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WO2006007760A1 - Nanotubes de carbone a double paroi - Google Patents

Nanotubes de carbone a double paroi Download PDF

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Publication number
WO2006007760A1
WO2006007760A1 PCT/CN2004/000828 CN2004000828W WO2006007760A1 WO 2006007760 A1 WO2006007760 A1 WO 2006007760A1 CN 2004000828 W CN2004000828 W CN 2004000828W WO 2006007760 A1 WO2006007760 A1 WO 2006007760A1
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WIPO (PCT)
Prior art keywords
carbon nanotubes
double
carbon
catalyst
walled carbon
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Ceased
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PCT/CN2004/000828
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English (en)
Chinese (zh)
Inventor
Lingyong Kong
Haiyan Yang
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Priority to PCT/CN2004/000828 priority Critical patent/WO2006007760A1/fr
Publication of WO2006007760A1 publication Critical patent/WO2006007760A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • 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
    • 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
    • C01B32/168—After-treatment
    • C01B32/17—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/04—Nanotubes with a specific amount of walls
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • Double-walled carbon nanotubes and preparation method thereof Double-walled carbon nanotubes and preparation method thereof
  • the present invention relates to a carbon material and a process for the preparation thereof, and more particularly to a method for preparing high-purity double-walled carbon nanotubes in large quantities and a double-walled carbon nanotube product produced by the method. Background technique
  • Carbon nanotubes show great potential for their excellent performance, while double-walled carbon nanotubes not only show many properties of single-walled carbon nanotubes. Moreover, since double-walled carbon nanotubes have a larger interlayer spacing (greater than 0.34 nm), they exhibit more excellent performance. For example, it is more conducive to hydrogen storage than a single-walled tube; in addition, the double-walled carbon nanotube inner layer can function as a single-walled carbon nanotube, and the outer layer can be modified to expand its application range. Reports show that double-walled carbon nanotubes are equivalent to an excellent wire, the outer layer is insulated, and the inner layer has a superconducting effect. At present, the research on the preparation of double-walled carbon nanotubes has attracted much attention.
  • Double-walled carbon nanotubes can be obtained by arc-discharge, chemical vapor deposition (Chemical Vapor Deposition), etc., but the existing methods are low in cost and low in yield (only a few grams or even milligrams). ), low purity (only about 40%), process control is not conducive to large-scale production.
  • Zhu Hongwei et al. reported in "Science, 2002, 296: 884 ⁇ 886" and "Carbon, 2002, 40: 2021 ⁇ 2025": using n-hexane solution as carbon source, ferrocene as catalyst, thiophene as accelerator, Double-walled carbon nanotubes were prepared, but the process parameters were difficult to control, and the yield was also low, less than 5 wt%.
  • Ci Lijie et al., "Chemical Physics Letters, 2002, 359: 63 ⁇ 67” reported the synthesis of double-walled carbon nanotubes using acetylene as a carbon source, but the daily production is less than lg, and the product is coated with a large amount of amorphous carbon (amorphous). Carbon) and catalyst impurities, purity is not high.
  • the inventors of the present invention conducted intensive studies and found that the preparation of double-walled carbon nanotubes by using a specific catalyst formulation and CVD method (chemical vapor deposition) can not only greatly reduce the cost.
  • the yield is also greatly improved (up to 1 kg/h), and the process is stable.
  • High-purity (more than 90%) double-walled nanotubes can be obtained by catalytic oxidation of amorphous carbon impurities by carbon dioxide.
  • the present invention provides the following aspects:
  • a method for producing double-walled carbon nanotubes comprising:
  • transition metal oxide is at least one selected from the group consisting of oxides of chromium, iron, cobalt, and manganese.
  • Fig. 1 is a scanning electron microscope (SEM) photograph of the double-walled carbon nanotube obtained in the double wall tube purification example 1 of the present invention.
  • Figure 2 is a high resolution transmission electron microscope (HRTEM) photograph obtained in the double wall tube purification example 2 of the present invention.
  • Fig. 3 is a Raman spectrum obtained in the second embodiment of the double wall tube of the present invention.
  • Fig. 4 is a HRTEM electron micrograph of a double-walled carbon nanotube bundle in the process of purification of the double-walled tube in the comparative example 1 of the present invention without carbon dioxide plus catalyst. detailed description
  • the invention provides a method for producing double-walled carbon nanotubes, which comprises the steps of performing gas phase reduction reaction and deposition with a reducing agent by a chemical vapor deposition method using petroleum liquefied gas or methane as a reaction carbon source under the action of a catalyst.
  • the reducing agent includes, but is not limited to, carbon monoxide, hydrogen, preferably hydrogen.
  • MgAO x (A is used in combination with one or more of iron, cobalt and nickel salts) as a catalyst main body, through a combustion agent (EDTA, malic acid, glucose, citric acid, etc.)
