WO2022047600A1 - Method for preparing multi-walled carbon nanotubes - Google Patents

Method for preparing multi-walled carbon nanotubes Download PDF

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WO2022047600A1
WO2022047600A1 PCT/CN2020/099327 CN2020099327W WO2022047600A1 WO 2022047600 A1 WO2022047600 A1 WO 2022047600A1 CN 2020099327 W CN2020099327 W CN 2020099327W WO 2022047600 A1 WO2022047600 A1 WO 2022047600A1
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carrier
carbon nanotubes
supported
catalyst
metal catalyst
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PCT/CN2020/099327
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French (fr)
Chinese (zh)
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刁贵强
李�浩
肖定书
IvanenkoIryna
DontsovaTetiana
AstrelinIhor
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惠州学院
乌克兰国立技术大学
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Priority to PCT/CN2020/099327 priority Critical patent/WO2022047600A1/en
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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

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  • the invention relates to the field of chemical synthesis, in particular to a method for preparing multi-walled carbon nanotubes.
  • Carbon nanotubes are a kind of carbon allotrope in which carbon and carbon are connected into hexagons to form a cylindrical tube structure. Nanotube. Due to its hollowness, light weight, high tensile strength and physical properties of bending to 90° without damage, and high thermal and electrical conductivity, this carbon nanotube presents conductors and semiconductors according to the angle at which the carbon layer is wrapped. nature. Carbon nanotubes are further classified into single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) according to the number of walls.
  • SWNTs single-walled carbon nanotubes
  • MWNTs multi-walled carbon nanotubes
  • the catalyst used in the process of multi-walled carbon nanotubes also needs to be reduced with hydrogen, which reduces the safety of the synthesis reaction.
  • the existing chemical vapor deposition (CVD) technology is expensive to prepare multi-walled carbon nanotubes.
  • CVD chemical vapor deposition
  • the production process of multi-walled carbon nanotubes disclosed in US Patent US 2012/0177545 ⁇ 1 uses benzene as a carbon source, and the synthesis temperature is 750 ° C. This production process can prepare 0.737 g of carbon nanotubes through 2.99 g of benzene, and the relative yield is 25 %.
  • methane is used as a carbon source
  • Fe/Al 2 O 3 is used as a catalyst
  • the reaction temperature is 900° C.
  • the catalyst is subjected to hydrogen reduction pretreatment.
  • the invention discloses a method for preparing multi-wall carbon nanotubes.
  • the catalyst used in the method does not need hydrogen reduction pretreatment, and the temperature and reaction time for preparing multi-wall carbon nanotubes are reduced, thereby reducing production cost.
  • the present invention adopts the following technical solutions: a method for preparing multi-walled carbon nanotubes, the method adopts a gas phase synthesis method, and the method can adopt chemical vapor deposition (CVD) equipment in the prior art.
  • the deposition (CVD) equipment includes a horizontal quartz reactor, and the catalyst used in the process is placed in a ceramic boat or a quartz boat in the middle of the reactor.
  • the method provided by the present invention comprises the following steps:
  • the mixed gas is cooled to room temperature under a protective gas atmosphere after reacting for no less than 30 min.
  • the heating rate of step S1 is 10 °C/min
  • the volume ratio of the protective gas to the hydrocarbon gas is 3:1, the hydrocarbon gas is methane, ethylene, acetylene, liquefied petroleum gas or a combination thereof, and the protective gas is nitrogen.
  • the hydrocarbon gas is acetylene
  • the protective gas is nitrogen
  • acetylene and nitrogen are supplied at flow rates of 50 mL/min and 150 mL/min, respectively, and the reaction temperature of acetylene and nitrogen is 550 °C.
  • the catalyst used in this method is a supported catalyst, and the supported catalyst used in the present invention can produce carbon nanotubes with improved physical properties (such as specific surface area and/or electrical conductivity), and the supported catalyst can also improve multi-walled carbon Yield of nanotubes.
  • the present invention uses a supported catalyst to synthesize multi-wall carbon nanotubes
  • the supported catalyst for synthesizing multi-wall carbon nanotubes includes a carrier and a metal catalyst supported on the carrier.
  • the support includes Al 2 O 3 , MgO, SiO 2 or a combination thereof.
  • Metal catalysts can be selected from Ni and Co metal catalysts, Ni and V metal catalysts or Ni, Co and V metal catalysts.
  • the supported catalyst includes a carrier and a metal catalyst containing Ni and Co supported on the carrier, and the molar ratio of Ni and Co in the metal catalyst is 1:2.4-2.6.
  • the supported catalyst includes a carrier and a metal catalyst containing Ni and V supported on the carrier, and the molar ratio of Ni and V in the metal catalyst is 1:1.1-1.3
  • the supported catalyst includes a support and a metal catalyst containing Ni, Co and V supported on the support, and the molar ratio of Ni, Co and V in the metal catalyst is 1:2.5-2.6:2.6-2.8.
  • Supported catalysts are prepared by the following steps:
  • the metal catalyst precursor is dissolved in a solvent to prepare an aqueous solution of the metal catalyst, and then the carrier is added and mixed to obtain a suspension;
  • step S3 the solid material prepared in step S2 is sintered at a high temperature of 350-550° C. for not less than 2 hours to obtain a supported catalyst.
  • the solvent in step S1 is water, alcohol or a combination thereof.
  • an activator such as manganese salt, may be added during the high temperature sintering process in step S3 to nanonize the material and prevent agglomeration between nano-sized metal catalysts, thereby making the supported catalyst into spherical particles.
