CN112758914A - Method for preparing carbon nano tube by using alkali metal in fly ash as catalyst - Google Patents
Method for preparing carbon nano tube by using alkali metal in fly ash as catalyst Download PDFInfo
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- CN112758914A CN112758914A CN202011513748.3A CN202011513748A CN112758914A CN 112758914 A CN112758914 A CN 112758914A CN 202011513748 A CN202011513748 A CN 202011513748A CN 112758914 A CN112758914 A CN 112758914A
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- 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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- 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
- C01B2202/30—Purity
Abstract
The invention discloses a method for preparing carbon nanotubes by using alkali metal in fly ash as a catalyst, belongs to the technical field of carbon materials, and aims to provide a method for efficiently utilizing the alkali metal in the fly ash, and a method for improving the efficiency of preparing the carbon nanotubes by using a fly ash catalyst. Alkali metal in the fly ash is used as a catalyst to catalyze coal pyrolysis to prepare the carbon nano tube, and can be used as a catalyst for generating the carbon nano tube to convert coal into the carbon nano tube. Compared with the prior art, the method utilizes coal resources and changes coal with low added value into coal-based carbon nano tubes with high added value. Therefore, the coal-based carbon nano tube prepared by using the fly ash as a catalyst generated by the carbon nano tube has more economic advantages and product advantages.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a method for preparing a carbon nano tube by using alkali metal in fly ash as a catalyst.
Background
The fly ash is fine solid particles in flue gas ash generated by fuel combustion, contains a large amount of oxides of silicon, iron, aluminum, calcium, magnesium, sodium, potassium and sulfur and various trace elements besides unburnt coal particles, wherein the main phase is vitreous body and accounts for 50-80%. It can be seen from the existing patent documents related to fly ash that fly ash is used as an adsorbent or filter aid for treating sewage and is mainly consumed as a building material, while there are many reports on the utilization of alkali metal in fly ash as a catalyst and research on extraction of heavy metal from fly ash, but there are few reports on the method for preparing a carbon nanotube catalyst by utilizing fly ash.
Coal is used as a main energy source for industry and civilian use in China, is mainly used for combustion power generation and coking at present, fly ash generated by combustion cannot be effectively controlled, reasonably utilized and converted, and pollution is increasingly serious. Meanwhile, resource utilization of coal is also imminent, and how to realize low-carbon and high-efficiency utilization becomes an important research direction.
Carbon nanotubes are unique one-dimensional carbon materials, have excellent mechanical, electromagnetic, optical and thermodynamic properties, and are widely used in various fields. The main methods for preparing carbon nanotubes include an arc method, a laser evaporation method, a plasma method, a catalytic chemical deposition method and the like. The catalytic chemical deposition method is considered to be the most potential method for preparing carbon nanotubes on a large scale at low cost and high yield. Under the action of catalyst, the carbon-containing gas is catalytically decomposed to form carbon nanotube. Nowadays, how to produce carbon nanotubes more efficiently and at low cost becomes a matter of great concern. The fly ash contains a large amount of oxides of silicon, iron, aluminum, calcium, magnesium, sodium, potassium and sulfur and various trace elements, iron can be used as a catalyst to catalyze coal pyrolysis to prepare the carbon nano tube, and when sodium and hydroxyl are combined, coal can be perforated, and simultaneously the coal can be used as a catalyst generated by the carbon nano tube to change the coal into the carbon nano tube.
In the patent of cn201610333775.x, the fly ash is used as a catalyst, the whole production steps and the catalytic product have large limitations, the alkali metal in the fly ash is not effectively utilized, and the alkali metal in the fly ash has a positive effect on the generation of the fly ash, so that the fly ash can be used as a catalyst with high efficiency, low price and low pollution in catalyzing the generation of carbon nanotubes.
The prior patent documents related to the fly ash show that the fly ash can be used as an adsorbent or a filter aid for treating sewage and can be used as a catalyst after the fly ash is activated, and the catalyst has more impurities and still has larger pollution because the fly ash is not subjected to fine treatment. But the method of using alkali metal in the fly ash as the catalyst for preparing the carbon nano tube does not exist. As a common domestic waste product, the fly ash can be used as a high-efficiency catalyst for generating the carbon nano tube by using the residual alkali metal contained in the fly ash.
