CN1140448C - Process of nickel catalytic cracking methane preparing carbon nanometer tube - Google Patents
Process of nickel catalytic cracking methane preparing carbon nanometer tube Download PDFInfo
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- CN1140448C CN1140448C CNB001028243A CN00102824A CN1140448C CN 1140448 C CN1140448 C CN 1140448C CN B001028243 A CNB001028243 A CN B001028243A CN 00102824 A CN00102824 A CN 00102824A CN 1140448 C CN1140448 C CN 1140448C
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Abstract
The present invention discloses a method for preparing a carbon nanotube with the catalytic cracking of methane by nickel, which comprises the steps as follows: nickel oxide is adopted as a catalyst precursor, and a certain amount of nickel oxide is placed in a reactor; the nickel oxide is heated to a certain temperature, and hydrogen gas is adopted for reducing reaction for a certain time; reaction gas is led to crack the nickel oxide to prepare a carbon nanotube. The present invention is characterized in that the reaction gas is the gas mixture containing methane, and the gas mixture is the mixture of methane and hydrogen gas or the mixture of methane, hydrogen gas and inactive gas containing argon. The present invention has the characteristics of high yield, simple technological process, stable reaction and low cost.
Description
The invention relates to a method for preparing a carbon nano tube by cracking methane by taking nickel as a catalyst, belonging to the preparation technology of the carbon nano tube.
The carbon nano tube has excellent comprehensive mechanical properties such as high elastic modulus, high Young modulus and low density, and excellent electrical properties, thermal properties and adsorption properties, so the carbon nano tube can play an important role in the fields of microelectronics, nano composite materials, energy, environmental protection, catalysis, biomedicine, national defense, aerospace and the like.
At present, some patents and literature reports on a method for preparing carbon nanotubes by cracking methane with a catalyst, such as a CN1170631A patent, disclose that an oxide of a transition metal is used as a catalyst to crack methane to prepare carbon nanotubes, the reaction temperature is 600 ℃, the space velocity for introducing methane is 2400/h, the reaction time is 20 minutes, and 33 mg of carbon nanotubes are obtained after a product is purified; the document "A.M.Cassell, et al.J.Phys.chem.B 1999, 103, 6484-: preparing a single-walled carbon nanotube by catalytically cracking methane by using a Fe/Mo bimetallic supported catalyst, wherein the reaction temperature is 900 ℃, the reaction time is 30 minutes, and the maximum yield is about 2%; the document "V.B.Fenelonov, et al., Carbon 1997, 35(8), 1129-: the Ni/Cu bimetallic supported catalyst is used for catalytically cracking methane to prepare the carbon nano tube, the reaction temperature is 565 ℃, and the reaction time can reach 38 hours at most.
The main technique of the carbon nanotube preparation method reported in the above patent and literature is to select a catalyst and then perform a methane cracking reaction by using a single methane gas or a single carbon monoxide gas.
The invention aims to provide a method for preparing a carbon nano tube by catalytically cracking methane with nickel. The method has the characteristics of high yield, simple process, stable reaction and low cost.
In order to achieve the above object, the present invention is realized by the following technical solutions. The nickel oxide prepared by adopting the known coprecipitation method is used as a catalyst matrix, firstly, quantitative nickel oxide is placed in a reactor, after the nickel oxide is heated to the temperature of 550 ℃ and 650 ℃, hydrogen is used for reducing for 0.5 to 1.5 hours, and then reaction gas is introduced to crack the nickel oxide to prepare the carbon nano tube, and the method is characterized in that: the introduced reaction gas is mixed gas containing methane, the flow rate of the mixed gas is 50-300 ml/min, and the reaction temperature is 500-800 ℃.
The mixed gas containing methane is a mixed gas of methane and hydrogen, and the ratio of the mixed gas containing methane to hydrogen is 20: 1-1: 1 (volume ratio); or the mixture of methane, hydrogen and inert gas including argon in the volume ratio of 4-6 to 1-2 to 3-5.
The optimal reaction temperature for the preparation reaction is 550-650 ℃.