  • citric acid is added and mixed, and the citric acid can activate the contact points of the support material with the metal catalyst, thereby promoting the metal catalyst to be loaded on the support.
  • the technical scheme of the present invention is to directly supply carbon-containing hydrocarbons and nitrogen into the reaction furnace, and the metal particles of the supported catalyst form carbon nanotubes as a seed, and the catalyst does not need to be pretreated by hydrogen reduction. , thereby improving the safety of the synthesis reaction;
  • the range of the reaction temperature in the technical solution of the present invention is 550-600 °C; and the reaction temperature of the technical solution for synthesizing multi-walled carbon nanotubes by chemical vapor deposition (CVD) disclosed in the prior art is not lower than 650 °C , so the technical solution of the present invention reduces the temperature of carbon nanotube synthesis;
  • the preparation method of the supported catalyst is simple, and the microstructure of the supported catalyst can be controlled by adding an activator (such as manganese salt, cerium salt, etc.) during the high-temperature sintering process.
  • the microstructure can produce carbon nanotubes with improved physical properties (such as specific surface area and/or electrical conductivity), and increase the yield of multi-walled carbon nanotubes, such as the addition of manganese nitrate during the high temperature sintering process to prepare supported catalysts to make the supported catalysts.
  • the catalyst can be made into spherical particles, thereby increasing the contact area of the supported catalyst, thereby increasing the specific surface area of the prepared carbon nanotubes and increasing the yield of multi-walled carbon nanotubes.
  • the method for preparing multi-walled carbon nanotubes disclosed in the present invention can obtain multi-walled carbon nanotubes with high yield and large specific area. Because the catalyst provided by the present invention does not need to use hydrogen reduction in the preparation process, and can obtain multi-walled carbon nanotubes with high yield at a lower temperature and a shorter time, the present invention is one of the existing industrial production methods. a good alternative.
  • Example 1 is a scanning electron microscope and a transmission electron microscope image of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
  • Example 2 is the nitrogen adsorption-desorption isotherm in the process of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
  • FIG. 3 is a pore size distribution diagram of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
  • 0.3 g of the prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) equipment, and nitrogen was introduced at a flow rate of 150 mL/min under normal pressure, while at a rate of 10 °C/min. Heating to 550 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanometers Tube.
  • CVD chemical vapor deposition
  • 0.1 g of the prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) apparatus, and nitrogen was fed at a flow rate of 150 mL/min under normal pressure, while at a rate of 10 °C/min. Heating to 600 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanometers Tube.
  • CVD chemical vapor deposition
  • 0.1 g of the as-prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) apparatus, and nitrogen was passed at a flow rate of 150 mL/min under normal pressure, while at 10 °C/min. Heating at a rate of 550 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanotubes.
  • CVD chemical vapor deposition
  • the average diameter of the prepared MWCNTs is about 15-35nm
  • the pore size of the MWCNTs is about 20-35nm
  • the specific surface area of the MWCNTs is about 310m 2 / g.
  • Y c 1 (W dep ⁇ W kat )/W kat , where W dep is the feed weight of the carbon source, and W kat is the prepared multi-wall carbon nanotubes.
  • the weight of the walled carbon nanotubes, the calculated relative yields of the multi-walled carbon nanotubes prepared in Examples 1 to 4 are shown in the following table:
  • the relative yields of the multi-walled carbon nanotubes prepared in Examples 1 to 4 are 80%, 76%, 45% and 41%, respectively, which are higher than those disclosed in the prior art using chemical vapor deposition (CVD) Relative yields of synthetic multi-walled carbon nanotubes.
  • the above-mentioned catalyst may comprise cobaltous acetate tetrahydrate, cobaltous dichloride hexahydrate, cobaltous nitrate hexahydrate and cobaltous sulfate heptahydrate as a substance containing cobalt (Co) selected from the group consisting of cobalt (Ni) containing Nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel sulfate hexahydrate and nickel halide as substances; ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate as substances containing vanadium (V) , sodium pyrovanadate, vanadyl sulfate, vanadyl oxalate, vanadium tetrachloride and vanadyl trichloride and the catalyst in the group consisting of combinations thereof, but not limited thereto.
  • cobalt (Co) selected from the group consisting of cobal

Abstract

A method for preparing multi-walled carbon nanotubes, comprising the following steps: S1, placing a supported catalyst in a chemical vapor deposition (CVD) device, and introducing a protective gas under atmospheric pressure and heating to 550-600 °C; S2, introducing hydrocarbon gases under atmospheric pressure; and S3, reacting the mixed gases for not more than 30 min, and then cooling same to room temperature in the protective gas atmosphere. The catalyst used in the method does not need to be pretreated by hydrogen reduction, and the temperature and reaction time for preparing the multi-walled carbon nanotubes are reduced, thereby reducing the production costs.

Description

一种制备多壁碳纳米管的方法A kind of method for preparing multi-walled carbon nanotubes 技术领域technical field
本发明涉及化学合成领域，特别是涉及一种制备多壁碳纳米管的方法。The invention relates to the field of chemical synthesis, in particular to a method for preparing multi-walled carbon nanotubes.
