CN112266261B - Method for in-situ growth of carbon nanotubes by using tail gas generated by polymer cracking - Google Patents

Method for in-situ growth of carbon nanotubes by using tail gas generated by polymer cracking Download PDF

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CN112266261B
CN112266261B CN202011176023.XA CN202011176023A CN112266261B CN 112266261 B CN112266261 B CN 112266261B CN 202011176023 A CN202011176023 A CN 202011176023A CN 112266261 B CN112266261 B CN 112266261B
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张雨雷
付艳芹
韩丽媛
张建
李贺军
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Northwestern Polytechnical University
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Abstract

The invention relates to a method for in-situ growth of a carbon nano tube by utilizing tail gas generated by polymer cracking, which is characterized in that an HfC nano wire and a carbon nano tube are prepared simultaneously by cracking an organic precursor of HfC. The method has the advantages of simple synthesis process, low cost, low requirement on equipment and the like. The method can be widely applied to the field of polymer conversion ceramics and has the potential of developing large-scale industrial production.

Description

Method for in-situ growth of carbon nanotubes by using tail gas generated by polymer cracking
Technical Field
The invention belongs to a nano material preparation technology, and relates to a method for in-situ growth of a carbon nano tube by utilizing tail gas generated by polymer pyrolysis.
Background
Polymer derived ceramics have been extensively studied for their unique advantages in ceramic fibers, ceramic coatings, nanocomposite ceramics, and in additive manufacturing. Ceramics converted from polymerDuring the process of porcelain, the organic precursor is continuously cracked to generate small molecular substances, such as H2O，CO，CO2，CH4And the like. Because part of the organic ceramic precursor is high in preparation cost and the ceramic yield of the polymer is less than 40%, more than 50% of the organic precursor is lost in a gas form in the using process. Before the invention is put forward, the micromolecular compound generated in the process of converting the polymer into the ceramic is taken as tail gas to be directly discharged into the air, which not only can cause a great deal of resource waste, but also is not beneficial to environmental protection. Economic benefits are created if these by-products from polymer cracking can be fully utilized.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a method for growing the carbon nano tube in situ by using tail gas generated by polymer pyrolysis, and provides a method for simultaneously synthesizing the HfC nano wire and the carbon nano tube in situ by using small molecular gas generated by polymer pyrolysis.
Technical scheme
A method for in-situ growth of carbon nanotubes by using tail gas generated by polymer cracking is characterized by comprising the following steps:
step 1, preparation of low-density C/C: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4Gas is deposited for 20-100 h to obtain the low-density C/C composite material;
step 2, preparing a catalyst solution: stirring nickel nitrate hexahydrate and ethanol until the nickel nitrate hexahydrate is dissolved, soaking the cleaned low-density C/C composite material and the carbon cloth in the prepared solution for 5-12 hours, taking out, and drying in an oven at 40-70 ℃;
and step 3: mixing an HfC organic precursor with the mass fraction of 1: 20-1: 5 with a solvent, and stirring until the HfC organic precursor is completely dissolved; putting the low-density C/C composite material obtained in the step 2 into the solution for soaking for 1-3 h, taking out, and putting the low-density C/C composite material into an oven at 120-180 ℃ for drying and curing for 3-8 h;
and 4, step 4: putting the carbon cloth obtained in the step 2 and the low-density C/C composite material obtained in the step 3 into a tubular furnace at the same time, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is respectively placed at different positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the temperature of the furnace is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured for 0.5-3 h at the temperature, then the temperature is increased to 1300-1800 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 1-10 h; and after the heat preservation is finished, closing the heating power supply to naturally cool. Through the preparation process, the HfC nanowire growing in situ is obtained on the surface and inside the low-density C/C composite material, and the carbon nanotube grows in situ on the surface of the carbon cloth.
The HfC organic precursor is replaced by an organic precursor of the ultra-high temperature ceramic.
Organic precursors of the ultra-high temperature ceramic include, but are not limited to: ZrC, TaC, HfB2Or ZrB2An organic precursor of a ceramic.
The molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L.
The HfC organic precursor is a solid or liquid HfC organic precursor or a mixture of solid and liquid HfC organic precursors.
Such solvents include, but are not limited to: toluene, xylene or divinylbenzene solutions can dissolve the organic solvent of the precursor.
Advantageous effects
The invention provides a method for in-situ growth of a carbon nano tube by utilizing tail gas generated by polymer cracking, which is characterized in that an HfC nano wire and a carbon nano tube are prepared simultaneously by cracking an organic precursor of HfC. The method has the advantages of simple synthesis process, low cost, low requirement on equipment and the like. The method can be widely applied to the field of polymer conversion ceramics and has the potential of developing large-scale industrial production.
Drawings
FIG. 1 is a schematic of the process of the present invention;
fig. 2 is a microstructure and XRD pattern of the HfC nanowire prepared by the present invention;
FIG. 3 shows the micro-morphology of the carbon nanotubes prepared by the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
the invention aims to provide a method for simultaneously in-situ synthesizing HfC nanowires and carbon nanotubes by cracking a polymer by using micromolecular gas generated by polymer pyrolysis, which is characterized by comprising the following steps of:
step 1: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4And (4) gas is deposited for 20-100 h to obtain the low-density C/C composite material.
Step 2: preparing a catalyst solution: respectively weighing nickel nitrate hexahydrate and ethanol in a beaker, wherein the molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L, and stirring on a magnetic stirrer until the nickel nitrate hexahydrate is completely dissolved; and (3) putting the cleaned low-density C/C composite material and the carbon cloth into the prepared solution, soaking for 5-12 h, taking out, and putting into an oven at 40-70 ℃ for drying for later use.
And step 3: weighing the following components in parts by mass of 1: 20-1: 5 of the HfC organic precursor and the divinylbenzene solution are placed in a beaker and heated and stirred on a magnetic stirrer until the HfC organic precursor is completely dissolved. And (3) putting the low-density C/C composite material obtained in the step (2) into the solution, soaking for 1-3 h, taking out, and putting into an oven at 120-180 ℃ for drying and curing for 3-8 h for later use.