Therefore, a technology for preparing the coal-based carbon nano tube by catalytic pyrolysis of coal by using alkali metal in the coal ash as a catalyst and adopting a simple preparation method is urgently needed, so that the utilization rate of the coal ash can be improved, and the resource utilization of carbon can be increased.
Disclosure of Invention
The invention aims to provide a method for efficiently utilizing alkali metal in fly ash, which is a method for improving the efficiency of preparing carbon nanotubes by using a fly ash catalyst.
The invention adopts the following technical scheme:
a method for preparing carbon nano-tubes by using alkali metal in fly ash as a catalyst comprises the following steps:
firstly, crushing and screening fly ash to obtain powdered fly ash A with the particle size of 1-10mm, and taking 1-10 parts of powdered fly ash A;
secondly, placing the fly ash A obtained in the first step in a muffle furnace, raising the temperature to 600 ℃ at the heating rate of 3-10 ℃/min, standing at 600 ℃ for 1-5 hours for roasting to obtain powder B, cooling the powder B to room temperature, adding 50-5000 parts of 2mol/L nitric acid solution, fully stirring for 2 hours for acidification treatment to obtain treated mixed solution containing alkali metal nitrate, standing the mixed solution for 30 minutes, filtering to obtain supernatant C without solid precipitate, and fully filtering for 3-5 times to obtain final supernatant D;
thirdly, crushing and screening the coal powder to obtain coal powder E with the particle size of 1-10mm, and taking 100 plus 1000 parts of coal powder E;
step four, dropwise adding the supernatant D obtained in the step two into the coal powder E obtained in the step three, loading by adopting an isometric dipping method, fully stirring while loading, wherein the overall stirring time is 3-12h, and after stirring for 2h, beginning dropwise adding 4-400 parts of strong ammonia water to finally obtain uniformly loaded coal powder F containing the alkali metal nitrate;
fifthly, putting the pulverized coal F obtained in the fourth step into a drying oven at 80-100 ℃ for drying for 6-24 hours until the pulverized coal F is completely dried to obtain dried pulverized coal F;
sixthly, transferring the dried coal powder F obtained in the fifth step into a muffle furnace, heating to 800-1000 ℃ at a heating rate of 3-5 ℃/min, and staying at the final heating temperature for 1-6h to enable the carbon nano tube to grow on the surface of the coal powder F, thereby finally obtaining coal powder G containing the coal-based carbon nano tube;
and seventhly, separating and purifying the coal powder G obtained in the sixth step to finally obtain the purified coal-based carbon nano tube.
In the third step, the pulverized coal comprises any one of lignite and long-flame coal.
In the fourth step, the dropping speed of the strong aqua ammonia is 1-10 drops/min.
And in the fifth step, the separation and purification are carried out by adopting 1mol/L nitric acid for acid washing to remove impurities.
The invention has the following beneficial effects:
the invention uses alkali metal in the fly ash coal as catalyst, and reduces the environmental pollution rate while using the alkali metal remained in the fly ash. Coal is used as a main energy source for industry and civilian use in China, fly ash generated by combustion cannot be effectively controlled, reasonably utilized and converted, and pollution is increasingly serious. Effectively utilizes alkali metal in the fly ash, thereby improving the utilization rate of the fly ash. The invention can utilize the positive promotion characteristic of alkali metals such as iron, sodium, potassium and the like in the fly ash to the generation of the carbon nano tube, can reduce the environmental pollution as much as possible, and simultaneously saves resources. Alkali metal in the fly ash is used as a catalyst to catalyze coal pyrolysis to prepare the carbon nano tube, and can be used as a catalyst for generating the carbon nano tube to convert coal into the carbon nano tube. Compared with the prior art, the method utilizes coal resources and changes coal with low added value into coal-based carbon nano tubes with high added value. Therefore, the coal-based carbon nano tube prepared by using the fly ash as a catalyst generated by the carbon nano tube has more economic advantages and product advantages.
