CN114940489B - Method for preparing carbon nano tube from coal liquefaction residues - Google Patents
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention discloses a method for preparing carbon nanotubes by using coal liquefaction residues, which belongs to the technical fields of coal science and material science, and comprises the following steps: firstly, placing coal liquefaction residues and an anti-polymerization agent in a first-stage area of a two-stage furnace, then placing a transition metal growth catalyst in a second-stage area of the two-stage furnace, controlling carrier gas to flow from the first-stage area to the second-stage area, and carrying out programmed temperature rise on the two-stage furnace; firstly, the second-stage area is heated to 650-1000 ℃, then the first-stage area is heated to 400-650 ℃ and kept for 60-90 min, the coal liquefaction residues are pyrolyzed under the action of a first-stage area anti-polymerization agent to generate precursor carbon source volatile matters containing arene, naphthene and the like, the precursor carbon source volatile matters are transferred into the second-stage area, and the carbon nano tubes are finally grown through pyrolysis and carbon rearrangement of the volatile matters under the action of a transition metal growth catalyst. The method takes the byproduct coal liquefaction residues of the direct coal liquefaction process as a carbon source to prepare the carbon nanotubes, so that the preparation cost of the carbon nanotubes is effectively reduced, and the utilization benefit of the coal liquefaction residues is improved.
Description
Technical Field
The invention relates to a method for preparing carbon nanotubes from coal liquefaction residues, and belongs to the technical fields of coal chemical industry and materials.
Background
Carbon nanotubes are an allotrope of carbon, which is a cylindrical tube rolled up from one or more graphene sheets. Because the carbon nano tube has a unique one-dimensional structure, the carbon nano tube has excellent characteristics in the aspects of mechanics, electricity, heat, adsorption and the like, so that the carbon nano tube has wide application prospect in a plurality of fields, and the preparation cost of the carbon nano tube at the present stage is higher because of the high price of raw materials, such as: the arc discharge method uses high purity graphite as raw material, and the chemical vapor deposition method uses organic matters such as methane, ethylene, benzene and the like as raw materials, which limits the large-scale application of the carbon nano tube to a great extent.
The coal liquefaction residues are solid residues generated in the direct coal liquefaction process, account for 30-40% of the input raw coal, and mainly comprise carbon-containing organic matters such as heavy oil, organic asphaltene, pre-asphaltene, organic macromolecular residues and the like, and are mainly used for gasification and pyrolysis. In recent years, in order to realize high-value utilization of coal liquefaction residues, research on preparing carbon materials from the coal liquefaction residues has been conducted.
Chinese patent CN101693533a discloses a method for preparing nano carbon fiber/foam carbon by using coal direct liquefaction residue, the method uses coal direct liquefaction residue as carbon source of foam carbon, firstly, the coal liquefaction residue is prepared into pre-oxidized foam carbon preform by supercritical foaming method or template method, and is carbonized by heating to 700-900 ℃ at 1-5 ℃/min under inert gas, after keeping constant temperature for 1h, naturally cooling to room temperature, thus obtaining metal/foam carbon composite material, and then obtaining nano fiber/foam carbon composite material by organic chemical vapor deposition. The method fully utilizes metal catalysts such as carbon-rich organic matters, iron-containing compounds and the like in the coal liquefaction residues to prepare the metal/foam carbon composite material.
Chinese patent CN111501134A discloses a method for preparing general-purpose pitch-based carbon fibers from coal liquefaction residues, wherein ash content in the coal liquefaction residues is greatly reduced through sedimentation and separation, pitch bases are effectively separated, then softening points of the pitch are further improved through decompression and suction filtration and oxidative polycondensation, the problems of deep crosslinking process, easy loss of fluidity and coking and the like during high-temperature polycondensation are solved, and finally general-purpose pitch-based carbon fibers with diameters of 8-28 mu m and strength of 500-1100 MPa are prepared through non-melting treatment and carbonization treatment.