When the reaction gas is a mixed gas of methane and hydrogen, the optimal CH4And H2The ratio of (A) to (B) is 10: 1-3: 1 (volume ratio).
The present invention will be described in detail below.
The reaction process expression of the invention is as follows: the catalyst is a nickel catalyst.
In the above reaction, there are many factors that affect the yield (or methane conversion) of carbon nanotubes and their morphology and crystallinity. Experiments prove that hydrogen with a certain concentration is kept in the feed gas, so that the stable and continuous growth of the carbon nano tube can be ensured, the yield (or methane conversion rate) of the carbon nano tube is improved, and the morphology of the carbon nano tube is improved; experiments also prove that the yield of the carbon nano tube (or the methane conversion rate) can be obviously increased by adding proper inert gas into the feed gas. In addition, the reduction reaction temperature is increased, and the catalyst with different amounts is adopted, so that the effects of improving the yield of the product and improving the appearance are influenced.
The carbon nanotube product has outer diameter of 10-80nm, inner diameter of 2-15nm and length of micron-mm level.
Compared with the prior art, the method has the characteristics that the carbon nano tube can stably and continuously grow, the product yield is high, generally 25-35%, and the maximum can reach 40%; low cost, high efficiency and simple method.
The invention is further illustrated by the following examples and comparative examples.
The first embodiment is as follows:
transferring 0.3g of catalyst into a quartz reaction tube, heating to 600 ℃, and reducing for 1 hour by using hydrogen; then introducing mixed gas with the ratio of methane to hydrogen being 20: 1, wherein the total flow rate is 110 ml/min; the reaction was carried out for 1 hour, and the product yieldwas 2%.
Example two:
the reaction was carried out for 1 hour with the same conditions and procedure as in the example one except that the ratio of methane to hydrogen was changed to 10: 1, and the product yield was 25%.
Example three:
the reaction was carried out for 1 hour with the same conditions and procedure as in the example one except that the ratio of methane to hydrogen was changed to 4: 1, and the product yield was 21%.
Example four:
the reaction was carried out for 1 hour with the same conditions and procedure as in the example one except that the ratio of methane to hydrogen was changed to 3: 2, and the product yield was 5%.
Example five:
the reaction was carried out for 1 hour with the same conditions and procedure as in the example one except that the ratio of methane to hydrogen was changed to 1: 1, and the product yield was 0.4%.
Example six:
the reaction was carried out for 1 hour under the same conditions and in the same manner as in the example-except that the ratio of methane to hydrogen to argon was 5: 1: 4, and the yield of the product was 40%.
Example seven:
transferring 0.3g of catalyst into a quartz reaction tube, heating to 600 ℃, and reducing for 0.5 hour by using hydrogen; then introducing mixed gas with the ratio of methane to hydrogen being 10: 1, wherein the total flow rate is 110 ml/min; the reaction was carried out for 1 hour, and the product yield was 18%.
Example eight:
the reaction was carried out for 2 hours under the same conditions and procedures as in example seven, and the product yield was 19%.
Example nine:
the reaction was carried out for 3 hours under the same conditions and in the same manner as in the seventh example, giving a product yield of 18%.
Example ten:
the reaction was carried out for 4 hours under the same conditions and in the same manner as in example seven, and the product yield was 19%.
Comparative example one:
the reaction temperature was 800 ℃ as in the other conditions and steps of the example, and only a very small amount of carbon nanotubes were produced, and the morphology was very poor.
Comparative example two:
the same procedure as in example one, except that CH was introduced4The reaction time is 2 hours, the product yield is less than 1 percent, and the nano carbon particles are more.
Claims (3)
1. A method for preparing carbon nanotube by catalytic cracking methane with nickel, it adopts nickel oxide that the coprecipitation method prepares as catalyst parent, put nickel oxide into reactor at first, after heating to 550 duC-650 duC, reduce carbon nanotube for 0.5-1.5 hours with hydrogen, then inject the reaction gas, make its rank prepare carbon nanotube, characterized by that: the introduced reaction gas is mixed gas containing methane, the flow rate of the mixed gas is 50-300 ml/min, and the reaction temperature is 500-; wherein the mixed gas containing methane is any one of the following gases:
1) the mixed gas of methane and hydrogen with the mixing ratio of 20: 1-1: 1;
2) the mixed gas of methane, hydrogen and inert gas including argon is mixed in the ratio of 4-6 to 1-2 to 3-5.
