CN114940489A - Method for preparing carbon nano tube from coal liquefaction residues - Google Patents
Method for preparing carbon nano tube from coal liquefaction residues Download PDFInfo
- Publication number
- CN114940489A CN114940489A CN202210683278.8A CN202210683278A CN114940489A CN 114940489 A CN114940489 A CN 114940489A CN 202210683278 A CN202210683278 A CN 202210683278A CN 114940489 A CN114940489 A CN 114940489A
- Authority
- CN
- China
- Prior art keywords
- coal liquefaction
- section
- area
- temperature
- liquefaction residues
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for preparing carbon nano tubes by using coal liquefaction residues, which belongs to the technical field of coal science and material science and comprises the following steps: firstly, placing coal liquefaction residues and an anti-aggregation agent in a first section area of a two-section furnace, then placing a transition metal growth catalyst in a second section area of the two-section furnace, controlling carrier gas to flow from the first section area to the second section area, and carrying out temperature programming on the two-section furnace; and firstly, raising the temperature of the second-stage area to 650-1000 ℃, then raising the temperature of the first-stage area to 400-650 ℃, keeping the temperature for 60-90 min, pyrolyzing the coal liquefaction residues under the action of the anti-polymerization agent of the first-stage area to generate precursor carbon source volatile matters containing aromatic hydrocarbon, cyclane and the like, transferring the precursor carbon source volatile matters into the second-stage area, and finally growing the carbon nano tube from the volatile matters through cracking and carbon rearrangement under the action of a transition metal growth catalyst. The method takes the byproduct coal liquefaction residue of the direct coal liquefaction process as a carbon source to prepare the carbon nano tube, thereby not only effectively reducing the preparation cost of the carbon nano tube, but also improving the utilization benefit of the coal liquefaction residue.
Description
Technical Field
The invention relates to a method for preparing carbon nanotubes from coal liquefaction residues, and belongs to the technical field of coal chemical industry and materials.
Background
A carbon nanotube is an allotrope of carbon, which is a cylindrical tube rolled from one or more graphene sheets. Because the carbon nano tube has a unique one-dimensional structure and has excellent characteristics in the aspects of mechanics, electricity, heat, adsorption and the like, the carbon nano tube has wide application prospects in many fields, and the preparation cost of the carbon nano tube at the present stage is higher because the raw materials are expensive, such as: the arc discharge method uses high-purity graphite as a raw material, and the chemical vapor deposition method uses organic matters such as methane, ethylene and benzene as raw materials, which greatly limits the large-scale application of the carbon nano tube.
The coal liquefaction residues are solid residues generated in the direct coal liquefaction process, account for 30-40% of the input raw coal, mainly comprise carbon-containing organic matters such as heavy oil, organic asphaltene, preasphaltene and organic macromolecular residues, and are mainly used for gasification and pyrolysis. In recent years, in order to achieve high-value utilization of coal liquefaction residues, studies have been conducted to produce carbon materials using the coal liquefaction residues as a raw material.
Chinese patent CN101693533A discloses a method for preparing carbon nanofiber/carbon foam by using coal direct liquefaction residues as a carbon source of the carbon foam, firstly, the coal liquefaction residues are prepared into a pre-oxidized carbon foam preform by a supercritical foaming method or a template method, the pre-oxidized carbon foam preform is heated to 700-900 ℃ at a speed of 1-5 ℃/min under inert gas for carbonization, the temperature is kept for 1h and then naturally cooled to room temperature, a metal/carbon foam composite material is obtained, and the nano fiber/carbon foam composite material is obtained by organic chemical vapor deposition. The method fully utilizes the carbon-rich organic matters, iron-containing compounds and other metal catalysts 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 fiber from coal liquefaction residues, wherein ash content in the coal liquefaction residues with rich asphaltene is greatly reduced by settling separation, pitch groups are effectively separated, then softening point of pitch is further improved by vacuum filtration and oxidative polycondensation reaction, the problems that cross-linking process is too deep during high-temperature polycondensation, fluidity is lost, coking is easy and the like are solved, and finally general-purpose pitch-based carbon fiber with diameter of 8-28 mu m and strength of 500-1100 MPa is prepared by non-melting treatment and carbonization treatment reaction.