Therefore, the carbon material can be prepared under a certain condition by utilizing the coal liquefaction residues, but no related method for preparing the carbon nanotubes is disclosed, and if the coal liquefaction residues are used as carbon sources for preparing the carbon nanotubes, the preparation cost of the carbon nanotubes can be effectively reduced, and the high-efficiency utilization of the coal liquefaction residues can be realized.
Disclosure of Invention
Aiming at the problems of high production cost and high-value utilization of coal liquefaction residues of the existing carbon nanotubes, the invention provides a method for preparing the carbon nanotubes by using the coal liquefaction residues.
The principle of the invention is as follows:
the first-stage anti-polymerization agent promotes the generation of hydrocarbon volatile matters containing aromatic hydrocarbon, naphthene and the like by inhibiting the polycondensation and coking of asphaltene substances in coal liquefaction residues in the pyrolysis process, the volatile matters are adsorbed on the surface of a second-stage transition metal growth catalyst and are subjected to cracking and carbon rearrangement, and then carbon-containing species are dissolved in the transition metal growth catalyst and are diffused in the transition metal growth catalyst; finally, after the carbon-containing species reach supersaturation in the transition metal growth catalyst, solid carbon is separated out on the surface of the transition metal growth catalyst, and carbon nanotubes are generated through structural reforming.
The invention provides a method for preparing carbon nanotubes by using coal liquefaction residues, which comprises the steps of firstly placing the coal liquefaction residues and an anti-polymerization agent in a first-stage area of a two-stage furnace, then placing a transition metal growth catalyst in a second-stage area of the two-stage furnace, controlling carrier gas to flow from the first-stage area to the second-stage area, and carrying out programmed temperature rise on the two-stage furnace; firstly, the second-stage area is heated to 650-1000 ℃, then the first-stage area is heated to 400-650 ℃ and kept for 60-90 min, the coal liquefaction residues are pyrolyzed, the generated volatile matters are transferred into the second-stage area, and finally, carbon nano tubes grow out of the surface of the growth catalyst of the second-stage area under the action of the transition metal growth catalyst.
Further, the method for preparing the carbon nano tube from the coal liquefaction residues comprises the following steps:
(1) The mass ratio is 10: placing the coal liquefaction residues and the anti-caking agent in a quartz boat in a range of 0.1-1, stirring into paste, and placing the quartz boat in a zone of a two-stage furnace; then placing the transition metal growth catalyst in a two-stage area of a two-stage furnace; the mass ratio of the coal liquefaction residues to the transition metal growth catalyst is 1:0.1-1;
(2) Controlling the carrier gas with the flow rate of 50-100 ml/min to flow from the first-stage area to the second-stage area, and carrying out programmed temperature rise on the two-stage furnace; firstly, raising the temperature of the two-stage area to 650-1000 ℃ at a heating rate of 1-30 ℃/min, then raising the temperature of the one-stage area to 400-650 ℃ at a heating rate of 1-20 ℃/min, keeping for 60-90 min, and finally growing carbon nanotubes on the surface of a catalyst grown in the two-stage area after the reaction is finished;
(3) And naturally cooling the two-stage furnace to room temperature after the reaction is finished, and separating and purifying the mixture of the catalyst and the carbon nano tube, thereby obtaining the pure carbon nano tube.
Further, the anti-polymerization agent in the step (1) is composed of Fe 2 O 3 With an alkali metal or alkaline earth metal compound. Further, the alkali metal or alkaline earth metal compound is K 2 CO 3 、Na 2 CO 3 One of CaO and MgO.
The transition metal growth catalyst is as follows: at A1 2 O 3 Or SiO 2 A catalyst obtained by loading transition metal on a carrier; wherein the transition metal comprises one or both of Fe, co, ni, cu.
Further, the carrier gas in the step (2) is N 2 And CH (CH) 4 The molar ratio is 1: 0-1.
Further, the separation and purification method in the step (3) comprises the following steps: soaking the product obtained in the step (2) in 1-5 mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes.