Drawings
Fig. 1 is a scanning electron microscope image i of a carbon nanotube grown on a carrier according to an embodiment of the present invention.
FIG. 2 is a scanning electron microscope II showing the carbon nanotubes grown on a carrier according to the second embodiment of the present invention.
Detailed Description
Example 1
Crushing and screening the fly ash to obtain the fly ash with the granularity radius of 10mm, and taking 10g of the fly ash;
step two, placing the fly ash obtained in the step one in a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 3 ℃/min, standing at 600 ℃ for 5 hours for roasting to obtain powder B, cooling the powder B to room temperature, adding 5000ml of 2mol/L nitric acid solution, fully stirring for 2 hours for acidification treatment to obtain treated mixed solution containing alkali metal nitrate, standing the mixed solution for 30 minutes, filtering to obtain supernatant C without solid precipitate, and fully filtering for 5 times to obtain final supernatant D;
crushing and screening pulverized lignite to obtain pulverized coal E with the particle size of 1-10mm, and taking 1000g of pulverized coal E;
step four, dropwise adding the supernatant D obtained in the step two into the coal powder E obtained in the step three, loading by adopting an isometric immersion method, fully stirring while loading, wherein the overall stirring time is 12 hours, and after stirring for 2 hours, dropwise adding 400ml of strong ammonia water at a dropping rate of 10 drops/min to finally obtain uniformly loaded coal powder F containing the alkali metal nitrate;
step five, putting the pulverized coal F obtained in the step four in a drying oven at 100 ℃ for drying for 24 hours until the pulverized coal F is completely dried to obtain dried pulverized coal F;
step six, transferring the dried coal powder F obtained in the step five into a muffle furnace, heating to 1000 ℃ at a heating rate of 5 ℃/min, and staying for 6 hours at the final heating temperature to enable the carbon nano tubes to grow on the surface of the coal powder F, so as to finally obtain coal powder G containing the coal-based carbon nano tubes;
and seventhly, separating and purifying the coal powder G obtained in the sixth step to finally obtain the purified coal-based carbon nano tube, and carrying out acid washing on the separated and purified coal-based carbon nano tube by adopting 1mol/L nitric acid to remove impurities.
Example 2
Crushing and screening the fly ash to obtain the fly ash with the granularity radius of 10mm, and taking 1g of the fly ash;
step two, placing the fly ash obtained in the step one in a muffle furnace, raising the temperature to 600 ℃ at a heating rate of 10 ℃, standing for 1h at 600 ℃ for roasting to obtain powder B, cooling the powder B to room temperature, adding 50ml of 2mol/L nitric acid solution, fully stirring for 2h for acidification treatment to obtain treated mixed solution containing alkali metal nitrate, standing the mixed solution for 30min, filtering to obtain supernatant C without solid precipitate, and fully filtering for 5 times to obtain final supernatant D;
crushing and screening the long flame coal powder to obtain coal powder E with the particle size of 5-10mm, and taking 1000g of the coal powder E;
step four, dropwise adding the supernatant D obtained in the step two into the coal powder E obtained in the step three, loading by adopting an isometric immersion method, fully stirring while loading, wherein the whole stirring time is 5 hours, and after stirring is carried out for 2 hours, beginning dropwise adding 4ml of strong ammonia water at a dropping rate of 1 drop/min to finally obtain uniformly loaded coal powder F containing the alkali metal nitrate;
step five, putting the pulverized coal F obtained in the step four in a drying oven at 100 ℃ for drying for 6 hours until the pulverized coal F is completely dried to obtain dried pulverized coal F;
step six, transferring the dried coal powder F obtained in the step five into a muffle furnace, heating to 800 ℃ at a heating rate of 3 ℃/min, and staying for 2 hours at the final heating temperature to enable the carbon nano tubes to grow on the surface of the coal powder F, so as to finally obtain coal powder G containing the coal-based carbon nano tubes;
and seventhly, separating and purifying the coal powder G obtained in the sixth step to finally obtain the purified coal-based carbon nano tube, and carrying out acid washing on the separated and purified coal-based carbon nano tube by adopting 1mol/L nitric acid to remove impurities.