Therefore, the carbon material can be prepared by utilizing the coal liquefaction residues under certain conditions, but a related method for preparing the carbon nano tube is not disclosed, and if the coal liquefaction residues are used as a carbon source to prepare the carbon nano tube, the preparation cost of the carbon nano tube can be effectively reduced, and the high-efficiency utilization of the coal liquefaction residues can be realized.
Disclosure of Invention
The invention provides a method for preparing carbon nano tubes by coal liquefaction residues, aiming at the problems of high production cost and high-valued utilization of the existing carbon nano tubes and the coal liquefaction residues.
The principle of the invention is as follows:
the anti-polymerization agent in the first section of the invention promotes the generation of hydrocarbon volatile matters containing aromatic hydrocarbon, cyclane and the like by inhibiting the condensation and coking of asphaltene substances in coal liquefaction residues in the pyrolysis process, the volatile matters are adsorbed on the surface of the transition metal growth catalyst in the second section of the section and are cracked and carbon rearranged, and then carbon-containing species are dissolved in the transition metal growth catalyst and are diffused in the transition metal growth catalyst; finally, when the carbon-containing species reach supersaturation in the transition metal growth catalyst, solid carbon is precipitated on the surface of the transition metal growth catalyst, and the carbon nanotubes are generated through structural reformation.
The invention provides a method for preparing carbon nano tubes by coal liquefaction residues, which comprises the steps of firstly placing the coal liquefaction residues and an anti-aggregation agent in a first section area of a two-section furnace, then placing a transition metal growth catalyst in a second section area of the two-section furnace, controlling carrier gas to flow from the first section area to the second section area, and carrying out temperature programming on the two-section furnace; and (3) firstly heating the two-stage area to 650-1000 ℃, then heating the first-stage area to 400-650 ℃, keeping the temperature for 60-90 min, pyrolyzing the coal liquefaction residues, transferring the generated volatile matters into the two-stage area, and finally growing carbon nanotubes on the surface of the growth catalyst in the two-stage area under the action of a transition metal growth catalyst.
Further, the method for preparing the carbon nano tube by using the coal liquefaction residues comprises the following steps:
(1) mixing the components in a mass ratio of 10: placing 0.1-1% of coal liquefaction residues and an anti-aggregation agent in a quartz boat, stirring the quartz boat into paste, and placing the quartz boat in a first section of a two-section furnace; then placing a transition metal growth catalyst in a two-section area of the two-section furnace; the mass ratio of the coal liquefaction residues to the transition metal growth catalyst is 1: 0.1 to 1;
(2) controlling the flow rate of carrier gas to be 50-100 ml/min to flow from the first-stage area to the second-stage area, and carrying out temperature programming on the two-stage furnace; firstly, the temperature of the second-stage zone is increased to 650-1000 ℃ at the temperature increasing rate of 1-30 ℃/min, then the temperature of the first-stage zone is increased to 400-650 ℃ at the temperature increasing rate of 1-20 ℃/min and is kept for 60-90 min, and finally, carbon nanotubes grow on the surface of the catalyst growing in the second-stage zone after the reaction is finished;
(3) after the reaction is finished, the temperature of the two-section furnace is naturally reduced to room temperature, and the mixture of the catalyst and the carbon nano tube is separated and purified, so that the pure carbon nano tube is obtained.
Further, the anti-aggregation agent in the step (1) is made of Fe 2 O 3 With alkali metal or alkaline earth metal compounds. Further, the alkali metal or alkaline earth metal compound is K 2 CO 3 、Na 2 CO 3 CaO, and MgO.
The transition metal growth catalyst is as follows: at A1 2 O 3 Or SiO 2 A catalyst obtained by loading a transition metal on a carrier; wherein the transition metal comprises one or two of Fe, Co, Ni and Cu.
Further, the carrier gas in the step (2) is N 2 And CH 4 The molar ratio is 1: 0 to 1 gas.
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 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the step once, performing centrifugal separation, washing with deionized water to neutrality, filtering, placing the sample in a drying oven, and drying at 110 ℃ for 12h to separate out pure carbon nanotubes.