The invention has the beneficial effects that:
(1) Compared with the traditional preparation of the carbon nano tube, the invention has the advantages that the used raw materials are cheap and easy to obtain, the preparation cost of the carbon nano tube is reduced, and the high-value utilization of the coal liquefaction residues is realized.
(2) Under the action of an anti-polymerization agent and a transition metal growth catalyst, the separation of the carbon source pyrolysis zone and the carbon nano tube growth zone can be realized by controlling the two-stage process; in addition, the anti-polymerization agent is used for inhibiting the condensation polymerization and coking of asphaltene substances in the coal liquefaction residues in the pyrolysis process in the first-stage zone, promoting the generation of precursor carbon source volatile matters containing aromatic hydrocarbon, naphthene and the like, and the volatile matters are adsorbed on the surface of the transition metal growth catalyst in the second-stage zone for cracking and carbon rearrangement to finally generate the carbon nano tube. The stepwise control of the release of the carbon-containing component of the coal liquefaction residue and the growth of the carbon nanotubes not only ensures that the generated carbon source is easier to be converted into the carbon nanotubes, but also is beneficial to the separation and purification of the subsequent carbon nanotubes.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing carbon nanotubes from coal liquefaction residues according to the present invention.
Fig. 2 is a scanning electron microscope image of the carbon nanotubes prepared in example 1.
FIG. 3 is a graph showing the pipe diameter distribution of the carbon nanotubes prepared in example 1.
In the figure: 1 is methane, 2 is nitrogen, 3 is a gas flowmeter, 4 is a first-stage area of a reaction furnace, 5 is a second-stage area of the reaction furnace, 6 is a temperature control device, 7 is coal liquefaction residues and an anti-polymerization agent, 8 is a transition metal growth catalyst, and 9 is tail gas.
Detailed Description
For a better understanding of the present invention, a detailed description of the present invention will be given below by way of specific examples, but the present invention is not limited to the following examples.
The invention adopts a reaction device as shown in figure 1, the reaction furnace is divided into a first-stage zone 4 of the reaction furnace and a second-stage zone 5 of the reaction furnace, a quartz boat is arranged in the first-stage zone 4 of the reaction furnace, and coal liquefaction residues and an anti-polymerization agent 7 are arranged in the quartz boat; meanwhile, a first section 4 of the reaction furnace is connected with a carrier gas conveying pipe, and two gas flow meters 3 are arranged on the carrier gas conveying pipe and are respectively used for controlling the flow rates of methane 1 and nitrogen 2; a transition metal growth catalyst 8 is arranged in the second section 5 of the reaction furnace; the first-stage zone 4 and the second-stage zone 5 of the reaction furnace are respectively provided with a respective temperature control device 6; after the reaction is finished, the two-stage furnace naturally cools to room temperature, the mixture of the catalyst and the carbon nano tube is separated and purified, so that pure carbon nano tube is obtained, and the tail gas 9 after the reaction is collected.
Example 1
In this example 1, an experiment was performed using a Shenhua coal liquefaction residue as a raw material.
(1) Preparing a transition metal growth catalyst by an impregnation method: firstly, mixing 1g of nickel nitrate, 2g of ferric nitrate, 5g of aluminum oxide and 20ml of water, stirring, then soaking for 10 hours at room temperature, drying overnight at 110 ℃, and finally roasting for 6h at 800 ℃ to obtain the aluminum oxide supported Fe-Ni bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe which are crushed to 200 meshes 2 O 3 0.25g each of CaO was placed in a quartz boat, stirred into a paste, and the quartz boat was placed in a one-stage zone of a two-stage furnace. Then, 5g of the transition metal growth catalyst prepared in (1) is placed in a two-stage zone of a two-stage furnace; controlling the flow rate of N at 50ml/min 2 And 10ml/min of CH 4 The two-stage furnace is subjected to programmed temperature rise from the first-stage region to the second-stage region, the second-stage region is firstly heated to 900 ℃ at a temperature rising rate of 15 ℃/min, then the first-stage region is heated to 600 ℃ at a temperature rising rate of 10 ℃/min and is kept for 60min, after the reaction is finished, the two-stage furnace naturally cools to room temperature, and finally carbon nanotubes grow on the surface of the catalyst in the second-stage region;
(3) Soaking the product obtained in step (2) in 2mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes;
fig. 2 and 3 show a scanning electron microscope image and a tube diameter distribution diagram of the carbon nanotubes prepared in this example, respectively. From the figure, it can be seen that the carbon nanotubes with the diameter of about 200nm, the length of about 5 μm and the complete structure are prepared in example 1, which shows that the method provided by the invention can prepare the carbon nanotubes with excellent quality.