背景技术Background technique
碳纳米管(Carbon nanotubes：CNTs)是以碳-碳相连为六边形而形成圆筒型管结构的一种碳同素异形体,呈直径为数nm程度的小的管形状，从而被称为纳米管。这种碳纳米管由于空心、质量轻，而且具有较大的拉伸强度及无损地弯曲至90°的物性，并且具有高的导热性及导电性，根据碳层被缠的角度呈现导体和半导体的性质。碳纳米管根据壁的数量还区分为单壁碳纳米管(single walled carbon nanotubes：SWNTs)、多壁碳纳米管(multi-walled carbonnanotubes：MWNTs)。Carbon nanotubes (CNTs) are a kind of carbon allotrope in which carbon and carbon are connected into hexagons to form a cylindrical tube structure. nanotube. Due to its hollowness, light weight, high tensile strength and physical properties of bending to 90° without damage, and high thermal and electrical conductivity, this carbon nanotube presents conductors and semiconductors according to the angle at which the carbon layer is wrapped. nature. Carbon nanotubes are further classified into single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) according to the number of walls.
现有的制备多壁碳纳米管技术包括放电法、激光蒸镀法、等离子体化学气相沉积法、热化学沉积法、气相合成法及电解法等。其中，化学气相沉积(在高温常压下反应炉内进料烃类气体和氢气)制备碳纳米管的技术已得到广泛应用。在现有的化学气相沉积(CVD)制备多壁碳纳米管的过程中，多壁碳纳米管合成温度不低于650℃且反应时间不低于2小时，而且该方法必须使用催化剂，在制备多壁碳纳米管的过程中所使用的催化剂还需要用氢还原，使得合成反应的安全性降低。其次，由于制备多壁碳纳米管的反应温度过高以及反应时间过久使得现有化学气相沉积(CVD)技术制备多壁碳纳米管的成本昂贵。Existing technologies for preparing multi-walled carbon nanotubes include discharge method, laser evaporation method, plasma chemical vapor deposition method, thermal chemical deposition method, gas phase synthesis method and electrolysis method. Among them, the technology of preparing carbon nanotubes by chemical vapor deposition (feeding hydrocarbon gas and hydrogen in a reaction furnace under high temperature and normal pressure) has been widely used. In the existing chemical vapor deposition (CVD) process for preparing multi-walled carbon nanotubes, the synthesis temperature of multi-walled carbon nanotubes is not less than 650 ° C and the reaction time is not less than 2 hours, and the method must use a catalyst. The catalyst used in the process of multi-walled carbon nanotubes also needs to be reduced with hydrogen, which reduces the safety of the synthesis reaction. Secondly, due to the excessively high reaction temperature and long reaction time for preparing multi-walled carbon nanotubes, the existing chemical vapor deposition (CVD) technology is expensive to prepare multi-walled carbon nanotubes.
美国专利US 2012/0114550А1中公开一种采用化学气相沉积(CVD)合成多壁碳纳米管的方法，该方法的反应温度为650℃，反应时间在120min内，采用甲苯作为碳源并且使用Fe/Al 2O 3作为催化剂，该方法能通过42g甲苯制备8.81g的碳纳米管，相对产率为21％(计算多壁碳纳米管相对产率的公式为：Y c 1＝(W dep–W kat)/W kat，其中W dep为碳源的进料重量，W kat为制备的多壁碳纳米管的重量)。美国专利US 2012/0177545А1中公开的多壁碳纳米管的生产工艺中采用苯作为碳源,合成温度为750℃，该生产工艺能通过2.99g苯制备0.737g碳纳米管，相对产率为25％。美国专利US2011/0150746A1公开的制备多壁碳纳米管的方法中采用甲烷作为碳源，使用Fe/Al 2O 3作为催化剂，反应温度为900℃，该方法对催化剂进行了氢还原预处理。 US 2012/0114550А1 discloses a method for synthesizing multi-walled carbon nanotubes by chemical vapor deposition (CVD), the reaction temperature of the method is 650 ° C, the reaction time is within 120 min, using toluene as a carbon source and using Fe/ Using Al 2 O 3 as a catalyst, this method can prepare 8.81 g of carbon nanotubes from 42 g of toluene with a relative yield of 21% (the formula for calculating the relative yield of multi-walled carbon nanotubes is: Y c 1 =(W dep −W kat )/W kat , where W dep is the feed weight of the carbon source and W kat is the weight of the prepared multi-walled carbon nanotubes). The production process of multi-walled carbon nanotubes disclosed in US Patent US 2012/0177545А1 uses benzene as a carbon source, and the synthesis temperature is 750 ° C. This production process can prepare 0.737 g of carbon nanotubes through 2.99 g of benzene, and the relative yield is 25 %. In the method for preparing multi-walled carbon nanotubes disclosed in US Patent US2011/0150746A1, methane is used as a carbon source, Fe/Al 2 O 3 is used as a catalyst, and the reaction temperature is 900° C. The catalyst is subjected to hydrogen reduction pretreatment.
本发明公开了一种制备多壁碳纳米管的方法，该方法使用的催化剂无需采用氢还原预处理，并且降低了制备多壁碳纳米管的温度和反应时间,降低生产成本。The invention discloses a method for preparing multi-wall carbon nanotubes. The catalyst used in the method does not need hydrogen reduction pretreatment, and the temperature and reaction time for preparing multi-wall carbon nanotubes are reduced, thereby reducing production cost.