And 4, step 4: and (3) simultaneously putting the carbon cloth obtained in the step (2) and the low-density C/C composite material obtained in the step (3) into a tubular furnace, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is placed at different temperature positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the temperature of the furnace is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured for 0.5-3 h at the temperature, the temperature is increased to 1300-1800 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 1-10 h. And after the heat preservation is finished, closing the heating power supply to naturally cool. Through the preparation process, the HfC nanowire growing in situ is obtained on the surface and inside the low-density C/C composite material, and the carbon nanotube grows in situ on the surface of the carbon cloth.
Example 1:
step 1: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4And (4) gas is deposited for 20-100 h to obtain the low-density C/C composite material.
Step 2: preparing a catalyst solution: respectively weighing nickel nitrate hexahydrate and ethanol in a beaker, wherein the molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L, and stirring on a magnetic stirrer until the nickel nitrate hexahydrate is completely dissolved; and (3) putting the cleaned low-density C/C composite material and the carbon cloth into the prepared solution, soaking for 5-12 h, taking out, and putting into an oven at 40-70 ℃ for drying for later use.
And step 3: weighing an HfC organic precursor and a divinylbenzene solution with the mass fraction of 1:20 in a beaker, heating and stirring the mixture on a magnetic stirrer until the HfC organic precursor is completely dissolved. And (3) putting the low-density C/C composite material obtained in the step (2) into the solution, soaking for 1-3 h, taking out, and putting into an oven at 120-180 ℃ for drying and curing for 3-8 h for later use.
And 4, step 4: and (3) simultaneously putting the carbon cloth obtained in the step (2) and the low-density C/C composite material obtained in the step (3) into a tubular furnace, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is placed at different temperature positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the furnace temperature is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured at the temperature for 0.5-3 h, then the temperature is increased to 1500 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 2 h. And after the heat preservation is finished, closing the heating power supply to naturally cool. Through the preparation process, the in-situ grown HfC nanowires are obtained on the surface and inside of the low-density C/C composite material, and the carbon nanotubes are grown on the surface of the carbon cloth in situ, so that the HfC nanowires prepared in the embodiment are uniformly distributed in the low-density C/C composite material as can be seen from fig. 2a, and fig. 2b is an XRD (X-ray diffraction) spectrum of the sample. It can be seen from fig. 3a that the carbon nanotubes prepared in this example are uniformly distributed on the surface of the carbon cloth, and fig. 3b is a TEM image of the prepared carbon nanotubes.
Example 2:
step 1: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4And (4) gas is deposited for 20-100 h to obtain the low-density C/C composite material.
Step 2: preparing a catalyst solution: respectively weighing nickel nitrate hexahydrate and ethanol in a beaker, wherein the molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L, and stirring on a magnetic stirrer until the nickel nitrate hexahydrate is completely dissolved; and (3) putting the cleaned low-density C/C composite material and the carbon cloth into the prepared solution, soaking for 5-12 h, taking out, and putting into an oven at 40-70 ℃ for drying for later use.
And step 3: weighing an HfC organic precursor and a divinylbenzene solution with the mass fraction of 1:10 in a beaker, heating and stirring the mixture on a magnetic stirrer until the HfC organic precursor is completely dissolved. And (3) putting the low-density C/C composite material obtained in the step (2) into the solution, soaking for 1-3 h, taking out, and putting into an oven at 120-180 ℃ for drying and curing for 3-8 h for later use.
And 4, step 4: and (3) simultaneously putting the carbon cloth obtained in the step (2) and the low-density C/C composite material obtained in the step (3) into a tubular furnace, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is placed at different temperature positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the furnace temperature is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured at the temperature for 0.5-3 h, then the temperature is increased to 1600 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 2 h. And after the heat preservation is finished, closing the heating power supply to naturally cool. Through the preparation process, the HfC nanowire growing in situ is obtained on the surface and inside the low-density C/C composite material, and the carbon nanotube grows in situ on the surface of the carbon cloth.
Example 3:
step 1: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4And (4) gas is deposited for 20-100 h to obtain the low-density C/C composite material.
Step 2: preparing a catalyst solution: respectively weighing nickel nitrate hexahydrate and ethanol in a beaker, wherein the molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L, and stirring on a magnetic stirrer until the nickel nitrate hexahydrate is completely dissolved; soaking the cleaned low-density C/C composite material and the carbon cloth in the prepared solution for 5-12 h, taking out, and drying in an oven at 40-70 ℃ for later use;
and step 3: weighing an HfC organic precursor and a divinylbenzene solution with the mass fraction of 1:10 in a beaker, heating and stirring the mixture on a magnetic stirrer until the HfC organic precursor is completely dissolved. And (3) putting the low-density C/C composite material obtained in the step (2) into the solution, soaking for 1-3 h, taking out, and putting into an oven at 120-180 ℃ for drying and curing for 3-8 h for later use.
And 4, step 4: and (3) simultaneously putting the carbon cloth obtained in the step (2) and the low-density C/C composite material obtained in the step (3) into a tubular furnace, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is placed at different temperature positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the furnace temperature is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured at the temperature for 0.5-3 h, then the temperature is increased to 1700 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 2 h. And after the heat preservation is finished, closing the heating power supply to naturally cool. Through the preparation process, the HfC nanowire growing in situ is obtained on the surface and inside the low-density C/C composite material, and the carbon nanotube grows in situ on the surface of the carbon cloth.