The invention has the beneficial effects that:
(1) the invention takes the coal liquefaction residue which is the byproduct of the direct coal liquefaction process as the raw material to prepare the carbon nano tube, compared with the traditional raw materials for preparing the carbon nano tube, such as high-purity graphite, organic gas and the like, the raw material used by the invention has the advantages of low price and easy obtaining, thereby not only reducing the preparation cost of the carbon nano tube, but also realizing the high-value utilization of the coal liquefaction residue.
(2) Under the action of the anti-aggregation agent and the transition metal growth catalyst, the separation of the carbon source pyrolysis area and the carbon nanotube growth area can be realized by controlling the two-stage process; in addition, in the first section, the anti-polymerization agent is utilized to inhibit the condensation and coking of asphaltene substances in the coal liquefaction residues in the pyrolysis process, the generation of precursor carbon source volatile matters containing aromatic hydrocarbon, cyclane and the like is promoted, and the volatile matters are adsorbed on the surface of the transition metal growth catalyst in the second section to be cracked and undergo carbon rearrangement to finally generate the carbon nano tube. The step-by-step regulation and control of the release of the carbon-containing components in the coal liquefaction residues and the growth of the carbon nanotubes not only enables the generated carbon source to be more easily converted into the carbon nanotubes, but also is beneficial to the subsequent separation and purification of the carbon nanotubes.
Drawings
FIG. 1 is a diagram of an apparatus for preparing carbon nanotubes using coal liquefaction residues according to the present invention.
Fig. 2 is a scanning electron micrograph of the carbon nanotube prepared in example 1.
Fig. 3 is a tube diameter distribution diagram of the carbon nanotube prepared in example 1.
In the figure: 1 is methane, 2 is nitrogen, 3 is a gas flowmeter, 4 is a first-stage zone of a reaction furnace, 5 is a second-stage zone of the reaction furnace, 6 is a temperature control device, 7 is coal liquefaction residue and an anti-aggregation agent, 8 is a transition metal growth catalyst, and 9 is tail gas.
Detailed Description
For a better understanding of the present invention, the following examples are provided to further illustrate the present invention, but the present invention is not limited to the following examples.
The invention adopts a reaction device as shown in figure 1, a reaction furnace is divided into a first section zone 4 of the reaction furnace and a second section zone 5 of the reaction furnace, a quartz boat is arranged in the first section zone 4 of the reaction furnace, and coal liquefaction residues and an anti-aggregation 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 of methane 1 and the flow of nitrogen 2; a transition metal growth catalyst 8 is arranged in the second-stage zone 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, naturally cooling the two-section furnace to room temperature, separating and purifying the mixture of the catalyst and the carbon nano tube to obtain a pure carbon nano tube, and collecting the tail gas 9 after the reaction.
Example 1
In this example 1, experiments were carried out using the Shenhua coal liquefaction residue as a raw material.
(1) Preparing a transition metal growth catalyst by an impregnation method: firstly, 1g of nickel nitrate, 2g of ferric nitrate, 5g of alumina and 20ml of water are mixed and stirred, then the mixture is soaked for 10 hours at room temperature, then dried overnight at 110 ℃, and finally roasted for 6 hours at 800 ℃ to obtain the alumina-loaded Fe-Ni bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe crushed to 200 mesh 2 O 3 And 0.25g of CaO respectively are placed in a quartz boat, stirred into paste, and the quartz boat is placed in a section of a two-section furnace. Then, 5g of the transition metal growth catalyst prepared in (1) is placed in a second-stage area of a two-stage furnace; controlling the flow rate to 50ml/min N 2 And 10ml/min CH 4 Flowing from the first-stage zone to the second-stage zone, performing temperature programming on the two-stage furnace, heating the second-stage zone to 900 ℃ at a temperature rise rate of 15 ℃/min, then heating the first-stage zone to 600 ℃ at a temperature rise rate of 10 ℃/min, keeping the temperature for 60min, and after the reaction is finished, heating the first-stage zone to 600 ℃ at a temperature rise rate of 10 ℃/minNaturally cooling the two-section furnace to room temperature, and finally growing carbon nanotubes on the surface of the catalyst in the two-section area;
(3) soaking the product obtained in the step (2) in 2mol/L HNO 3 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the step once, performing centrifugal separation, washing with deionized water to neutrality, filtering, placing the sample in a drying oven, and drying at 110 ℃ for 12h to separate out pure carbon nanotubes;
fig. 2 and fig. 3 show a scanning electron microscope image and a tube diameter distribution diagram of the carbon nanotube prepared in this example, respectively. It can be seen from the figure that example 1 produces carbon nanotubes with a diameter of about 200nm, a length of about 5 μm, and a complete structure, which illustrates that the method of the present invention can produce carbon nanotubes with excellent quality.