发明内容SUMMARY OF THE INVENTION
为实现上述目的，本发明采用如下技术方案：一种制备多壁碳纳米管的方法，该方法采用气相合成法，该方法可以采用现有技术中的化学气相沉积(CVD)设备，该化学气相沉积(CVD)设备包括水平石英反应器，本方法所使用的催化剂被放置在陶瓷舟或石英舟在放置在反应器的中间。本发明提供的方法包括以下步骤：In order to achieve the above object, the present invention adopts the following technical solutions: a method for preparing multi-walled carbon nanotubes, the method adopts a gas phase synthesis method, and the method can adopt chemical vapor deposition (CVD) equipment in the prior art. The deposition (CVD) equipment includes a horizontal quartz reactor, and the catalyst used in the process is placed in a ceramic boat or a quartz boat in the middle of the reactor. The method provided by the present invention comprises the following steps:
[根据细则26改正04.09.2020]　
S1，将负载型催化剂放到化学气相沉积(CVD)设备中，在常压下通入保护气体，同时加热至550-600 ℃； [Correction 04.09.2020 according to Rule 26]
S1, put the supported catalyst into a chemical vapor deposition (CVD) equipment, pass a protective gas under normal pressure, and heat it to 550-600 °C at the same time;
S2，常压下通入烃类气体；S2, pass hydrocarbon gas under normal pressure;
S3，混合气体反应不少于30min后在保护气体氛围下冷却至室温。S3, the mixed gas is cooled to room temperature under a protective gas atmosphere after reacting for no less than 30 min.
[根据细则26改正04.09.2020]　
在一实施例中，步骤S1的加热速率为10 ℃/min[Correction 04.09.2020 according to Rule 26]
In one embodiment, the heating rate of step S1 is 10 ℃/min
在一实施例中，保护气体与烃类气体的体积比为3:1，烃类气体是甲烷、乙烯、乙炔、液化石油气或它们的组合，保护气体为氮气。In one embodiment, the volume ratio of the protective gas to the hydrocarbon gas is 3:1, the hydrocarbon gas is methane, ethylene, acetylene, liquefied petroleum gas or a combination thereof, and the protective gas is nitrogen.
[根据细则26改正04.09.2020]　
在一实施例中，烃类气体是乙炔，保护气体为氮气，乙炔和氮气分别以50mL/min、150mL/min的流速供给，乙炔和氮气的反应温度为550 ℃。 [Correction 04.09.2020 according to Rule 26]
In one embodiment, the hydrocarbon gas is acetylene, the protective gas is nitrogen, acetylene and nitrogen are supplied at flow rates of 50 mL/min and 150 mL/min, respectively, and the reaction temperature of acetylene and nitrogen is 550 °C.
本方法向反应炉内直接供给含碳的烃类和氮气，负载型催化剂的金属粒子作为一个种源(seed)的作用来形成碳纳米管，该方法无需采用氢还原的过程，并且降低了碳纳米管合成的温度和持续时间，降低生产成本。In this method, carbon-containing hydrocarbons and nitrogen are directly supplied into the reaction furnace, and the metal particles of the supported catalyst act as a seed to form carbon nanotubes. This method does not require the process of hydrogen reduction, and reduces carbon Temperature and duration of nanotube synthesis, reducing production costs.
本方法所使用的催化剂为负载型催化剂，本发明中使用的负载型催化剂可以生产具有改善的物理性质(如比表面积和/或电导率)的碳纳米管，负载型催化剂还能够提高多壁碳纳米管的产量。The catalyst used in this method is a supported catalyst, and the supported catalyst used in the present invention can produce carbon nanotubes with improved physical properties (such as specific surface area and/or electrical conductivity), and the supported catalyst can also improve multi-walled carbon Yield of nanotubes.
本发明使用负载型催化剂合成多壁碳纳米管，用于合成多壁碳纳米管的负载型催化剂包括载体以及负载于所述载体上的金属催化剂。载体包括Al 2O 3、MgO、SiO 2或者它们的组合。金属催化剂可选用Ni和Co金属催化剂、Ni和V金属催化剂或Ni、Co和V金属催化剂。 The present invention uses a supported catalyst to synthesize multi-wall carbon nanotubes, and the supported catalyst for synthesizing multi-wall carbon nanotubes includes a carrier and a metal catalyst supported on the carrier. The support includes Al 2 O 3 , MgO, SiO 2 or a combination thereof. Metal catalysts can be selected from Ni and Co metal catalysts, Ni and V metal catalysts or Ni, Co and V metal catalysts.
在一实施例中，负载型催化剂包括载体以及含有负载于载体上的Ni和Co金属催化剂，金属催化剂中Ni和Co的摩尔比为1：2.4-2.6。In one embodiment, the supported catalyst includes a carrier and a metal catalyst containing Ni and Co supported on the carrier, and the molar ratio of Ni and Co in the metal catalyst is 1:2.4-2.6.
在一实施例中，负载型催化剂包括载体以及含有负载于载体上的Ni和V金属催化剂，金属催化剂中Ni和V的摩尔比为1：1.1-1.3In one embodiment, the supported catalyst includes a carrier and a metal catalyst containing Ni and V supported on the carrier, and the molar ratio of Ni and V in the metal catalyst is 1:1.1-1.3
在一实施例中，负载型催化剂包括载体以及含有负载于载体上的Ni、Co和V金属催化剂，金属催化剂中Ni、Co和V的摩尔比为1：2.5-2.6：2.6-2.8。In one embodiment, the supported catalyst includes a support and a metal catalyst containing Ni, Co and V supported on the support, and the molar ratio of Ni, Co and V in the metal catalyst is 1:2.5-2.6:2.6-2.8.
