JP7069055B2 - ガスの貯蔵および放出システムにおいて体積分析容量を高めるための方法 - Google Patents
ガスの貯蔵および放出システムにおいて体積分析容量を高めるための方法 Download PDFInfo
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Description
本出願は、2016年7月1日に出願された米国特許仮出願第62/357,613号および2017年2月28日に出願された米国仮特許出願第62/464,955号の優先権を主張する。これらの仮出願の両方とも、その全体が参照により本明細書に組み込まれる。
1.技術分野
本開示は、ガス貯蔵システムに関し、特に、改善された貯蔵容量および供給容量を備える吸着性ガス用の多孔質ガス吸着性モノリスおよび貯蔵システムに関する。さらに、本明細書は、吸着剤密度と重量分析作業容量の少なくとも一方を改善することによって、吸着ガス貯蔵システムの作業容量または可逆的な貯蔵(例えば、活性炭含有貯蔵システムや吸着モノリス含有貯蔵システムを含む吸着天然ガス貯蔵システムからの天然ガスの貯蔵および供給)を改善する方法を提供する。
吸着天然ガス(ANG)貯蔵システムは、相対的に低い作動圧力に起因して、現在使用されている圧縮天然ガス(CNG)シリンダに代わるものである。作動圧力の低下は、家庭用燃料補給ユニットの使用を可能にし、圧縮のコストを削減し、本質的に比較的安全である。通常、ANG貯蔵システムは、3,000~3,600psigの範囲の作動圧力を有するCNGシリンダと比較して、1,000psig未満の作動圧力を有する。
本明細書は、多孔質ガス吸蔵モノリス(例えば、活性炭モノリス)、多孔質ガス吸蔵モノリスの製造方法、ならびにそれを使用するための方法およびシステムに関する。特に、約9~27Åの顕著な細孔体積を特徴とするガス収着剤材料と本明細書に記載の非水性結合剤との特定の組み合わせが、より優れていて良好な予測可能な寸法、体積分析容量および/または重量分析容量を備える多孔質ガス吸蔵モノリスを提供することが、意外にも、また予想外に発見された。
いくつかの実施形態では、モノリスは以下の、本開示の非水性結合剤がフルオロポリマー、ポリアミド、ポリイミド、フィブリル化セルロース、高性能プラスチック(例えばポリフェニレンスルフィド)、フルオロポリマーとのコポリマー、ポリアミドとのコポリマー、ポリイミドとのコポリマー、またはそれらの組合せからなる群から選択される少なくとも1つの結合剤であること、あるいは、ガス吸着材料が、活性炭、ゼオライト、シリカ、共有結合有機骨格、または有機金属骨格からなる群から選択されることの少なくとも1つを有する。
本明細書に組み込まれてその一部を形成する添付の図面は、本開示のいくつかの実施形態を例示し、その説明と共に、本開示の原理を説明するのに役立つ。図面は、本開示の実施形態を例示する目的のためだけのものであり、本発明を限定するものとして解釈するべきではない。本発明のさらなる目的、特徴および利点は、本開示の例示的な実施形態を示す添付の図面と併せて解釈される以下の詳細な説明から明らかになる。
以下は、本開示を実施する際に当業者を補助するために提供される詳細な説明である。当業者は、本開示の精神または範囲から逸脱することなく、本明細書に記載の実施形態に修正および変形を加えることができる。本明細書で言及されたすべての刊行物、特許出願、特許、図面、および他の参考文献は、その全体が参照により明示的に組み込まれる。
非水性結合剤のモノリスと水性結合剤のモノリスとの比較3種類のモノリスについて、天然ガスの可逆的な体積分析容量と重量分析容量を調べた。データを表1および2に示す。水性結合剤のモノリスは、約34~約48lb/GGEの範囲の重量分析容量および約25~約31L/GGEの範囲の体積分析容量を有していた。本明細書中に記載されるような非水性結合剤のモノリスは、約24~約30lb/GGEの範囲の改善された作業重量分析容量および約23~約27L/GGEの範囲の体積分析容量を有した。
表3、図7、および図8では、代替結合剤配合物を用いて調製した円筒状モノリスの寸法および体積の一貫性を比較している。以下に説明するように、天然ガス貯蔵モノリスを製造するステップを経ても、寸法の変化または体積の変化がほとんどないこと、およびそれらの変化の変動がほとんどないことは、燃料タンクの貯蔵能力を最大にするために、高く評価される。
比較的狭い表面積(例えば、N2のBET表面積で測定して<1400m2/g)を有する「硬質」の炭素は、結合したモノリスブロックの製造に使用されてきた。これらの炭素が、製造業の知られている最新技術を容易に受け入れ(例えば、国際公開第2017/031260号)、これらのブロックが典型的に使用される濾過の用途に、満足のいくものであるためである。これとは対照的に、1400+m2/gの面積を有する軟質の炭素はモノリスの安価な製造をもたらさないが、それでもこれらの材料は天然ガスの貯蔵に優れていることが発見された。
一態様によれば、本開示はガスを貯蔵する方法を提供する。方法は、ガスを、≦40lb/GGEの作業重量分析容量および/または≦35L/GGEの体積分析容量を有する少なくとも1つの多孔質ガス吸蔵モノリスを含むガス貯蔵システムと接触させることを含む。
≦35L/GGEの体積分析容量、約9~27Å、すなわち>0.5cc/gの範囲の大きさの細孔に対する細孔体積、ガス吸着材料が少なくとも90wt%の量で存在すること、非水性結合剤が10wt%以下の量で存在すること、またはそれらの組み合わせの少なくとも1つを有する。