Example 2
In this example 2, experiments were conducted using the Shenhua coal liquefaction residue as a raw material.
(1) Preparation of transition metal growth catalyst by impregnation: firstly, 2g of copper nitrate, 4g of ferric nitrate, 10g of alumina and 40ml of water are mixed and stirred, then the mixture is soaked for 12 hours at room temperature, then dried overnight at 110 ℃, and finally roasted for 6 hours at 800 ℃ to obtain the alumina-supported Fe-Cu bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe crushed to 200 meshes 2 O 3 And 0.75g of MgO are respectively placed in a quartz boat, stirred into paste, and the quartz boat is placed in a section of a two-section furnace. Then, 10g of the transition metal growth catalyst prepared in (1) is placed in a second-stage area of a two-stage furnace; controlling the flow rate to 50ml/min N 2 Flowing from the first-stage area to the second-stage area, carrying out temperature programming on the two-stage furnace, firstly heating the second-stage area to 700 ℃ at the heating rate of 10 ℃/min, then heating the first-stage area to 490 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 80min, naturally cooling the two-stage furnace to room temperature after the reaction is finished, and finally growing the carbon nano tube on the surface of the catalyst growing in the second-stage area;
(3) soaking the product obtained in the step (2) in 2mol/L HNO 3 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the steps once, and separatingAnd (3) performing centrifugal separation, washing the sample to be neutral by deionized water, filtering the sample, and drying the sample in a drying box at 110 ℃ for 12 hours to separate pure carbon nanotubes.
Example 3
In example 3, experiments were conducted using the Shenhua coal liquefaction residue as a raw material.
(1) Preparation of transition metal growth catalyst by impregnation: firstly, 2g of cobalt nitrate, 4g of ferric nitrate, 10g of silicon dioxide and 40ml of water are mixed and stirred, then the mixture is soaked for 12 hours at room temperature, then dried overnight at 110 ℃, and finally roasted for 6 hours 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 crushed to 200 meshes 2 O 3 、K 2 CO 3 0.5g each was placed in a quartz boat, stirred to a paste, and the quartz boat was placed in one zone of a two-zone furnace. Then, 10g of the transition metal growth catalyst prepared in (1) is placed in a second-stage area of a two-stage furnace; controlling the flow rate to be 70ml/min N 2 Flowing from the first-stage area to the second-stage area, carrying out temperature programming on the two-stage furnace, firstly heating the second-stage area to 800 ℃ at the heating rate of 16 ℃/min, then heating the first-stage area to 550 ℃ at the heating rate of 11 ℃/min, keeping the temperature for 70min, naturally cooling the two-stage furnace to room temperature after the reaction is finished, and finally growing the carbon nano tube on the surface of the catalyst growing in the second-stage area;
(3) soaking the product obtained in the step (2) in 2mol/L HNO 3 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the step once, performing centrifugal separation, washing with deionized water to neutrality, filtering, placing the sample in a drying oven, and drying at 110 ℃ for 12h to separate out pure carbon nanotubes.
Example 4
In example 4, an experiment was performed using the shenhua coal liquefaction residue as a raw material.
(1) Preparing a transition metal growth catalyst by an impregnation method: firstly, 1g of nickel nitrate, 2g of ferric nitrate, 5g of alumina and 20ml of water are mixed and stirred, then the mixture is soaked for 10 hours at room temperature, then dried overnight at 110 ℃, and finally roasted for 6 hours at 800 ℃ to obtain the alumina-loaded Fe-Ni bimetallic catalyst, namely the transition metal growth catalyst.
