ガスの流れ方向に直交する円形断面の直径がφ103mmで長手方向の長さLが105mmであり、セル密度が600cpsi(93個/cm2)であり、セルの格子形状は四角形である。
ハニカム構造体2およびハニカム構造体1の中央領域は250g/Lであり、ハニカム構造体1の周辺領域は実施例や比較例によって相違する。
Ptが1.0g/L、Rhが0.3g/Lである。
各触媒コンバーターをV型8気筒4.3リットルカ゛ソリンエンシ゛ンの排気系にそれぞれ装着し、触媒床温を1000℃で1分間にフィードバック、フューエルカット、リッチ、リーンを含む条件で50時間の耐久試験を施した。
各触媒コンバーターに6m3/分の空気を流した際の圧力損失(25℃換算)を測定し、比較例2の値に対する比率で評価した。
実機エンジンに各触媒コンバーターをセットし、A/Fをリッチ(14.1)、リーン(15.1)を1秒で切り替えた際のNOx排出量をそれぞれ測定し、比較例1の値に対する比率で評価した。以下、表1と図4に各触媒コンバーターの水準と圧損比、エミッション比に関する実験結果を示す。
Claims (2)
- セル構造の基材のセル壁面においてガスが流通する基材の長手方向に貴金属触媒が担体に担持されてなる触媒層が形成されている触媒コンバーターであって、
基材は、セル密度が相対的に高い第1の領域と、セル密度が相対的に低い第2の領域とから構成され、
第1の領域における触媒層の厚みに対する第2の領域における触媒層の厚みの比率が0.95倍より大きく1.2倍以下の範囲である触媒コンバーター。 - 基材における、ガスが流通する方向に直交する断面において、中央領域とその周辺領域の2つの領域にセル密度の異なる領域が形成されており、
前記第1の領域が前記中央領域であり、前記第2の領域が前記周辺領域である請求項1に記載の触媒コンバーター。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112015019300-5A BR112015019300B1 (pt) | 2013-02-13 | 2013-12-19 | Conversor catalítico |
CN201380072823.9A CN104994951A (zh) | 2013-02-13 | 2013-12-19 | 催化转换器 |
DE112013006663.7T DE112013006663B4 (de) | 2013-02-13 | 2013-12-19 | Katalytischer Wandler |
US14/767,123 US9782753B2 (en) | 2013-02-13 | 2013-12-19 | Catalytic converter |
ZA2015/06225A ZA201506225B (en) | 2013-02-13 | 2015-08-26 | Catalytic converter |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013025580A JP5888259B2 (ja) | 2013-02-13 | 2013-02-13 | 触媒コンバーター |
JP2013-025580 | 2013-02-13 |
Publications (1)
Publication Number | Publication Date |
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WO2014125733A1 true WO2014125733A1 (ja) | 2014-08-21 |
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PCT/JP2013/084080 WO2014125733A1 (ja) | 2013-02-13 | 2013-12-19 | 触媒コンバーター |
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US (1) | US9782753B2 (ja) |
JP (1) | JP5888259B2 (ja) |
CN (1) | CN104994951A (ja) |
BR (1) | BR112015019300B1 (ja) |
DE (1) | DE112013006663B4 (ja) |
WO (1) | WO2014125733A1 (ja) |
ZA (1) | ZA201506225B (ja) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10598068B2 (en) | 2015-12-21 | 2020-03-24 | Emissol, Llc | Catalytic converters having non-linear flow channels |
JP6587565B2 (ja) * | 2016-03-17 | 2019-10-09 | 日本碍子株式会社 | ハニカム構造体 |
JP6625920B2 (ja) * | 2016-03-25 | 2019-12-25 | トヨタ自動車株式会社 | 触媒コンバーター |
JP6620049B2 (ja) * | 2016-03-25 | 2019-12-11 | 日本碍子株式会社 | ハニカム構造体 |
US11141713B2 (en) * | 2017-04-28 | 2021-10-12 | Umicore Shokubai Japan Co., Ltd. | Exhaust gas purification catalyst and exhaust gas purification method using the same |
JP2020040004A (ja) * | 2018-09-07 | 2020-03-19 | いすゞ自動車株式会社 | パティキュレートフィルタ及びその製造方法 |
JP2020044461A (ja) * | 2018-09-14 | 2020-03-26 | 三菱日立パワーシステムズ株式会社 | 脱硝装置 |
GB2581776B (en) * | 2019-02-19 | 2022-08-17 | Jaguar Land Rover Ltd | Catalytic converter core having first and second regions with different thermal inertia |
WO2020183496A1 (en) * | 2019-03-11 | 2020-09-17 | Hero MotoCorp Limited | Catalyst system for treatment of exhaust gas of automobile and process for making the same |
KR102211944B1 (ko) * | 2019-04-04 | 2021-02-03 | 희성촉매 주식회사 | 귀금속 박층을 최상층으로 포함하는 다층구조의 배기가스 정화용 촉매 및 이의 제조방법 |
CN113828360B (zh) * | 2021-10-12 | 2024-04-26 | 浙江三元龙兴科技股份有限公司 | 车用蜂窝陶瓷载体 |
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WO2010113585A1 (ja) * | 2009-03-31 | 2010-10-07 | 日本碍子株式会社 | ハニカムフィルタ及びその製造方法 |
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WO2010113585A1 (ja) * | 2009-03-31 | 2010-10-07 | 日本碍子株式会社 | ハニカムフィルタ及びその製造方法 |
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BR112015019300B1 (pt) | 2021-04-27 |
JP2014151305A (ja) | 2014-08-25 |
DE112013006663T5 (de) | 2015-11-26 |
BR112015019300A2 (pt) | 2017-07-18 |
JP5888259B2 (ja) | 2016-03-16 |
DE112013006663B4 (de) | 2021-11-25 |
US9782753B2 (en) | 2017-10-10 |
ZA201506225B (en) | 2016-12-21 |
CN104994951A (zh) | 2015-10-21 |
US20150375204A1 (en) | 2015-12-31 |
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