<35L/GGEの体積分析容量、約9~27Å、すなわち≧0.5cc/gの範囲の大きさの細孔に対する細孔体積、ガス吸着材料が少なくとも93wt%の量で存在すること、非水性結合剤が7wt%以下の量で存在すること、非水性結合剤が結合剤の約55wt%~約65wt%の分散液であること、またはそれらの組み合わせの少なくとも1つを有する。
Claims (13)
- 9Åの大きさより小さい細孔における44.2~129.4cc/L-Mの体積、9~27Åの大きさの細孔における200.3~277.7cc/L-Mの体積、27~490Åの大きさの細孔における27.9~226.1cc/L-Mの体積、および0.396~0.718g/ccの部分密度を含むガス吸蔵材料を含む多孔質ガス吸蔵モノリスであって、
22.4~51.5lb/GGEの作業重量分析容量および/または20.6~32.5L/GGEの体積分析容量を有する多孔質ガス吸蔵モノリス。 - 非水性結合剤をさらに含む、請求項1に記載のモノリス。
- 前記非水性結合剤が60wt%または60.75wt%の量で存在する、請求項1または2に記載のモノリス。
- 前記非水性結合剤が、フルオロポリマー、ポリアミド、ポリイミド、フィブリル化セルロース、高性能プラスチック、フルオロポリマーとのコポリマー、ポリアミドとのコポリマー、ポリイミドとのコポリマー、高性能プラスチックとのコポリマー、またはそれらの組み合わせの少なくとも1つである、および/または
前記ガス吸着材料が、活性炭、ゼオライト、シリカ、有機金属骨格、共有結合有機骨格、またはそれらの組み合わせの少なくとも1つである、請求項2または3に記載のモノリス。 - 前記フルオロポリマーが、ポリ(ビニリデンジフルオリド)、フッ素化エチレンプロピレン、ペルフルオロアルコキシアルカン、およびポリテトラフルオロエチレンからなる群から選択される少なくとも1つのフルオロポリマーであり、
前記ポリアミドが、ナイロン-6,6’、ナイロン-6、およびナイロン6,12からなる群から選択される少なくとも1つのポリアミドであり、前記活性炭が、木材、ピートモス、ココナッツの殻、石炭、クルミの殻、合成ポリマーおよび/または天然ポリマーに由来し、および/または
前記活性炭が、熱的に活性化されている、化学的に活性化されている、またはそれらの組み合わせである、請求項4に記載のモノリス。 - 多孔質ガス吸蔵モノリスの製造方法であって、
ガス吸着材料と非水性結合剤とを混合すること、および
前記混合物を成形構造物に圧縮するか、前記混合物をある形状に押し出すこと
を含み、
前記モノリスは、以下の
9Åの大きさより小さい細孔における44.2~129.4cc/L-Mの体積、
9~27Åの大きさの細孔における200.3~277.7cc/L-Mの体積、
27~490Åの大きさの細孔における27.9~226.1cc/L-Mの体積、
0.396~0.718g/ccの部分密度、
22.4~51.5lb/GGEの作業重量分析容量、
20.6~32.5L/GGEの体積分析容量、
前記ガス吸着材料が少なくとも90wt%の量で存在し、
前記非水性結合剤が60wt%または60.75wt%の量で存在する、方法。 - 前記圧縮した混合物に熱を加えることをさらに含む、請求項6に記載の方法。
- 前記モノリスが、以下の
前記非水性結合剤が、フルオロポリマー、ポリアミド、ポリイミド、フィブリル化セルロース、高性能プラスチック、フルオロポリマーとのコポリマー、ポリアミドとのコポリマー、ポリイミドとのコポリマー、高性能プラスチックとのコポリマーもしくはそれらの組み合わせの少なくとも1つである、または
前記ガス吸着材料が、活性炭、ゼオライト、シリカ、有機金属骨格、共有結合有機骨格、もしくはそれらの組み合わせの少なくとも1つである、または
それらの組み合わせ
の少なくとも1つを有する、請求項6に記載の方法。 - 前記フルオロポリマーが、ポリ(ビニリデンジフルオリド)、フッ素化エチレンプロピレン、ペルフルオロアルコキシアルカン、およびポリテトラフルオロエチレンからなる群から選択される少なくとも1つのフルオロポリマーであり、
前記ポリアミドが、ナイロン-6,6’、ナイロン-6、およびナイロン6,12からなる群から選択される少なくとも1つのポリアミドであり、前記活性炭が、木材、ピートモス、ココナッツの殻、石炭、クルミの殻、合成ポリマーおよび/または天然ポリマーに由来し、および/または
前記活性炭が、熱的に活性化されている、化学的に活性化されている、またはそれらの組み合わせである、請求項6~8のいずれかに記載の方法。 - 前記混合物を圧縮することが、少なくとも1,250psiの圧力を加えることを含み、および/または
前記成形構造物または前記押出し形状が、円柱、長円形の柱体、立方体、楕円形の柱体、または直方体である、請求項6~9のいずれかに記載の方法。 - 容器と、
その中に配置された請求項1~5のいずれかに記載の多孔質ガス吸蔵モノリスを含むガス貯蔵システム。 - 前記容器が少なくとも1,000psiに耐えるように構成されている、請求項11に記載のガス貯蔵システム。
- ガスを貯蔵する方法であって、
前記方法は、前記ガスを請求項11または12のガス貯蔵システムと接触させることを含む、方法。
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