2. The method for preparing carbon nanotubes by catalytically cracking methane with nickel according to claim 1, wherein: the reaction temperature is 550-650 ℃.
3. The method for preparing carbon nanotubes by catalytically cracking methane with nickel according to claim 1, wherein: the mixing ratio of the methane and the hydrogen is 10: 1-3: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001028243A CN1140448C (en) | 2000-03-07 | 2000-03-07 | Process of nickel catalytic cracking methane preparing carbon nanometer tube |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001028243A CN1140448C (en) | 2000-03-07 | 2000-03-07 | Process of nickel catalytic cracking methane preparing carbon nanometer tube |
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| CN1266018A CN1266018A (en) | 2000-09-13 |
| CN1140448C true CN1140448C (en) | 2004-03-03 |
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| CNB001028243A Expired - Fee Related CN1140448C (en) | 2000-03-07 | 2000-03-07 | Process of nickel catalytic cracking methane preparing carbon nanometer tube |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141250C (en) * | 2001-05-25 | 2004-03-10 | 清华大学 | Process and reactor for continuously preparing nm carbon tubes with fluidized bed |
| CN100337909C (en) | 2005-03-16 | 2007-09-19 | 清华大学 | Growth method carbon nanotube array |
| CN100376477C (en) | 2005-03-18 | 2008-03-26 | 清华大学 | Growth appts. of carson nanotube array and growth method of multi-wall carbon nanotube array |
| CN100344532C (en) | 2005-03-25 | 2007-10-24 | 清华大学 | Carbon nanotube array growing device |
| CN100337910C (en) | 2005-03-31 | 2007-09-19 | 清华大学 | Carbon nanotube array growing method |
| CN100431950C (en) * | 2005-06-03 | 2008-11-12 | 中国科学院长春应用化学研究所 | Method for synthesizing carbon nanotube and its compounds by polyolefin combustion with nickel oxide as catalyst |
| CN100519408C (en) * | 2005-08-10 | 2009-07-29 | 中国科学院长春应用化学研究所 | Preparing hydrogen and Nano carbon tube through catalytic cracking polyolefine |
| CN100368080C (en) * | 2005-08-29 | 2008-02-13 | 天津大学 | Process for preparing carbon nano tube and carbon onion by Ni/Al catalyst chemical gas phase deposition |
| CN1775671B (en) * | 2005-12-16 | 2010-05-05 | 中国科学院长春应用化学研究所 | Method for preparing carbon nano tube by nickel compound catalytic combustion of polyolefin |
| CN102659429B (en) * | 2012-05-02 | 2014-01-01 | 濮阳濮耐高温材料（集团）股份有限公司 | Ventilation functional element for carbon nanotube reinforced ventilation channel and preparation method thereof |
| CN105006376B (en) * | 2015-07-13 | 2018-12-21 | 华北电力大学 | A kind of preparation method of carbon nanotube and nickel oxide composite material |
| EP3775113B1 (en) | 2018-04-09 | 2023-06-14 | Shell Internationale Research Maatschappij B.V. | A process for producing hydrogen and solid carbon products |
| CN108642430A (en) * | 2018-05-16 | 2018-10-12 | 安徽三环水泵有限责任公司 | A kind of process of surface treatment of slush pump pump shaft |
| CN111167460A (en) * | 2019-12-31 | 2020-05-19 | 四川天采科技有限责任公司 | Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof |
| CN111362253B (en) * | 2020-03-13 | 2021-09-21 | 成都科汇机电技术有限公司 | Carbon nano tube prepared by catalytic cracking of hydrocarbon by gas-phase damping method, device and method |
| CN113371694A (en) * | 2021-07-16 | 2021-09-10 | 中国石油化工股份有限公司 | Method and device for preparing carbon nano tube and hydrogen |
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