Example 2
In this example 2, an experiment was performed using a Shenhua coal liquefaction residue as a raw material.
(1) The transition metal growth catalyst is prepared by an impregnation method: firstly, 2g of copper nitrate, 4g of ferric nitrate, 10g of aluminum oxide and 40ml of water are mixed and stirred, then are immersed in 12h at room temperature, are dried overnight at 110 ℃, and finally are baked at 800 ℃ for 6h, thus obtaining the aluminum oxide supported Fe-Cu bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe which are crushed to 200 meshes 2 O 3 MgO, each 0.75g, was placed in a quartz boat, stirred into a paste, and the quartz boat was placed in one section of a two-section furnace. Next, 10g of the transition metal growth catalyst prepared in (1) was placed in the two-stage zone of a two-stage furnace; controlling the flow rate of N at 50ml/min 2 The two-stage furnace is subjected to programmed temperature rise from the first-stage region to the second-stage region, the second-stage region is firstly heated to 700 ℃ at a temperature rising rate of 10 ℃/min, then the first-stage region is heated to 490 ℃ at a temperature rising rate of 7 ℃/min and is kept for 80min, after the reaction is finished, the two-stage furnace naturally cools to room temperature, and finally carbon nanotubes grow on the surface of the catalyst in the second-stage region;
(3) Soaking the product obtained in step (2) in 2mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes.
Example 3
In this example 3, an experiment was performed using a Shenhua coal liquefaction residue as a raw material.
(1) The transition metal growth catalyst is prepared by an impregnation method: firstly, mixing and stirring 2g of cobalt nitrate, 4g of ferric nitrate, 10g of silicon dioxide and 40ml of water, then soaking 12h at room temperature, drying overnight at 110 ℃, and finally roasting 6h at 800 ℃ to obtain the silicon dioxide supported Fe-Co bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe which are crushed to 200 meshes 2 O 3 、K 2 CO 3 Each 0.5g was placed in a quartz boat, stirred into a paste, and the quartz boat was placed in one section of a two-section furnace. Next, 10g of the transition metal growth catalyst prepared in (1) was placed in the two-stage zone of a two-stage furnace; n controlling the flow rate to be 70ml/min 2 The two-stage furnace is subjected to programmed temperature rise from the first-stage region to the second-stage region, the second-stage region is firstly heated to 800 ℃ at a temperature rising rate of 16 ℃/min, then the first-stage region is heated to 550 ℃ at a temperature rising rate of 11 ℃/min and kept for 70min, after the reaction is finished, the two-stage furnace naturally cools to room temperature, and finally carbon nanotubes grow on the surface of the catalyst in the second-stage region;
(3) Soaking the product obtained in step (2) in 2mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes.
Example 4
In this example 4, an experiment was performed using a Shenhua coal liquefaction residue as a raw material.