  • EDTA ethylene glycol
  • One or more of the organic substances are mixed and uniformly fired to form nano-sized oxide particles, and then fired at 300 ° C to 1000 ° C in a muffle furnace to form a catalyst powder.
  • the prepared catalyst is laid in a constant temperature zone of the reactor, such as a hydrocarbon gas (such as methane, natural gas, petroleum liquefied gas, acetylene, ethylene, etc.), an oxygen compound (methanol, ethanol, methyl formate, etc.), carbon monoxide or carbon dioxide.
  • a hydrocarbon gas such as methane, natural gas, petroleum liquefied gas, acetylene, ethylene, etc.
  • an oxygen compound methanol, ethanol, methyl formate, etc.
  • carbon monoxide or carbon dioxide One or more of the combinations are used as a carbon source, combined with hydrogen (a carrier gas stream composed of a carbon source and hydrogen), and heated to 600 ° C ⁇ lOOO 'C reaction 10rain ⁇ 60min. Collect the product after cooling.
  • the transition metal element oxide powder is added to the carbon nanotubes, and after thorough mixing, carbon dioxide is introduced, the reaction time is 10 min to 50 min, and the temperature is controlled at 60 (TC ⁇ 900 ° C, and then acid. Washing, the final method of synthesizing more than 90% of the product into bundles of fibers.
  • the carrier gas stream preferably contains at least 80% by volume.
  • more than 90% of the product has hollow carbon nanotubes having an outer diameter of 10A to 35A and an inner diameter of 5 to 30 ⁇ .
  • the bundled product bundle is comprised primarily of carbon nanotubes constructed from double walls.
  • the catalyst was placed in a tube-type resistance furnace controlled at 60 (TC ⁇ 1000O), and the temperature was increased (from 600 ⁇ to 1000 ° C, the heating rate was 15 ° C/min), and the carbon source was cracked [methyl hydrazine, petroleum liquefaction). Gas (propane accounts for 75% by volume, Ding ⁇ accounts for 20% by volume)], controls the flow rate of hydrogen and carbon source, so that the volume ratio is greater than 2: 1, and the reaction is 20min ⁇ 60min to obtain crude double-walled carbon nanotubes.
  • the crude double-walled carbon nanotubes just prepared include impurities such as catalyst particles and amorphous carbon. ⁇ Using gas-liquid flexible oxidation method, the crude carbon nanotubes are first soaked with, for example, 25% hydrochloric acid (for example, 10 min), washed with deionized water until neutral, and added to the carbon nanotubes as lwt% ⁇ 5 wt of the weight of the carbon nanotubes.
  • transition metal oxide preferably one or several oxides of chromium, iron, cobalt, manganese
  • the temperature is controlled at 500 ° C ⁇ 900 ° C, reaction time 10min ⁇ 50min, after the reaction is completed, it is cooled and taken out, and the product is dissolved in nitric acid (preferably 10% nitric acid), filtered and dried to obtain a finished carbon nanotube, and passed SEM (Scanning Electron Microscopy JEM-2010) It was observed that the purity of carbon nanotubes was greater than 95%.
  • the carbon nanotubes obtained by the method of the present invention are mainly composed of bundles of carbon nanotubes entangled with each other, and the defined ends of the bundles of carbon nanotubes are not seen, and the bundles are clean and dense.
  • Figure 1 shows that after purification, the purity of the carbon nanotubes exceeds 95% (no amorphous carbon impurities are observed under electron microscope, a small amount of catalyst particles are present, and the catalyst impurity is 1.6 wt% after ash analysis.)
  • the sample mainly consists of a bundle of double-walled carbon nanotubes.
  • the pipe diameter is about 2 nm.
  • the present invention creatively utilizes the CVD method and creatively utilizes liquefied petroleum gas to synthesize carbon nanotubes, which can be produced at a very low production cost in large quantities (e.g., lkg/h). High purity double-walled carbon nanotubes.
  • the present invention adds ammonia water during the preparation of the catalyst, and can convert a large amount of toxic excess nitric acid and nitrate decomposition gas generated during the combustion into nitrogen and water vapor discharge, thereby achieving environmental friendliness. the goal of.
  • 210 g of the prepared catalyst 1 was plated in a quartz tube (tube diameter: 300 mm) to control a hydrogen flow rate of 0 m 3 /h, formazan 0.5 m 3 /h, and the reaction furnace temperature was between 600 ⁇ ⁇ : LOOO 'C , the reaction was stopped after 30 minutes, and the product was collected.