Claims (4)
1. A method for preparing carbon nano-tubes by using alkali metal in fly ash as a catalyst is characterized in that: the method comprises the following steps:
firstly, crushing and screening fly ash to obtain powdered fly ash A with the particle size of 1-10mm, and taking 1-10 parts of powdered fly ash A;
secondly, placing the fly ash A obtained in the first step in a muffle furnace, raising the temperature to 600 ℃ at a speed of 3-10 ℃/min, standing at 600 ℃ for 1-5 hours for roasting to obtain powder B, cooling the powder B to room temperature, adding 50-5000 parts of 2mol/L nitric acid solution, fully stirring for 2 hours for acidification treatment to obtain treated mixed solution containing alkali metal nitrate, standing the mixed solution for 30 minutes, filtering to obtain supernatant C without solid precipitate, and fully filtering for 3-5 times to obtain final supernatant D;
thirdly, crushing and screening the coal powder to obtain coal powder E with the particle size of 1-10mm, and taking 100 plus 1000 parts of coal powder E;
step four, dropwise adding the supernatant D obtained in the step two into the coal powder E obtained in the step three, loading by adopting an isometric dipping method, fully stirring while loading, wherein the overall stirring time is 3-12h, and after stirring for 2h, beginning dropwise adding 4-400 parts of strong ammonia water to finally obtain uniformly loaded coal powder F containing the alkali metal nitrate;
fifthly, putting the pulverized coal F obtained in the fourth step into a drying oven at 80-100 ℃ for drying for 6-24 hours until the pulverized coal F is completely dried to obtain dried pulverized coal F;
sixthly, transferring the dried coal powder F obtained in the fifth step into a muffle furnace, heating to 800-1000 ℃ at a speed of 3-5 ℃/min, and staying at the final heating temperature for 1-6h to enable the carbon nano tube to grow on the surface of the coal powder F, thereby finally obtaining coal powder G containing the coal-based carbon nano tube;
and seventhly, separating and purifying the coal powder G obtained in the sixth step to finally obtain the purified coal-based carbon nano tube.
2. The method for preparing carbon nanotubes by using alkali metal in fly ash as a catalyst according to claim 1, wherein: in the third step, the pulverized coal comprises any one of lignite and long-flame coal.
3. The method for preparing carbon nanotubes by using alkali metal in fly ash as a catalyst according to claim 1, wherein: in the fourth step, the dropping speed of the strong aqua ammonia is 1-10 drops/min.
4. The method for preparing carbon nanotubes by using alkali metal in fly ash as a catalyst according to claim 1, wherein: and in the fifth step, the separation and purification are carried out by adopting 1mol/L nitric acid for acid washing to remove impurities.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232539A (en) * | 2022-09-05 | 2022-10-25 | 华电电力科学研究院有限公司 | Wear-resistant UV (ultraviolet) coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130078374A1 (en) * | 2011-09-28 | 2013-03-28 | King Abdulaziz University | Method of forming carbon nanotubes from carbon-rich fly ash |
| CN106006604A (en) * | 2016-05-31 | 2016-10-12 | 太原理工大学 | Method for producing carbon nanotubes through catalytic pyrolysis of solid carbon materials |
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- 2020-12-21 CN CN202011513748.3A patent/CN112758914A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130078374A1 (en) * | 2011-09-28 | 2013-03-28 | King Abdulaziz University | Method of forming carbon nanotubes from carbon-rich fly ash |
| CN106006604A (en) * | 2016-05-31 | 2016-10-12 | 太原理工大学 | Method for producing carbon nanotubes through catalytic pyrolysis of solid carbon materials |
Non-Patent Citations (1)
| Title |
|---|
| 于晓彩著: "《粉煤灰与造纸废水资源化技术的研究》", 31 August 2013, 辽宁教育出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115232539A (en) * | 2022-09-05 | 2022-10-25 | 华电电力科学研究院有限公司 | Wear-resistant UV (ultraviolet) coating and preparation method thereof |
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