(1) Preparing a transition metal growth catalyst by an impregnation method: firstly, mixing 1g of nickel nitrate, 2g of ferric nitrate, 5g of aluminum oxide and 20ml of water, stirring, then soaking for 10 hours at room temperature, drying overnight at 110 ℃, and finally roasting for 6h at 800 ℃ to obtain the aluminum oxide supported Fe-Ni bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe which are crushed to 200 meshes 2 O 3 、Na 2 CO 3 Each 0.5g was placed in a quartz boat, stirred into a paste, and the quartz boat was placed in one section of a two-section furnace. Next, 10g of the transition metal growth catalyst prepared in (1) was placed in the two-stage zone of a two-stage furnace; controlling the flow rate of N at 50ml/min 2 And 10ml/min of CH 4 From the first zone to the second zone, the two-zone furnace is programmedHeating, namely heating the second-stage zone to 930 ℃ at a heating rate of 15 ℃/min, heating the first-stage zone to 620 ℃ at a heating rate of 10 ℃/min, keeping for 60min, naturally cooling the second-stage furnace to room temperature after the reaction is finished, and finally growing carbon nanotubes on the surface of the catalyst grown in the second-stage zone;
(3) Soaking the product obtained in step (2) in 2mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes.
Claims (3)
1. A method for preparing carbon nanotubes from coal liquefaction residues is characterized by comprising the following steps: firstly, placing coal liquefaction residues and an anti-polymerization agent in a first-stage area of a two-stage furnace, then placing a transition metal growth catalyst in a second-stage area of the two-stage furnace, controlling carrier gas to flow from the first-stage area to the second-stage area, and carrying out programmed temperature rise on the two-stage furnace; firstly, raising the temperature of the second-stage region to 650-1000 ℃, then raising the temperature of the first-stage region to 400-650 ℃ and keeping for 60-90 min, pyrolyzing coal liquefaction residues, transferring generated volatile matters into the second-stage region, and finally growing carbon nano tubes on the surface of a growth catalyst of the second-stage region under the action of a transition metal growth catalyst;
the method for preparing the carbon nano tube from the coal liquefaction residues comprises the following steps:
(1) Placing the coal liquefaction residues and the anti-polymerization agent into a quartz boat, stirring into paste, and placing the quartz boat into a section of a two-section furnace; the mass ratio of the coal liquefaction residues to the anti-polymerization agent is 10: 0.1-1; then placing the transition metal growth catalyst in a two-stage area of a two-stage furnace; the mass ratio of the coal liquefaction residues to the transition metal growth catalyst is 1:0.1-1; the anti-polymerization agent is made of Fe 2 O 3 A mixture with an alkali metal or alkaline earth metal compound; the alkali metal or alkaline earth metal compound is K 2 CO 3 、Na 2 CO 3 One of CaO and MgO;
(2) Controlling the carrier gas with the flow rate of 50-100 ml/min to flow from the first-stage area to the second-stage area, carrying out programmed heating on the two-stage area, firstly raising the temperature of the second-stage area to 650-1000 ℃ at the heating rate of 1-30 ℃/min, then raising the temperature of the first-stage area to 400-650 ℃ at the heating rate of 1-20 ℃/min, keeping for 60-90 min, and finally growing carbon nanotubes on the surface of the catalyst grown in the second-stage area after the reaction is finished;
(3) After the reaction is finished, naturally cooling the two-stage furnace to room temperature, and separating and purifying the mixture of the catalyst and the carbon nano tube to obtain the pure carbon nano tube;
the transition metal growth catalyst is as follows: at Al 2 O 3 Or SiO 2 A catalyst obtained by loading transition metal on a carrier; wherein the transition metal comprises one or both of Fe, co, ni, cu.
2. The method for preparing carbon nanotubes from the coal liquefaction residues according to claim 1, wherein: the carrier gases in the step (2) are as follows: n (N) 2 And CH (CH) 4 The molar ratio is 1: 0-1.
3. The method for preparing carbon nanotubes from the coal liquefaction residues according to claim 1, wherein: the separation and purification method in the step (3) comprises the following steps: soaking the product obtained in the step (2) in 1-5 mol/L HNO 3 After ultrasonic dispersion for 2 hours at room temperature, standing and soaking for 6 hours, repeating the steps once, centrifugally separating, washing with deionized water to be neutral, filtering, placing a sample in a drying box, and drying at 110 ℃ for 12 hours to separate pure carbon nanotubes.
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