JP5066492B2 - セルロース繊維を用いた触媒支持体、その製造方法、触媒支持体の表面に直接成長した炭素ナノチューブ及び炭素ナノチューブの表面にナノ金属触媒が担持された担持触媒及びその製造方法 - Google Patents
セルロース繊維を用いた触媒支持体、その製造方法、触媒支持体の表面に直接成長した炭素ナノチューブ及び炭素ナノチューブの表面にナノ金属触媒が担持された担持触媒及びその製造方法 Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/001—Modification of pulp properties
- D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
- D21C9/004—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives inorganic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
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- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Textile Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Carbon And Carbon Compounds (AREA)
Description
第1段階:セルロース触媒支持体を製造する段階
第2段階:炭素ナノチューブを成長させる段階
第3段階:炭素ナノチューブにナノ金属触媒を担持する段階
<実施形態>
実施例1
比較例1
比較例2
試験例1.BET表面積、細孔体積及び細孔面積の測定
試験例2.担持触媒のCO化学吸着の分析
試験例3.メタンの二酸化炭素改質反応試験
Claims (12)
- セルロース繊維を炭化して触媒支持体を製造する第1段階と、
製造された触媒支持体の表面に炭素ナノチューブを成長させる第2段階と、
炭素ナノチューブが成長した触媒支持体の炭素ナノチューブの表面にナノサイズの金属触媒粒子であるナノ金属触媒を担持する第3段階と
を含んでなるナノ金属担持触媒の製造方法。 - セルロース繊維を炭化して触媒支持体を製造する第1段階は、
(A)セルロース繊維を数マイクロメータの厚さの繊維に分離し、分離された繊維を所定の長さに切断する段階と、
(B)切断されたセルロース繊維を炭化させる段階と
を含んでなることを特徴とする請求項1に記載のナノ金属担持触媒の製造方法。 - 前記セルロース繊維は、へネケ麻、ケナフ、アバカ、竹、大麻、亜麻、苧麻、パイナップル、カラムシ及びサイザル麻からなるグループより選択されることを特徴とする請求項1に記載のナノ金属担持触媒の製造方法。
- 製造された触媒支持体の表面に炭素ナノチューブを成長させる第2段階は、
(C)炭化したセルロース触媒支持体の表面に炭素ナノチューブ成長用触媒金属を担持する段階と、
(D)炭素ナノチューブ成長用触媒金属が担持されたセルロース触媒支持体の表面に炭素源を供給して炭素ナノチューブを成長させる段階と
を含んでなることを特徴とする請求項1から3のいずれか一に記載のナノ金属担持触媒の製造方法。 - 前記(C)段階は、炭素ナノチューブ成長用触媒金属としてニッケル、コバルト及び鉄からなるグループより選択されるいずれか1つ又は2つ以上の混合金属を前駆体として用いた水溶液を用いて行われることを特徴とする請求項4に記載のナノ金属担持触媒の製造方法。
- 炭素ナノチューブが成長した触媒支持体の炭素ナノチューブの表面にナノサイズの金属触媒粒子であるナノ金属触媒を担持する第3段階は、
(E)セルロース触媒支持体の表面に成長した炭素ナノチューブから炭素ナノチューブ成長用触媒金属成分を除去し、ナノ金属触媒の担持のための前処理を施す段階と、
(F)前処理されたセルロース触媒支持体の表面に成長した炭素ナノチューブの表面に化学気相蒸着法を用いてナノ金属触媒を担持する段階と
を含んでなることを特徴とする請求項1から5のいずれか一に記載のナノ金属担持触媒の製造方法。 - 前記(E)前処理を施す段階は、塩酸溶液で処理した後、水洗及び乾燥させ、硝酸と硫酸の混合酸溶液で50〜70℃で5〜360分間処理して行われることを特徴とする請求項6に記載のナノ金属担持触媒の製造方法。
- 前記ナノ金属触媒は、白金、パラジウム、コバルト、モリブデン及びルテニウムからなる群より選択された1種以上であることを特徴とする請求項1に記載のナノ金属担持触媒の製造方法。
- セルロース繊維を数マイクロメータの厚さの繊維に分離した後、分離された繊維を所定の長さに切断する段階と、
切断されたセルロース繊維を熱処理により炭化させて触媒支持体として製造する段階と、
製造されたセルロース触媒支持体の表面に炭素ナノチューブ成長用触媒金属を担持した後、一定温度で炭素源を供給して炭素ナノチューブを直接成長させる段階と、
炭素ナノチューブが成長したセルロース触媒支持体を酸で処理した後、化学的気相蒸着法を用いてナノサイズの金属触媒粒子であるナノ金属触媒を担持する段階と
を含んでなるナノ金属担持触媒の製造方法。 - セルロース繊維を炭化して製造された触媒支持体と、
前記触媒支持体の表面に直接成長した炭素ナノチューブと、
炭素ナノチューブの表面に担持されたナノサイズの金属触媒粒子であるナノ金属触媒粒子と
を含んでなるメタンの二酸化炭素改質反応に用いられるナノ金属担持触媒。 - 前記セルロース繊維は、へネケ麻、ケナフ、アバカ、竹、大麻、亜麻、苧麻、パイナップル、カラムシ及びサイザル麻からなるグループより選択されることを特徴とする請求項10に記載のナノ金属担持触媒。
- 前記ナノ金属触媒は、白金、パラジウム、コバルト、モリブデン及びルテニウムからなる群より選択された1種以上であることを特徴とする請求項10に記載のナノ金属担持触媒。
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