JP2015061820A - 水素貯蔵のためのイオン性液体を使用する方法 - Google Patents
水素貯蔵のためのイオン性液体を使用する方法 Download PDFInfo
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- JP2015061820A JP2015061820A JP2014228521A JP2014228521A JP2015061820A JP 2015061820 A JP2015061820 A JP 2015061820A JP 2014228521 A JP2014228521 A JP 2014228521A JP 2014228521 A JP2014228521 A JP 2014228521A JP 2015061820 A JP2015061820 A JP 2015061820A
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- ionic liquid
- cation
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 92
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 62
- 150000001768 cations Chemical class 0.000 claims abstract description 39
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- -1 thiazolium Chemical compound 0.000 claims description 8
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- 229910000510 noble metal Inorganic materials 0.000 claims description 7
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- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
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- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
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- KCUGPPHNMASOTE-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium Chemical compound CC=1N(C)C=C[N+]=1C KCUGPPHNMASOTE-UHFFFAOYSA-N 0.000 claims description 2
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 2
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- IRGDPGYNHSIIJJ-UHFFFAOYSA-N 1-ethyl-2,3-dimethylimidazol-3-ium Chemical compound CCN1C=C[N+](C)=C1C IRGDPGYNHSIIJJ-UHFFFAOYSA-N 0.000 claims 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims 1
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Images
Classifications
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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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/09—Organic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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Abstract
【解決手段】水素貯蔵の方法であり、前記方法は:カチオンとボレート、特にメタボレートを含むアニオンを含む第二のイオン性液体にボロヒドリドを導入して第一のイオン性液体を形成し;及び前記第二のイオン性液体を前記第一のイオン性液体から水及び/又は触媒を用いて水素を放出させる、ことを含む。
【選択図】図1
Description
本発明の例示的実施態様によれば、前記カチオンは、ピペラジニウム、ピロリジニウム及びモルホリニウムを含む群からのひとつであり、前記1から4の基の1又は2つの基が前記窒素原子に結合し及び/又は前記1から4の基の1から3の基が前記炭素環の炭素原子に結合する。
このイオン性液体は水素の十分高い貯蔵密度を提供することができ、この水素は触媒を用いて制御して放出されることができる。一般的に、例えば自動車のために十分な範囲を保証する貯蔵媒体を提供することができる。貯蔵媒体としてイオン性液体を用いることで、質量当たりの高い貯蔵容量及び/又は容積当たりの高い貯蔵容量を保証することができる。さらに、高い貯蔵安全性を導く低い漏れも達成可能である。さらに、記載されたイオン性液体は、化学的及び/又は熱影響及び/又は防火性について長時間にわたり高い安定性を有することができる。
ここで、トリオクチルメチルアンモニウムはカチオンを形成し、ボロヒドリドはアニオンを形成し、またその後放出される水素を含む。TOMA−BH4は水に可溶ではないが、水及び触媒と接触して水素を放出することができる(図1では102で示される)。
すなわち、トリオクチルメチルアンモニウム−メタボレート(TOMA−BO2)が形成され、これも水に対する混和性はない。メタボレートアニオンは特に、高温度で部分的に又は完全に反応してボレート又はポリボレートアニオンとなるが、どちらにしても、このボレート又はポリボレートアニオンは該プロセスに干渉せず、メタボレートとほとんど同じ性質を示す。
ここで「メタボレート」とは、より一般的な意味であり、メタボレート及び/又はボレート及び/又はポリボレートの混合物を意味する。前記サイクルステップの次のステップでは、TOMA−BO2をナトリウムボロヒドリド(NaBH4)の水溶液と接触させ(図1での矢印103で示される)、TOMA−BH4及びナトリウムメタボレート(NaBO2)の水溶液とする。ここでTOMA−BH4及びNaBO2は得られる液体で2相を形成する。これらの2相は分離されてさらにリサイクルTOMA−BH4とする。留意すべきは、TOMA−BH4中の少量の水は悪い影響は与えないということである。なぜならTOMA−BH4は触媒の存在なしでは水とは反応しないからである。
これらの球体は、六方体、立方体又は面中心立方体配列を持つ構造に形成される。特に、該配置は可能な限り密にして触媒とイオン性液体が接触する表面積を増加させるべきである。単一の球体201は金属粉末を焼結して形成し得る。ここで粉末粒子はマイクロメータ又はナノメータ範囲(例えば1nm及び50ミクロンメータ、より具体的には10nmから5ミクロンメータ)のサイズを持つ。触媒コンバータは複数のボール又は球体を持つという事実から、触媒コンバータはほとんどすべての望ましい形状に適合させることができる(例えば望ましい形状に切断され得る)。