(2) 20g of coal liquefaction residue and Fe crushed to 200 mesh 2 O 3 、Na 2 CO 3 0.5g each was placed in a quartz boat, stirred to a paste, and the quartz boat was placed in one zone of a two-zone furnace. Then, 10g of the transition metal growth catalyst prepared in (1) is placed in a second-stage area of a two-stage furnace; controlling the flow rate to 50ml/min N 2 And 10ml/min CH 4 Flowing from the first-stage area to the second-stage area, carrying out temperature programming on the two-stage furnace, firstly raising the temperature of the second-stage area to 930 ℃ at the temperature raising rate of 15 ℃/min, then raising the temperature of the first-stage area to 620 ℃ at the temperature raising rate of 10 ℃/min, keeping the temperature for 60min, naturally lowering the temperature of the two-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 area;
(3) soaking the product obtained in the step (2) in 2mol/L HNO 3 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the step once, performing centrifugal separation, washing with deionized water to neutrality, filtering, placing the sample in a drying oven, and drying at 110 ℃ for 12h to separate out pure carbon nanotubes.
Claims (7)
1. A method for preparing carbon nanotubes by coal liquefaction residues is characterized by comprising the following steps: firstly, placing coal liquefaction residues and an anti-aggregation agent in a first section area of a two-section furnace, then placing a transition metal growth catalyst in a second section area of the two-section furnace, controlling carrier gas to flow from the first section area to the second section area, and carrying out temperature programming on the two-section furnace; and (3) firstly heating the second-stage area to 650-1000 ℃, then heating the first-stage area to 400-650 ℃, keeping the temperature for 60-90 min, carrying out pyrolysis on the coal liquefaction residues, transferring the generated volatile matters into the second-stage area, and finally growing carbon nanotubes on the surface of the growth catalyst in the second-stage area under the action of a transition metal growth catalyst.
2. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 1, characterized by comprising the steps of:
(1) placing the coal liquefaction residues and the anti-aggregation agent in a quartz boat, stirring the quartz boat into paste, and placing the quartz boat in a first section of a two-section furnace; the mass ratio of the coal liquefaction residues to the anti-aggregation agent is 10: 0.1 to 1; then placing a transition metal growth catalyst in a two-section area of the two-section furnace; the mass ratio of the coal liquefaction residues to the transition metal growth catalyst is 1: 0.1 to 1;
(2) controlling the flow rate of carrier gas to be 50-100 ml/min to flow from the first-stage area to the second-stage area, carrying out temperature programming on the two-stage furnace, firstly raising the temperature of the second-stage area to 650-1000 ℃ at the temperature raising rate of 1-30 ℃/min, then raising the temperature of the first-stage area to 400-650 ℃ at the temperature raising rate of 1-20 ℃/min, keeping the temperature for 60-90 min, and finally growing carbon nanotubes on the surface of a growth catalyst in the second-stage area after the reaction is finished;
(3) after the reaction is finished, naturally cooling the two-section 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.
3. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 2, wherein the method comprises the following steps: the anti-polymerization agent in the step (1) is Fe 2 O 3 And an alkali metal or alkaline earth metal compound.
4. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 3, wherein the method comprises the following steps: the alkali metal or alkaline earth metal compound is K 2 CO 3 、Na 2 CO 3 CaO, and MgO.
5. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 2, wherein the method comprises the following steps: the transition metal growth catalyst is as follows: at A1 2 O 3 Or SiO 2 A catalyst obtained by loading a transition metal on a carrier; wherein the transition metal comprises one or two of Fe, Co, Ni and Cu.
6. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 2, wherein the method comprises the following steps: the carrier gas in the step (2) is as follows: n is a radical of 2 And CH 4 The molar ratio is 1: 0 to 1 gas.