负载型催化剂通过以下步骤进行制备：Supported catalysts are prepared by the following steps:
S1，将金属催化剂前驱体溶解在溶剂中来制备金属催化剂的水溶液，再加入载体混合得到悬浮液；S1, the metal catalyst precursor is dissolved in a solvent to prepare an aqueous solution of the metal catalyst, and then the carrier is added and mixed to obtain a suspension;
[根据细则26改正04.09.2020]　
S2，将悬浮液蒸发，得到的沉淀物在不低于110 ℃下干燥不少于12h； [Correction 04.09.2020 according to Rule 26]
S2, the suspension is evaporated, and the obtained precipitate is dried at not less than 110 °C for not less than 12 hours;
[根据细则26改正04.09.2020]　
S3，将步骤S2制备的固体材料在350-550 ℃下高温烧结不少于2h得到负载型催化剂。 [Correction 04.09.2020 according to Rule 26]
S3, the solid material prepared in step S2 is sintered at a high temperature of 350-550° C. for not less than 2 hours to obtain a supported catalyst.
在一实施例中，步骤S1中的溶剂是水、醇或它们的组合。In one embodiment, the solvent in step S1 is water, alcohol or a combination thereof.
在一实施例中，在步骤S3的高温烧结过程期间可以加入活化剂，如锰盐使材料纳米化并阻止纳米尺寸的金属催化剂之间的团聚，从而使得负载型催化剂制成球形颗粒。In one embodiment, an activator, such as manganese salt, may be added during the high temperature sintering process in step S3 to nanonize the material and prevent agglomeration between nano-sized metal catalysts, thereby making the supported catalyst into spherical particles.
在一实施例中，步骤S1中制备悬浮液后加入柠檬酸并混合，柠檬酸能活化载体材料的与金属催化剂的接触点，从而促进金属催化剂负载于所述载体上。In one embodiment, after the suspension is prepared in step S1, citric acid is added and mixed, and the citric acid can activate the contact points of the support material with the metal catalyst, thereby promoting the metal catalyst to be loaded on the support.
与现有技术相比，本发明提供的技术方案具有以下的技术效果；Compared with the prior art, the technical solution provided by the present invention has the following technical effects;
1.本发明的技术方案是向反应炉内直接供给含碳的烃类和氮气，负载型催化剂的金属粒子作为一个种源(seed)的作用来形成碳纳米管，催化剂无需采用氢还原预处理，从而提高了合成反应的安全性；1. The technical scheme of the present invention is to directly supply carbon-containing hydrocarbons and nitrogen into the reaction furnace, and the metal particles of the supported catalyst form carbon nanotubes as a seed, and the catalyst does not need to be pretreated by hydrogen reduction. , thereby improving the safety of the synthesis reaction;
[根据细则26改正04.09.2020]　
2.本发明的技术方案中反应温度的范围为550-600 ℃；而现有技术中所公开的采用化学气相沉积(CVD)合成多壁碳纳米管的技术方案的反应温度不低于650℃，因此本发明的技术方案降低了碳纳米管合成的温度； [Correction 04.09.2020 according to Rule 26]
2. The range of the reaction temperature in the technical solution of the present invention is 550-600 °C; and the reaction temperature of the technical solution for synthesizing multi-walled carbon nanotubes by chemical vapor deposition (CVD) disclosed in the prior art is not lower than 650 °C , so the technical solution of the present invention reduces the temperature of carbon nanotube synthesis;
3.本发明的技术方案中，负载型催化剂的制备方法简单，并且负载型催化剂的微观结构能在高温烧结过程中加入活化剂(如锰盐、铈盐等)来控制，通过控制负载型催化剂的微观结构可以生产具有改善的物理性质(如比表面积和/或 电导率)的碳纳米管，并且提高多壁碳纳米管的产量，例如制备负载型催化剂的高温烧结过程期间加入硝酸锰使得负载型催化剂制成球形颗粒，从而提高负载型催化剂的接触面积从而提高制备的碳纳米管的比表面积并提高多壁碳纳米管的产量。3. In the technical scheme of the present invention, the preparation method of the supported catalyst is simple, and the microstructure of the supported catalyst can be controlled by adding an activator (such as manganese salt, cerium salt, etc.) during the high-temperature sintering process. The microstructure can produce carbon nanotubes with improved physical properties (such as specific surface area and/or electrical conductivity), and increase the yield of multi-walled carbon nanotubes, such as the addition of manganese nitrate during the high temperature sintering process to prepare supported catalysts to make the supported catalysts. The catalyst can be made into spherical particles, thereby increasing the contact area of the supported catalyst, thereby increasing the specific surface area of the prepared carbon nanotubes and increasing the yield of multi-walled carbon nanotubes.
本发明的有益效果为：本发明公开的制备多壁碳纳米管的方法可以获得产率高、比面积大的多壁碳纳米管。因为本发明提供的催化剂在制备过程中无需采用氢还原，并且可以在较低的温度和较短的时间内获得产量较高的多壁碳纳米管，因此本发明是现有工业生产方法的一种很好的替代方法。The beneficial effects of the present invention are as follows: the method for preparing multi-walled carbon nanotubes disclosed in the present invention can obtain multi-walled carbon nanotubes with high yield and large specific area. Because the catalyst provided by the present invention does not need to use hydrogen reduction in the preparation process, and can obtain multi-walled carbon nanotubes with high yield at a lower temperature and a shorter time, the present invention is one of the existing industrial production methods. a good alternative.
附图说明Description of drawings
附图对本发明作进一步说明，但附图中的实施例不构成对本发明的任何限制。The accompanying drawings further illustrate the present invention, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention.
