JP5328351B2 - 炭素膜 - Google Patents
炭素膜 Download PDFInfo
- Publication number
- JP5328351B2 JP5328351B2 JP2008524590A JP2008524590A JP5328351B2 JP 5328351 B2 JP5328351 B2 JP 5328351B2 JP 2008524590 A JP2008524590 A JP 2008524590A JP 2008524590 A JP2008524590 A JP 2008524590A JP 5328351 B2 JP5328351 B2 JP 5328351B2
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- carbon
- membrane
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- film
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 62
- 239000012528 membrane Substances 0.000 claims abstract description 59
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- 230000008569 process Effects 0.000 claims abstract description 23
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- 239000001913 cellulose Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 15
- 229920002488 Hemicellulose Polymers 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 30
- 238000003763 carbonization Methods 0.000 claims description 30
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 29
- 238000011069 regeneration method Methods 0.000 claims description 26
- 230000008929 regeneration Effects 0.000 claims description 25
- 239000010409 thin film Substances 0.000 claims description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 239000001569 carbon dioxide Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 3
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- 238000001035 drying Methods 0.000 abstract description 3
- 238000005266 casting Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 230000035699 permeability Effects 0.000 description 18
- 239000002243 precursor Substances 0.000 description 18
- 238000000926 separation method Methods 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
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- 239000003822 epoxy resin Substances 0.000 description 5
- 239000012510 hollow fiber Substances 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
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- 238000010586 diagram Methods 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- -1 transition metal salts Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910018194 SF 6 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
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- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
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- 125000000188 beta-D-glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
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- 238000002309 gasification Methods 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- TWNIBLMWSKIRAT-VFUOTHLCSA-N levoglucosan Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@H]2CO[C@@H]1O2 TWNIBLMWSKIRAT-VFUOTHLCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 229920006395 saturated elastomer Polymers 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01D53/22—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 by diffusion
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- C04B38/0032—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof obtained by a chemical conversion or reaction other than those relating to the setting or hardening of cement-like material or to the formation of a sol or a gel, e.g. by carbonising or pyrolysing preformed cellular materials based on polymers, organo-metallic or organo-silicon precursors one of the precursor materials being a monolithic element having approximately the same dimensions as the final article, e.g. a paper sheet which after carbonisation will react with silicon to form a porous silicon carbide porous body
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00793—Uses not provided for elsewhere in C04B2111/00 as filters or diaphragms
- C04B2111/00801—Membranes; Diaphragms
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- C—CHEMISTRY; METALLURGY
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
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- 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
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- 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
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Description
(1)酸を用いてセルロースとヘミセルロースの混合物を反応させ、
(2)上記混合物を型に入れて薄膜を形成し、
(3)上記薄膜を乾燥し、
(4)上記薄膜を炭化する。
パルプ(セルロースとヘミセルロースとの混合物)が、約1重量%の濃度のトリフルオロ酢酸(TFA)に溶解された。加水分解時間は、6日間、14日間または74日間であった。
実施例2:炭化
薄膜は、アルミナの作動管と薄膜の支持体としてステンレス鋼の格子を使用した管状炉(登録商標がCarboliteである、TZF12/100/900のもの)において、真空下で炭化された。その概略試験装置は図1に示されている。
実施例3:透過度試験
円形の炭素の薄膜は、特定の透過領域を残して、不透過のアルミニウムのテープを使用して覆われた。エポキシ樹脂が、アルミニウムのテープと炭素薄膜の境界面に付着された。フィルター紙で覆われた焼結済みの金属のディスクが試験セルにおける薄膜の支持体として使用された。30℃において、標準圧力上昇機器(登録商標がMKS Baratronの圧力変換器で、0から100mbarのレンジのもの)を用いて2バールの供給圧力(透過側に排気した)で、登録商標がLabViewの機器でデータを記録しながら、複数の単一ガスについて試験をした。その試験方法と機器は、K.C.O'Brien, W.J.Koros, T.A.BarbariおよびE.S.Sandersによる重合体薄膜を用いた多種ガス成分を測定するための新しい技術(J.Membrane Sci., 29(1986))の第229頁から238頁およびM.R.Colemanによるガス分離膜のためのフッ素含有ポリイミドの異性体(米国テキサス州オースチンのテキサス大学の博士論文, 1989)に記載されている。
実施例4:金属の添加物がない場合のパルプ由来の炭素の性能に及ぼす加水分解の効果
実施例5:
実施例1ないし3が、パルプ(セルロースとヘミセルロースの混合物)を出発材料として加水分解時間を変えることによって繰り返された。得られたヘミセルロース由来の重量損失が図3に示されている。
実施例6:透過度の結果
実施例5の膜を使用した数種類のガスに対する透過度試験の結果が、表2と図4においてCO2/CH4に対して示されている。
実施例7:再生
実施例1ないし3が、木材のパルプを出発材料として14日間のTFA処理をすることにより繰り返された。硝酸第二鉄が、TFA/パルプ溶液に各種の濃度で添加された。金属の含有量は、あるバッチに対しては1.8重量%であり、他のバッチに対しては4.4重量%であった。
実施例8:劣化と再生
4.4重量%の金属含有量の硝酸第二鉄に由来する炭素が、高い導電性のゆえに、劣化および再生試験のために選択された。表4は、電線につないだ炭素と電線につながなかった炭素についての重要な結果を示す。
2 エンドキャップ
3 管状炉
4 可撓性の管
5 ダイヤフラム弁
6 真空ポンプ
7 冷却トラップ
8 粒子フィルター
9 圧力伝達器
10 炭素膜
11 Oリング
12 アルミニウムテープ
13 エポキシ樹脂
14 接着剤
15 コアケーブル
16 環状ディスク
17 貫通孔
18 電力供給源
Claims (16)
- 以下の(1)ないし(4)の工程を有する炭素膜の製造方法。
(1)酸を用いてセルロースとヘミセルロースの混合物を反応させ、セルロースの連鎖を加水分解し、オリゴ糖または単糖類を形成し、
(2)上記混合物を型に入れて薄膜を形成し、
(3)上記薄膜を乾燥し、
(4)上記薄膜を炭化する。 - 上記酸がトリフルオロ酢酸(TFA)である請求項1に記載の方法。
- 金属塩が工程(1)の混合物に添加される請求項1または2に記載の方法。
- 金属塩は混合物の0.5ないし6重量%を占める請求項3に記載の方法。
- 金属塩は硝酸第二鉄である請求項3または4に記載の方法。
- セルロースとヘミセルロースの混合物は、木材のパルプを使って提供される請求項1ないし5のいずれか1項に記載の方法。
- 工程(1)ないし(3)は、7日間ないし100日間を要する請求項1ないし6のいずれか1項に記載の方法。
- 工程(1)ないし(3)は、21日間ないし35日間を要する請求項7に記載の方法。
- 最終炭化温度は500ないし600℃である請求項1ないし8のいずれか1項に記載の方法。
- 炭化工程(4)は少なくとも2回の休止を含む請求項1ないし9のいずれか1項に記載の方法。
- 工程(4)は触媒なしで実行される請求項1ないし10のいずれか1項に記載の方法。
- 電流が炭素膜に通される再生工程(5)をさらに含む請求項1ないし11のいずれか1項に記載の方法。
- 電流は1ないし60mAである請求項12に記載の方法。
- ガスを含有するガス混合物から当該ガスを分離するための方法であって、ガス混合物を請求項1に記載の炭素膜を通過させる工程を有している方法。
- 直流を膜に通すことによって、上記膜は定期的または連続的に再生される請求項14に記載の方法。
- 分離されるガスは二酸化炭素または水素である請求項14または15に記載の方法。
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GBGB0516154.2A GB0516154D0 (en) | 2005-08-05 | 2005-08-05 | Carbon membranes |
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PCT/GB2006/002926 WO2007017650A1 (en) | 2005-08-05 | 2006-08-04 | Carbon membranes |
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US6427944B1 (en) * | 2000-07-13 | 2002-08-06 | Bbnt Solutions Llc | Systems and methods for using airborne communication nodes |
TWI288025B (en) | 2000-09-14 | 2007-10-11 | Showa Denko Kk | Adsorbent for purifying perfluorocarbon, process for producing same, high purity octafluoropropane and octafluorocyclobutane, and use thereof |
JP2002355538A (ja) | 2001-05-30 | 2002-12-10 | Asahi Medical Co Ltd | 炭素繊維中空糸膜用セルロース中空糸膜およびその製造方法 |
US20040028901A1 (en) * | 2002-02-25 | 2004-02-12 | Rumpf Frederick H. | Compositions comprising continuous networks and monoliths |
JP4465433B2 (ja) * | 2002-10-02 | 2010-05-19 | 独立行政法人科学技術振興機構 | リグニン系マトリックスを有するガラス複合材料 |
US7267710B2 (en) * | 2003-03-28 | 2007-09-11 | Mitsubishi Heavy Industries, Ltd. | Method of and apparatus for regenerating adsorbent |
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JP7423171B2 (ja) | 2022-03-30 | 2024-01-29 | 本田技研工業株式会社 | トルクリミッタ |
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ATE505259T1 (de) | 2011-04-15 |
US7947114B2 (en) | 2011-05-24 |
JP2009502724A (ja) | 2009-01-29 |
CN101277754A (zh) | 2008-10-01 |
EP1909949A1 (en) | 2008-04-16 |
EP1909949B1 (en) | 2011-04-13 |
CN101277754B (zh) | 2012-06-06 |
WO2007017650A1 (en) | 2007-02-15 |
GB0516154D0 (en) | 2005-09-14 |
ES2364912T3 (es) | 2011-09-16 |
US20100162887A1 (en) | 2010-07-01 |
DK1909949T3 (da) | 2011-07-11 |
DE602006021313D1 (de) | 2011-05-26 |
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