さらに、容器300はチャンバ304に設けられる出口結合306を含んでいてよい。これは外部ハウジング307と結合されここには触媒コンバータが配置される。ハウジング内で、水素が水素リッチイオン性液体から放出され、水素を放出したイオン性液体が再生される。さらに、ハウジングは容器300とインプット結合308で結合され、インプット結合はチャンバ305に配置される。
Claims (18)
- 水素貯蔵の方法であり、前記方法は:
カチオンとボレート、特にメタボレートを含むアニオンを含む第二のイオン性液体にボロヒドリドを導入して第一のイオン性液体を形成し;及び
前記第二のイオン性液体を前記第一のイオン性液体から水及び/又は触媒を用いて水素を放出させる、ことを含む。 - 請求項1に記載の方法であり、前記カチオンが第4級カチオン又はプロトン化カチオンである、方法。
- 請求項2に記載の方法であり、前記カチオンが、水素、Cl−C20−アルキル、Cl−C20−アルケニル、Cl−C20−アルキニル、Cl−C20−シクロアルキル、Cl−C20−シクロアルケニル、Cl−C20−アリル及びCl−C20−ヘテロアリルを含む群からの基を1から4個含む、方法。
- 請求項3に記載の方法であり、前記カチオンが、ピリジニウム、ピロリニウム、チアゾリウム、オキサゾリウム及びキノリニウムを含む群のひとつであり、前記1から4の基が、前記窒素原子に結合し及び/又は前記1から4の基の1から3の基が前記炭素環の炭素に結合する、方法。
- 請求項3に記載の方法であり、前記カチオンが、アンモニウム、ホスホニウム及びスルホニウムを含む群のひとつである、方法。
- 請求項3に記載の方法であり、前記カチオンが、ピペラジニウム、ピロリジニウム及びモルホリニウムを含む群からのひとつであり、前記1から4の基の1又は2つの基が前記窒素原子に結合し及び/又は前記1から4の基の1から3の基が前記炭素環の炭素原子に結合する、方法。
- 請求項3に記載の方法であり、前記カチオンが、イミダゾリウム、ベンズイミダゾリウム、ピラゾリウム及びベンゾトリアゾリウムを含む群からのひとつであり、前記4つの基のそれぞれのひとつがそれぞれの窒素に結合し及び/又は前記1から4の基の1から3の基が前記炭素環の炭素原子に結合する、方法。
- 請求項2に記載の方法であり、前記カチオンが、トリオクチルメチルアンモニウム、テトラヘキシルアンモニウム、テトラオクチルアンモニウム及び1−オクチル−3−メチルイミダゾリウム、トリヘキシルメチルアンモニウム、トリエチルメチルアンモニウム、トリブチルメチルアンモニウム、1−エチル−3−メチルイミダゾリウム、1、3−ジメチルイミダゾリウム、1−ブチル−3−メチルイミダゾリウム、1、2、3−トリメチルイミダゾリウム、l−エチル−3−メチルイミダゾリウム、l−エチル−2、3−ジメチルイミダゾリウム及びl−ブチル−2、3−ジメチルイミダゾリウムを含む群のひとつである、方法。
- 請求項1乃至8のいずれか一項に記載の方法であり、前記触媒が、遷移金属及び/又は貴金属である、方法。
- 請求項1乃至9のいずれか一項に記載の方法であり、前記触媒が、ミクロ結晶又はナノ結晶構造である、方法。
- 請求項1乃至10のいずれか一項に記載の方法であり、前記水素を放出してボレートを形成する、方法。
- 請求項1乃至11のいずれか一項に記載の方法であり、前記第一のイオン性液体及び/又は前記第二のイオン性液体が、既定の粘度を持つ、方法。
- 請求項12に記載の方法であり、前記粘度レベルが添加剤を添加することで既定の粘度に設定される、方法。
- 請求項13に記載の方法であり、前記添加剤が、アミド、サイクリック又はポリエーテルを含むエーテル、アセタール、ケタール、ポリアルコールを含むアルコール、芳香族炭化水素、脂肪族炭化水素、ジブチルエーテル、ジエチルエーテル、メチルtert−ブチルエーテル、1、2−ジエトキシエタン、ホルムアルデヒドジメチルアセタール、ポリエチレングリコールジメチルエーテル及びポリビニルアルコールを含む群からのひとつである、方法。
- 請求項1乃至14のいずれか一項に記載の方法であり、さらに、前記第一のイオン性液体及び/又は前記第二のイオン性液体へ塩基性添加剤を添加することを含む、方法。
- 請求項15に記載の方法であり、前記塩基性添加剤が、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属カーボネート、アルカリ土類金属カーボネート、第4級テトラアルキルアンモニウム水酸化物、第4級テトラアルキルアンモニウムカーボネート、第4級テトラアルキルホスホニウム水酸化物、第4級テトラアルキルホスホニウムカーボネート及び第4級テトラアルキルホスホニウムアルキルカーボネートを含む群からの少なくともひとつである、方法。
- 水素貯蔵のためのイオン性液体であり、カチオン及びボロヒドリドを含む、イオン性液体。
- 水素貯蔵のためのイオン性液体であり、カチオン及びボレート、特にメタボレートを含む、イオン性液体。
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JP2001516871A (ja) * | 1997-09-16 | 2001-10-02 | ブリティッシュ・ニュークリア・フューエルズ・パブリック・リミテッド・カンパニー | 溶融塩再加工廃棄物の処理 |
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US20120027669A1 (en) | 2012-02-02 |
JP6012691B2 (ja) | 2016-10-25 |
KR101685589B1 (ko) | 2016-12-12 |
JP5649586B2 (ja) | 2015-01-07 |
AU2010205941B2 (en) | 2015-08-06 |
EA201101062A1 (ru) | 2012-02-28 |
EP2376371A1 (en) | 2011-10-19 |
CN102307805B (zh) | 2015-08-05 |
US20150259200A1 (en) | 2015-09-17 |
US9051182B2 (en) | 2015-06-09 |
WO2010081657A1 (en) | 2010-07-22 |
AU2010205941A1 (en) | 2011-07-14 |
CN105037174B (zh) | 2018-11-02 |
EP2376371B1 (en) | 2018-02-21 |
NO2376371T3 (ja) | 2018-07-21 |
CN105037174A (zh) | 2015-11-11 |
JP2012515134A (ja) | 2012-07-05 |
US9580311B2 (en) | 2017-02-28 |
CA2748923A1 (en) | 2010-07-22 |
AU2015230792A1 (en) | 2015-10-15 |
CN102307805A (zh) | 2012-01-04 |
BRPI1007291A2 (pt) | 2017-01-17 |
KR20110120869A (ko) | 2011-11-04 |
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