7. The method for preparing carbon nanotubes from coal liquefaction residues as claimed in claim 2, wherein the method comprises the following steps: 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 Performing ultrasonic dispersion at room temperature for 2h, standing and soaking for 6h, repeating the steps once, performing centrifugal separation, washing with deionized water to neutrality, filtering, placing the sample in a drying oven, and drying at 110 ℃ for 12h to separate out pure carbon nanotubes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210683278.8A CN114940489B (en) | 2022-06-17 | 2022-06-17 | Method for preparing carbon nano tube from coal liquefaction residues |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210683278.8A CN114940489B (en) | 2022-06-17 | 2022-06-17 | Method for preparing carbon nano tube from coal liquefaction residues |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114940489A true CN114940489A (en) | 2022-08-26 |
| CN114940489B CN114940489B (en) | 2023-08-22 |
Family
ID=82910461
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210683278.8A Active CN114940489B (en) | 2022-06-17 | 2022-06-17 | Method for preparing carbon nano tube from coal liquefaction residues |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114940489B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621163A (en) * | 2023-06-01 | 2023-08-22 | 重庆中润新材料股份有限公司 | Synthesis method of carbon nano tube |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002081371A2 (en) * | 2001-04-05 | 2002-10-17 | Honda Giken Kogyo Kabushiki Kaisha | Chemical vapor deposition growth of single-wall carbon nanotubes |
| US20030181328A1 (en) * | 2002-03-25 | 2003-09-25 | Industrial Technology Research Institute | Supported metal catalyst for synthesizing carbon nanotubes by low-temperature thermal chemical vapor deposition and method of synthesizing carbon nanotubes using the same |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
| CN104804708A (en) * | 2015-03-27 | 2015-07-29 | 大连理工大学 | Method for preparing structural type wave-absorbing material |
| KR20160062810A (en) * | 2014-11-25 | 2016-06-03 | 전자부품연구원 | Method for preparing carbon nanotube and hybrid carbon nanotube composite |
| CN107754835A (en) * | 2017-11-27 | 2018-03-06 | 成都欣华源科技有限责任公司 | A kind of wear-resisting residual oil hydrocatalyst |
| US20190194364A1 (en) * | 2017-12-22 | 2019-06-27 | Ramaco Carbon, Llc | Methods for forming resins and other byproducts from raw coal |
| CN111185174A (en) * | 2020-01-19 | 2020-05-22 | 华东理工大学 | Catalyst for preparing olefin by CO hydrogenation and preparation method and application thereof |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111905737A (en) * | 2020-08-14 | 2020-11-10 | 郑州大学 | Preparation method and application of single iron catalyst and alkali metal modified catalyst |
| WO2020253104A1 (en) * | 2019-06-19 | 2020-12-24 | 江西铜业技术研究院有限公司 | Carbon nano tube preparation device and method |
| CN112408364A (en) * | 2020-11-30 | 2021-02-26 | 青岛科技大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste thermosetting plastic |
| WO2022097949A1 (en) * | 2020-11-09 | 2022-05-12 | 주식회사 코본 | Method for continuously synthesizing carbon nanotubes |
-
2022
- 2022-06-17 CN CN202210683278.8A patent/CN114940489B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002081371A2 (en) * | 2001-04-05 | 2002-10-17 | Honda Giken Kogyo Kabushiki Kaisha | Chemical vapor deposition growth of single-wall carbon nanotubes |
| US20030181328A1 (en) * | 2002-03-25 | 2003-09-25 | Industrial Technology Research Institute | Supported metal catalyst for synthesizing carbon nanotubes by low-temperature thermal chemical vapor deposition and method of synthesizing carbon nanotubes using the same |
| CN101693533A (en) * | 2009-10-23 | 2010-04-14 | 大连理工大学 | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials |
| KR20160062810A (en) * | 2014-11-25 | 2016-06-03 | 전자부품연구원 | Method for preparing carbon nanotube and hybrid carbon nanotube composite |
| CN104804708A (en) * | 2015-03-27 | 2015-07-29 | 大连理工大学 | Method for preparing structural type wave-absorbing material |
| CN107754835A (en) * | 2017-11-27 | 2018-03-06 | 成都欣华源科技有限责任公司 | A kind of wear-resisting residual oil hydrocatalyst |