  • Double wall tube synthesis example 2 Double wall tube synthesis example 2:
  • Double wall tube synthesis example 3 Double wall tube synthesis example 3:
  • the catalyst 3 was placed in a quartz tube (300 mm diameter), and the hydrogen flow rate was controlled to be 2.0 m 3 /h, and the flow rate of the petroleum liquefied gas was 0. 5 m 3 /h, and the temperature of the reaction furnace was 600 ° C. Between 950 ° C, the reaction was stopped after 30 min, and the product was collected 1310 g .
  • Double wall tube synthesis example 5 Double wall tube synthesis example 5:
  • the catalyst 3 is placed in a quartz tube (300 mm diameter), and the hydrogen flow rate is controlled to be 2. 5 m 3 /h, and the flow rate of the formazan is 0. 5 m 3 /h, and the temperature of the reaction furnace is 600 ° C to 1000 Between ° C, the reaction was stopped after 30 min, and 1010 g of product was collected.
  • Double wall tube synthesis example 6 Double wall tube synthesis example 6:
  • the catalyst 3 is placed in a quartz tube (300 mm diameter), and the hydrogen flow rate is controlled to be 2.0 m 3 /h, methane is 0.5 m 7 h, and the temperature of the reaction furnace is between 600 ° C and 1000 ° C. After the reaction was stopped for 60 min, the product was collected 880 g. Double wall tube purification example 1
  • the crude product (obtained in Example 1) was immersed in a 25% by volume hydrochloric acid for 10 minutes, and then added to the carbon nanotubes to have a weight of 2 wt.
  • the chromium oxide powder is thoroughly mixed and put into the reaction furnace, and carbon dioxide is introduced into the reaction furnace.
  • the temperature is controlled at 500 ° C, the reaction time is 40 min, the reaction is completed, and then cooled and taken out, and the product is dissolved in 10% by volume of nitric acid. 6wt% ⁇
  • the ash content of the product is 1. 6wt%. See Figure 1 for SEM electron micrographs. Double wall tube purification example 2
  • Example 2 The crude product obtained in Example 1 was immersed in a 25% by volume hydrochloric acid solution for 10 minutes, and then chromic oxide powder containing 2% by weight of the carbon nanotubes was added to the carbon nanotubes, and the mixture was uniformly mixed and placed in a reaction furnace.
  • the ash content of the product is 1. 5wt.
  • the ash content of the product is 1. 00wt. %. See Figure 2 for HRTEM electron micrographs of the product.
  • the crude product was immersed in 25% hydrochloric acid for 10 min, and then iron oxide powder containing 2% by weight of the carbon nanotubes was added to the carbon nanotubes, and after fully mixing, the carbon dioxide was introduced into the reaction furnace.
  • the temperature was controlled at 900 ° C and the reaction time was 20 min.
  • the mixture was cooled and taken out, and the product was dissolved in 10% nitric acid, and dried by filtration to obtain 483 g of a finished carbon nanotube.
  • Ash analysis the product ash content was 1. 5wt%.
  • Double wall tube purification Example 4 In Example 2, 800 g of crude product was immersed in 25% hydrochloric acid for 10 min, and then added to the carbon nanotubes, iron oxide and oxide complex accounted for 1 wt% of the weight of the carbon nanotubes (mass ratio 1:1) Powder, fully mixed, put into the reaction furnace and pass carbon dioxide, the temperature is controlled at 750 ° C, the reaction time is 20 min, after the reaction is completed, it is cooled and taken out, the product is dissolved in 10% nitric acid, and dried by filtration to obtain carbon nanotubes. Finished product 525g. After Ash analysis, the product ash content was 1. 8wt%. . Double wall tube purification example 5
  • the crude product 800g was immersed in 25% hydrochloric acid for 10 minutes, and then the manganese oxide powder which accounts for 4% by weight of the carbon nanotubes was added to the carbon nanotubes, and after being uniformly mixed, the carbon dioxide was introduced into the reaction furnace, and the temperature was controlled. At 750 ° C, the reaction time was 20 min. After the completion of the reaction, the mixture was cooled and taken out, and the product was dissolved in 10% nitric acid, and dried by filtration to obtain 485 g of a carbon nanotube product. After Ash analysis, the product has an ash content of 1.4% by weight. Comparative purification example 1
  • the double wall tube is purified in Example 2, but the transition metal oxide is added as a catalyst reaction process, the carbon nanotubes are directly dissolved in nitric acid, and finally 716 g of the product is obtained.
  • the product ash content is 20 %.
  • the surface is covered with a large amount of amorphous carbon, as shown in Figure 4. This is because a large amount of amorphous carbon is not removed and covers the surface of the catalyst so that the acid cannot enter the dissolved catalyst, so that the purity of the obtained product is low.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé de production de nanotubes de carbone à double paroi, qui comprend: a) une étape de réaction et de dépôt de réduction en phase gazeuse, dans laquelle un gaz de pétrole liquéfié ou un méthane est utilisé en tant que source de carbone, un agent de réduction étant sélectionné dans le groupe constitué d'hydrogène, de monoxyde de carbone, ou un mélange de ceux-ci, la source de carbone étant mise en réaction avec l'agent de réduction sous catalyseur à une température comprise entre 600 et 1 000 °C par dépôt en phase gazeuse chimique, le produit primaire du carbone à double paroi étant ainsi obtenu; et b) une étape de purification dans laquelle l'oxyde de carbone et les oxydes de métal de transition sont utilisés en tant que catalyseur combiné et le carbone amorphe dans les nanotubes de carbone est purifié sous catalyseur combiné à une température comprise entre 600 et 900 °C. Cette invention concerne également des nanotubes de carbone à double paroi produits selon le procédé susmentionné, ces nanotubes possédant une pureté élevée (90%), un rendement élevé (1 kg/h), et pouvant être produits à grande échelle.
PCT/CN2004/000828 2004-07-19 2004-07-19 Nanotubes de carbone a double paroi Ceased WO2006007760A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101941692A (zh) * 2010-09-21 2011-01-12 上海大学 高结晶性双壁碳纳米管的制备方法
EP2828212A4 (fr) * 2012-04-18 2015-10-28 Exxonmobil Upstream Res Co Extraction de nanotubes de carbone d'un circuit d'eau
CN108502870A (zh) * 2018-05-25 2018-09-07 湖南大学 改性碳纳米管材料及其制备方法和应用
CN114643061A (zh) * 2022-03-17 2022-06-21 无锡东恒新能源科技有限公司 一种用于制备碳纳米管的催化剂的还原方法
CN117509619A (zh) * 2023-12-01 2024-02-06 江西中科景合新能源科技有限责任公司 一种新型碳纳米管的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1170631A (zh) * 1996-07-17 1998-01-21 厦门大学 过渡金属催化剂及用于制备均匀管径碳纳米管的方法
WO2002030816A1 (fr) * 2000-10-06 2002-04-18 Fullerene International Corporation Nanotubes de carbone a double paroi et leurs procedes de production d'application
CN1448335A (zh) * 2002-04-01 2003-10-15 财团法人工业技术研究院 适用于低温热化学气相沉积合成纳米碳管的负载金属触媒及使用此触媒的纳米碳管合成方法
CN1477057A (zh) * 2003-07-08 2004-02-25 浙江大学 用于制备成束多壁纳米碳管的金属氧化物催化剂及其制备和使用方法
CN1506304A (zh) * 2002-12-10 2004-06-23 中国科学院金属研究所 一种超长定向、层数可控的纳米碳管及纳米碳管绳的制备方法
CN1508065A (zh) * 2002-12-13 2004-06-30 中国科学院金属研究所 一种膜状和定向绳状双壁纳米碳管的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1170631A (zh) * 1996-07-17 1998-01-21 厦门大学 过渡金属催化剂及用于制备均匀管径碳纳米管的方法
WO2002030816A1 (fr) * 2000-10-06 2002-04-18 Fullerene International Corporation Nanotubes de carbone a double paroi et leurs procedes de production d'application
CN1448335A (zh) * 2002-04-01 2003-10-15 财团法人工业技术研究院 适用于低温热化学气相沉积合成纳米碳管的负载金属触媒及使用此触媒的纳米碳管合成方法
CN1506304A (zh) * 2002-12-10 2004-06-23 中国科学院金属研究所 一种超长定向、层数可控的纳米碳管及纳米碳管绳的制备方法
CN1508065A (zh) * 2002-12-13 2004-06-30 中国科学院金属研究所 一种膜状和定向绳状双壁纳米碳管的制备方法
CN1477057A (zh) * 2003-07-08 2004-02-25 浙江大学 用于制备成束多壁纳米碳管的金属氧化物催化剂及其制备和使用方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101941692A (zh) * 2010-09-21 2011-01-12 上海大学 高结晶性双壁碳纳米管的制备方法
EP2828212A4 (fr) * 2012-04-18 2015-10-28 Exxonmobil Upstream Res Co Extraction de nanotubes de carbone d'un circuit d'eau
CN108502870A (zh) * 2018-05-25 2018-09-07 湖南大学 改性碳纳米管材料及其制备方法和应用
CN114643061A (zh) * 2022-03-17 2022-06-21 无锡东恒新能源科技有限公司 一种用于制备碳纳米管的催化剂的还原方法
CN114643061B (zh) * 2022-03-17 2023-06-02 无锡东恒新能源科技有限公司 一种用于制备碳纳米管的催化剂的还原方法
CN117509619A (zh) * 2023-12-01 2024-02-06 江西中科景合新能源科技有限责任公司 一种新型碳纳米管的制备方法

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