Claims (3)

1. A method for in-situ growth of carbon nanotubes by using tail gas generated by polymer cracking is characterized by comprising the following steps:
step 1, preparation of low-density C/C: placing the 2D needled carbon felt in an isothermal furnace or a thermal gradient furnace, vacuumizing to 1kPa, and introducing Ar or N2The furnace temperature is increased to 1000-1300 ℃ at the temperature rising speed of 5-10 ℃/min by using protective gas; when the furnace temperature reaches the deposition temperature, CH is introduced4Gas is deposited for 20-100 h to obtain the low-density C/C composite material;
step 2, preparing a catalyst solution: stirring nickel nitrate hexahydrate and ethanol until the nickel nitrate hexahydrate is dissolved, soaking the cleaned low-density C/C composite material and the carbon cloth in the prepared solution for 5-12 hours, taking out, and drying in an oven at 40-70 ℃;
and step 3: mixing an HfC organic precursor with the mass fraction of 1: 20-1: 5 with a solvent, and stirring until the HfC organic precursor is completely dissolved; putting the low-density C/C composite material obtained in the step 2 into the solution for soaking for 1-3 h, taking out, and putting the low-density C/C composite material into an oven at 120-180 ℃ for drying and curing for 3-8 h;
and 4, step 4: putting the carbon cloth obtained in the step 2 and the low-density C/C composite material obtained in the step 3 into a tubular furnace at the same time, wherein the low-density C/C is placed in a set temperature zone range of the tubular furnace, the carbon cloth is respectively placed at different positions between the set temperature zone and an air outlet, Ar gas is used as protective gas, the temperature of the furnace is increased to 200-400 ℃ at the temperature increasing speed of 3-10 ℃/min, so that the precursor polymer is fully crosslinked and cured for 0.5-3 h at the temperature, then the temperature is increased to 1300-1800 ℃ at the temperature increasing speed of 3-10 ℃/min, and the heat preservation time is 1-10 h; and after the heat preservation is finished, closing the heating power supply to naturally cool, obtaining the HfC nanowire growing in situ on the surface and inside the low-density C/C composite material, and growing the carbon nanotube on the surface of the carbon cloth in situ.
2. The method for growing carbon nanotubes in situ by using the tail gas generated by the cracking of the polymer as claimed in claim 1, wherein: the molar concentration of the nickel nitrate hexahydrate is 0.05-2 mol/L.
3. The method for growing carbon nanotubes in situ by using the tail gas generated by the cracking of the polymer as claimed in claim 1, wherein: the HfC organic precursor is a solid or liquid HfC organic precursor or a mixture of solid and liquid HfC organic precursors.
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