图1为本发明实施例4制备的多壁碳纳米管的扫描电镜和透射电镜图像。1 is a scanning electron microscope and a transmission electron microscope image of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
图2为本发明实施例4制备的多壁碳纳米管过程中氮吸附-解吸等温线。2 is the nitrogen adsorption-desorption isotherm in the process of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
图3为本发明实施例4制备的多壁碳纳米管的孔径分布图。FIG. 3 is a pore size distribution diagram of the multi-walled carbon nanotubes prepared in Example 4 of the present invention.
具体实施方式detailed description
以下，参照附图详细说明本发明的实例及实施例，以便本发明所属技术领域的普通技术人员能够容易实施。但是，本发明能够以多种不同的方式实现，并不局限于在此说明的实例及实施例。为了明确说明本发明，省略了与说明无关的部分。Hereinafter, examples and embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art to which the present invention pertains can be easily implemented. However, the present invention can be implemented in many different ways and is not limited to the examples and embodiments described herein. In order to clearly describe the present invention, parts irrelevant to the description are omitted.
在说明书全文中，当某一部分“包含”某种结构要素时，这是在无特别相反的记载的情况下，不是排除其他结构要素，而是意味着还包含其他结构要素。In the whole specification, when a certain part "includes" a certain structural element, it is not excluding other structural elements, but means that other structural elements are also included in the case of no special description to the contrary.
以下，参照附图对本发明的实例及实施例进行详细说明。但是本发明并不局限于这些实例及实施例和附图。Hereinafter, examples and embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to these examples and embodiments and drawings.
实施例1Example 1
[根据细则26改正04.09.2020]　
将2.8g Ni(NO 3) 2·6H 2O、5.3g Co(NO 3) 2·6H 2O溶解在150ml蒸馏水中，再加入5g的MgO载体以制备催化剂组合物的溶液，在110℃下在常压下将上述悬浊液进行蒸发获得沉淀物，再将沉淀物在110℃下干燥12h，再于350℃下加热2h以制备负载型催化剂。将0.3g所制备的负载型催化剂放置到陶瓷舟中并将 陶瓷舟放置到化学气相沉积(CVD)设备中，在常压下以150mL/min的流速通入氮气，同时以10 ℃/min速率加热至550 ℃；常压下以50mL/min的流速通入乙炔气体直至氮气与乙炔气体的体积比为3:1；将混合气体反应30min后在氮气氛围下冷却至室温制备得到多壁碳纳米管。 [Correction 04.09.2020 according to Rule 26]
2.8 g Ni(NO 3 ) 2 .6H 2 O, 5.3 g Co(NO 3 ) 2 .6H 2 O were dissolved in 150 ml of distilled water, and 5 g of MgO carrier was added to prepare a solution of the catalyst composition at 110° C. The above suspension was evaporated under normal pressure to obtain a precipitate, which was then dried at 110 °C for 12 h, and then heated at 350 °C for 2 h to prepare a supported catalyst. 0.3 g of the prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) equipment, and nitrogen was introduced at a flow rate of 150 mL/min under normal pressure, while at a rate of 10 °C/min. Heating to 550 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanometers Tube.
实施例2Example 2
[根据细则26改正04.09.2020]　
将9g Ni(NO 3) 2·6H 2O、4.5gNH 4VO 3溶解在100ml蒸馏水中，再加入5g的MgO载体以制备催化剂组合物的溶液，在110 ℃下在常压下将上述悬浊液进行蒸发获得沉淀物，再将沉淀物在110 ℃下干燥12h，再于350 ℃下加热2h以制备负载型催化剂。将0.5g所制备的负载型催化剂放置到陶瓷舟中并将陶瓷舟放置到化学气相沉积(CVD)设备中，在常压下以150mL/min的流速进通入氮气，同时以10 ℃/min速率加热至550 ℃; 常压下以50mL/min的流速通入乙炔气体直至氮气与乙炔气体的体积比为3:1；将混合气体反应30min后在氮气氛围下冷却至室温制备得到多壁碳纳米管。 [Correction 04.09.2020 according to Rule 26]
Dissolve 9g Ni(NO 3 ) 2 ·6H 2 O and 4.5g NH 4 VO 3 in 100ml of distilled water, and then add 5g of MgO carrier to prepare a solution of the catalyst composition. The liquid was evaporated to obtain a precipitate, which was then dried at 110 °C for 12 h, and then heated at 350 °C for 2 h to prepare a supported catalyst. 0.5 g of the prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) equipment, and nitrogen was introduced at a flow rate of 150 mL/min under normal pressure, while at 10 °C/min. Heating at a rate of 550 °C; under normal pressure, acetylene gas was introduced at a flow rate of 50 mL/min until the volume ratio of nitrogen to acetylene gas was 3:1; the mixed gas was reacted for 30 min and then cooled to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanotube.
实施例3Example 3
[根据细则26改正04.09.2020]　
将9g Ni(NO 3) 2·6H 2O、4.5gNH 4VO 3溶解在150ml蒸馏水中，再加入5g的C 6H 8O 7·H 2O和5g的MgO以制备催化剂组合物的溶液，在110 ℃下在常压下将上述悬浊液进行蒸发获得沉淀物，再将沉淀物在110 ℃下干燥12h，再于350℃下加热2h以制备负载型催化剂。将0.1g所制备的负载型催化剂放置到陶瓷舟中并将陶瓷舟放置到化学气相沉积(CVD)设备中，在常压下以150mL/min的流速进料氮气，同时以10 ℃/min速率加热至600 ℃；常压下以50mL/min的流速通入乙炔气体直至氮气与乙炔气体的体积比为3:1；将混合气体反应30min后在氮气氛围下冷却至室温制备得到多壁碳纳米管。 [Correction 04.09.2020 according to Rule 26]
9g Ni(NO 3 ) 2 ·6H 2 O, 4.5g NH 4 VO 3 were dissolved in 150ml distilled water, and 5g C 6 H 8 O 7 ·H 2 O and 5g MgO were added to prepare a solution of the catalyst composition, The above suspension was evaporated at 110 °C under normal pressure to obtain a precipitate, then the precipitate was dried at 110 °C for 12 h, and then heated at 350 °C for 2 h to prepare a supported catalyst. 0.1 g of the prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) apparatus, and nitrogen was fed at a flow rate of 150 mL/min under normal pressure, while at a rate of 10 °C/min. Heating to 600 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanometers Tube.
实施例4Example 4
[根据细则26改正04.09.2020]　
将2.2g Ni(NO 3) 2·6H 2O、4.2g Co(NO 3) 2·6H 2O和2.4g NH 4VO 3溶解在150ml蒸馏水中，再加入5g的Al 2O 3载体以制备催化剂组合物的溶液，在110 ℃下在常压下将上述悬浊液进行蒸发获得沉淀物，再将沉淀物在110 ℃下干燥12h，再于350 ℃下加热2h以制备负载型催化剂。将0.1g所制备的负载型催化剂放置到陶瓷船中并将陶瓷船放置到化学气相沉积(CVD)设备中，在常压下以150 mL/min的流速通入氮气，同时以10 ℃/min速率加热至550 ℃；在常压下以50mL/min的流速通入乙炔气体直至氮气与乙炔气体的体积比为3:1；将混合气体反应30min后在氮气氛围下冷却至室温制备得到多壁碳纳米管。 [Correction 04.09.2020 according to Rule 26]
2.2g Ni(NO 3 ) 2 .6H 2 O, 4.2g Co(NO 3 ) 2 .6H 2 O and 2.4g NH 4 VO 3 were dissolved in 150ml distilled water, and 5g of Al 2 O 3 carrier was added to prepare For the solution of the catalyst composition, the above suspension was evaporated at 110 °C under normal pressure to obtain a precipitate, then the precipitate was dried at 110 °C for 12 h, and then heated at 350 °C for 2 h to prepare a supported catalyst. 0.1 g of the as-prepared supported catalyst was placed in a ceramic boat and the ceramic boat was placed in a chemical vapor deposition (CVD) apparatus, and nitrogen was passed at a flow rate of 150 mL/min under normal pressure, while at 10 °C/min. Heating at a rate of 550 °C; passing acetylene gas at a flow rate of 50 mL/min under normal pressure until the volume ratio of nitrogen to acetylene gas is 3:1; reacting the mixed gas for 30 min and cooling to room temperature under nitrogen atmosphere to prepare multi-walled carbon nanotubes.
如图1-图3所示，制备的多壁碳纳米管平均直径约为15-35nm，多壁碳纳米管孔径大小约为20-35nm，多壁碳纳米管的比表面积约为310m 2/g。 As shown in Figures 1-3, the average diameter of the prepared MWCNTs is about 15-35nm, the pore size of the MWCNTs is about 20-35nm, and the specific surface area of the MWCNTs is about 310m 2 / g.
在上述实施例中，根据多壁碳纳米管相对产率的公式：Y c 1＝(W dep–W kat)/W kat，其中W dep为碳源的进料重量，W kat为制备的多壁碳纳米管的重量，计算得到实施例1至实施例4所制备的多壁碳纳米管的相对产率如下表所示： In the above embodiments, according to the formula of the relative yield of multi-walled carbon nanotubes: Y c 1 =(W dep −W kat )/W kat , where W dep is the feed weight of the carbon source, and W kat is the prepared multi-wall carbon nanotubes. The weight of the walled carbon nanotubes, the calculated relative yields of the multi-walled carbon nanotubes prepared in Examples 1 to 4 are shown in the following table:
序号serial number W dep,g/g W dep ,g/g W kat,g/g W kat ,g/g Y c 1,％ Y c 1 ,%
实施例1Example 1 15.8415.84 8.88.8 8080
实施例2Example 2 13.9013.90 7.97.9 7676
实施例3Example 3 6.826.82 4.74.7 4545
实施例4Example 4 4.654.65 3.33.3 4141
实施例1至实施例4所制备的多壁碳纳米管的相对产率分别为80％、76％、45％和41％，均高于现有技术中所公开的采用化学气相沉积(CVD)合成多壁碳纳米管的相对产率。The relative yields of the multi-walled carbon nanotubes prepared in Examples 1 to 4 are 80%, 76%, 45% and 41%, respectively, which are higher than those disclosed in the prior art using chemical vapor deposition (CVD) Relative yields of synthetic multi-walled carbon nanotubes.
在上述实施例中，上述催化剂可包含选自作为包含钴(Co)的物质的四水合乙酸亚钴、六水合二氯化钴、六水合硝酸钴及七水合硫酸钴；作为含镍(Ni)的物质的六水合氯化镍、六水合硝酸镍、六水合硫酸镍及卤化镍；作为包含钒(V)的物质的偏钒酸铵、偏钒酸钠、偏钒酸钾、正钒酸钠、焦钒酸钠、硫酸氧钒、草酸氧钒、四氯化钒及三氯氧钒及它们的组合组成的组中的催化剂，但并不局限于此。In the above-mentioned embodiment, the above-mentioned catalyst may comprise cobaltous acetate tetrahydrate, cobaltous dichloride hexahydrate, cobaltous nitrate hexahydrate and cobaltous sulfate heptahydrate as a substance containing cobalt (Co) selected from the group consisting of cobalt (Ni) containing Nickel chloride hexahydrate, nickel nitrate hexahydrate, nickel sulfate hexahydrate and nickel halide as substances; ammonium metavanadate, sodium metavanadate, potassium metavanadate, sodium orthovanadate as substances containing vanadium (V) , sodium pyrovanadate, vanadyl sulfate, vanadyl oxalate, vanadium tetrachloride and vanadyl trichloride and the catalyst in the group consisting of combinations thereof, but not limited thereto.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity, all possible combinations of the technical features in the above-described embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be regarded as the scope described in this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的 普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only represent several embodiments of the present invention, and the descriptions thereof are specific and detailed, but should not be construed as a limitation on the scope of the invention patent. It should be pointed out that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention should be subject to the appended claims.

Claims (10)

  1. 一种制备多壁碳纳米管的方法，其特征在于，包括如下步骤：A method for preparing multi-walled carbon nanotubes, comprising the steps of:
    S1，将负载型催化剂置于化学气相沉积(CVD)设备中，在常压下通入保护气体，同时加热至550-600℃；S1, the supported catalyst is placed in a chemical vapor deposition (CVD) equipment, and a protective gas is introduced under normal pressure, while heating to 550-600 ° C;
    S2，常压下通入烃类气体；S2, pass hydrocarbon gas under normal pressure;
    S3，混合气体反应不超过30min后在所述保护气体氛围下冷却至室温。S3, the mixed gas is cooled to room temperature under the protective gas atmosphere after the reaction of the mixed gas does not exceed 30 min.
  2. 根据权利要求1所述的方法，其特征在于：所述保护气体与所述烃类气体的体积比为3:1，所述烃类气体是甲烷、乙烯、乙炔、液化石油气或它们的组合，所述保护气体为氮气或氩气。The method according to claim 1, wherein the volume ratio of the protective gas to the hydrocarbon gas is 3:1, and the hydrocarbon gas is methane, ethylene, acetylene, liquefied petroleum gas or a combination thereof , the protective gas is nitrogen or argon.
  3. 根据权利要求2所述的方法，其特征在于：所述烃类气体是乙炔，所述乙炔和氮气分别以50mL/min、150mL/min的流速供给。The method according to claim 2, wherein the hydrocarbon gas is acetylene, and the acetylene and nitrogen are supplied at flow rates of 50 mL/min and 150 mL/min, respectively.
  4. 根据权利要求3所述的方法，其特征在于：所述步骤S1的加热速率为10℃/min。The method according to claim 3, wherein the heating rate of the step S1 is 10°C/min.
  5. 根据权利要求4所述的方法，其特征在于：所述负载型催化剂包括载体以及含有负载于所述载体上的Ni和Co金属催化剂，金属催化剂中Ni和Co的摩尔比为1：2.4-2.6。The method according to claim 4, wherein the supported catalyst comprises a carrier and a metal catalyst containing Ni and Co supported on the carrier, and the molar ratio of Ni and Co in the metal catalyst is 1:2.4-2.6 .
  6. 根据权利要求5所述的方法，其特征在于：所述负载型催化剂包括载体以及含有负载于所述载体上的Ni和V金属催化剂，金属催化剂中Ni和V的摩尔比为1：1.1-1.3The method according to claim 5, wherein the supported catalyst comprises a carrier and a metal catalyst containing Ni and V supported on the carrier, and the molar ratio of Ni and V in the metal catalyst is 1:1.1-1.3
  7. 根据权利要求6所述的方法，其特征在于：所述负载型催化剂包括载体以及含有负载于所述载体上的Ni、Co和V金属催化剂，金属催化剂中Ni、Co和V的摩尔比为1：2.5-2.6：2.6-2.8。The method according to claim 6, wherein the supported catalyst comprises a carrier and a metal catalyst containing Ni, Co and V supported on the carrier, and the molar ratio of Ni, Co and V in the metal catalyst is 1 :2.5-2.6:2.6-2.8.
  8. 根据权利要求5-7任一项权利要求所述的方法，其特征在于：所述载体包括Al 2O 3、MgO、SiO 2或者它们的组合。 The method according to any one of claims 5-7, wherein the carrier comprises Al 2 O 3 , MgO, SiO 2 or a combination thereof.
  9. 根据权利要求8所述的方法，其特征在于：所述负载型催化剂通过以下步骤进行制备：将金属催化剂溶解在溶剂中来制备金属催化剂的水溶液，再加入载体混合，将悬浮液蒸发，得到的沉淀物在110℃下干燥12h,在350-550℃下加热2h得到所述负载型催化剂。The method according to claim 8, wherein the supported catalyst is prepared by the following steps: dissolving the metal catalyst in a solvent to prepare an aqueous solution of the metal catalyst, then adding a carrier to mix, evaporating the suspension, and obtaining The precipitate was dried at 110 °C for 12 h, and heated at 350-550 °C for 2 h to obtain the supported catalyst.
  10. 根据权利要求9所述的方法，其特征在于：所述溶剂是水、醇或它们的组合；并且进一步包括柠檬酸，作为所述载体材料的水溶液中的活化剂。 10. The method of claim 9, wherein: the solvent is water, alcohol, or a combination thereof; and further comprising citric acid as an activator in the aqueous solution of the carrier material.
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CN115477300A (en) * 2022-08-03 2022-12-16 烯湾科城(广州)新材料有限公司 Carbon nano tube, fluidized bed preparation process thereof and conductive agent

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