| US20190194364A1 (en) * | 2017-12-22 | 2019-06-27 | Ramaco Carbon, Llc | Methods for forming resins and other byproducts from raw coal |
| US20190194544A1 (en) * | 2017-12-22 | 2019-06-27 | Ramaco Carbon, Llc | Methods for producing advanced carbon materials from coal |
| WO2020253104A1 (en) * | 2019-06-19 | 2020-12-24 | 江西铜业技术研究院有限公司 | Carbon nano tube preparation device and method |
| CN111185174A (en) * | 2020-01-19 | 2020-05-22 | 华东理工大学 | Catalyst for preparing olefin by CO hydrogenation and preparation method and application thereof |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111905737A (en) * | 2020-08-14 | 2020-11-10 | 郑州大学 | Preparation method and application of single iron catalyst and alkali metal modified catalyst |
| WO2022097949A1 (en) * | 2020-11-09 | 2022-05-12 | 주식회사 코본 | Method for continuously synthesizing carbon nanotubes |
| CN112408364A (en) * | 2020-11-30 | 2021-02-26 | 青岛科技大学 | Method for preparing carbon nano tube by catalytic pyrolysis of waste thermosetting plastic |
Non-Patent Citations (3)
| Title |
|---|
| 周颖;张艳;李振涛;余桂红;邱介山;: "以煤炭直接液化残渣为原料制备炭纳米管", 煤炭转化, vol. 30, no. 03, pages 41 - 44 * |
| 张军;王志坚;赵江红;宋金玲;朱珍平;: "由重质碳源合成碳纳米管", 煤炭转化, no. 01 * |
| 赵龙涛;陈垒;王方然;吕和坤;杨柳;张浩;: "煤直接液化残渣利用的发展现状和趋势", 河南化工, no. 02 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116621163A (en) * | 2023-06-01 | 2023-08-22 | 重庆中润新材料股份有限公司 | Synthesis method of carbon nano tube |
| CN116621163B (en) * | 2023-06-01 | 2024-03-12 | 重庆中润新材料股份有限公司 | Synthesis method of carbon nano tube |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114940489B (en) | 2023-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fathy | Carbon nanotubes synthesis using carbonization of pretreated rice straw through chemical vapor deposition of camphor | |
| CN109437157B (en) | Floating catalyst chemical vapor deposition method for single-walled carbon nanotube | |
| CN101693533B (en) | Method for preparing nanometer carbon fiber/foam coal through taking coal liquefaction residues as raw materials | |
| MX2014012549A (en) | Method for producing solid carbon by reducing carbon dioxide. | |
| CN111495381A (en) | Preparation method of flaky catalyst, flaky catalyst and application of flaky catalyst in preparation of superfine carbon nano tube | |
| Zhang et al. | Formation of carbon nanotubes from potassium catalyzed pyrolysis of bituminous coal | |
| CN110451485B (en) | Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof | |
| CN112973625B (en) | Lignin-based carbon nanotube and preparation method and application thereof | |
| CN114940489B (en) | Method for preparing carbon nano tube from coal liquefaction residues | |
| CN111634902B (en) | Method for preparing carbon nano tube by secondary catalytic reforming of lignin pyrolysis gas | |
| CN112547106A (en) | Carbon-nitrogen material supported nickel catalyst with adjustable mesoporous aperture and preparation method and application thereof | |
| CN111250092B (en) | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst | |
| CN111167460A (en) | Preparation of H by direct cracking of natural gas2Catalyst with CNTs (carbon nanotubes), and preparation method and application thereof | |
| CN108514872B (en) | Preparation method of alkali metal catalyst for carbon nano tube | |
| CN110844900A (en) | Method for preparing carbon nano tube by taking waste tire as raw material | |
| CN115057429A (en) | Method for co-production of nitrogen-doped lignin-based carbon nanotube and biochar | |
| CN108114753B (en) | Biomass oil reforming catalyst | |
| CN113088324B (en) | Method for extracting carbon nano material from waste lubricating oil, heavy oil or asphalt | |
| CN110745809B (en) | Method for preparing carbon nanotubes from coal | |
| CN111620321B (en) | Method for preparing carbon nano tube by using high-sulfur high-sodium coal | |
| CN1378974A (en) | Process and equipment for preparing nano carbon tubes | |
| Liu et al. | Novel synthesis of SiC/SiO2 nanochain heterojunctions from agricultural waste | |
| CN113955742B (en) | Process for preparing carbon nano tube by carbon dioxide-methane reforming technology | |
| CN114870846B (en) | Carbon dioxide methanation catalyst and preparation method and application thereof | |
| CN101209834B (en) | Method for preparing spiral nano carbon tube rope |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |