CN110451485B - Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof - Google Patents

Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof Download PDF

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CN110451485B
CN110451485B CN201910812557.8A CN201910812557A CN110451485B CN 110451485 B CN110451485 B CN 110451485B CN 201910812557 A CN201910812557 A CN 201910812557A CN 110451485 B CN110451485 B CN 110451485B
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lignin
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reconstruction
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carbon nanomaterial
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CN110451485A (en
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沈德魁
孙宇婷
石婧
秦可欣
田葆
王章鸿
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Southeast University
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Abstract

The invention discloses a lignin thermal reconstruction assembled carbon nanomaterial and a preparation method thereof, wherein transition metal salt is loaded on lignin through an excessive impregnation method, and the lignin-based carbon material rich in nano transition metal oxide particles is obtained after pyrolysis and muffle furnace calcination; placing the lignin-based carbon material into a vertical fixed bed, introducing a gaseous carbon source such as ethylene or mixed gas of methane and nitrogen, reacting at a certain temperature, and finally collecting and obtaining the carbon nano tube-lignin-based carbon material mixture after thermal reconstruction. The invention converts low-value lignin carbon materials into high-value carbon nano materials by using renewable resource lignin, has simple and easily obtained raw materials, controllable preparation conditions and wide application range, successfully develops and utilizes the low-value renewable resource of lignin, has great significance on resource utilization and environmental protection, and has popularization and application values.

Description

Lignin thermal reconstruction assembled carbon nanomaterial and preparation method thereof
Technical Field
The invention belongs to the technical field of energy materials, and particularly relates to a lignin thermal reconstruction assembly carbon nanomaterial and a preparation method thereof.
Background
Lignin is an important component (15-35%) of biomass, and is also a main component (more than 80%) of solid wastes such as papermaking black liquor residues, hydrolysis residues and the like. Therefore, the development and utilization of low-price renewable resources such as lignin and the preparation of high-value biomass-based carbon materials are of great significance for comprehensive utilization of resources and environmental protection. Among them, lignin is one of important uses of lignin in preparing carbon materials, and lignin is a renewable resource with the highest carbon content, which is unique and can be replaced in preparing carbon materials. However, the current lignin-based carbon materials mainly use low-quality carbon such as activated carbon and biochar, and cannot meet the requirements of high-performance carbon materials (such as carbon nano-tubes, carbon nano-fibers, graphene, fullerene and other carbon nano-materials) in the market. On the other hand, the carbon material mixture containing the carbon nano material has great application value in catalysis, energy storage and environment because of the multi-level pore structure, electric conduction, heat conduction and mass transfer. The current preparation method mainly comprises the steps of mixing and grafting two carbon materials, namely a carbon nano material and a conventional carbon material (active carbon or biochar and the like). Although the resulting carbon material mixture containing carbon nanomaterial has excellent properties, there are some problems that need to be solved. For example, the nano effect of the carbon nanomaterial itself is remarkable, and it is difficult to disperse and uniformly mix with another carbon material (activated carbon or biochar, etc.), thereby resulting in limited properties, poor stability, and unsatisfactory service life and regeneration ability of the obtained carbon material. Therefore, a simple lignin thermal reconstruction method for assembling the carbon nanomaterial is urgently needed, the preparation of a carbon material mixture containing the carbon nanomaterial is realized, and the high-value utilization of biomass solid waste to the carbon nanomaterial is realized.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides the lignin thermal reconstruction assembled carbon nanomaterial and the preparation method thereof. The simple lignin thermal reconstruction assembly carbon nanomaterial method provided by the invention can realize the preparation of a carbon material mixture containing carbon nanomaterial, and has better uniformity and stability.
The technical scheme is as follows: in order to achieve the above object, the method for preparing the lignin thermal reconstruction assembly carbon nanomaterial according to the present invention is characterized by comprising the following steps: loading transition metal salt onto lignin by an excessive impregnation method, and obtaining a lignin-based carbon material rich in nano transition metal oxide particles after pyrolysis and calcination; and introducing a gaseous carbon source and nitrogen mixed gas into the lignin-based carbon material, reacting at a high temperature, and finally collecting and obtaining a carbon nanotube-lignin-based carbon material mixture after thermal reconstruction, namely the lignin thermal reconstruction assembled carbon nanomaterial.
The excessive impregnation method is to mix transition metal salt solution and lignin, heat the mixture in water bath at 60 ℃ for 2 hours, and then put the mixture into an oven to stand for 12 hours.
Wherein the transition metal salt is chloride or nitrate. Preferably NiCl 2 、Ni(NO 3 ) 2 、FeNO 3 、FeCl 3 、Co(NO 3 ) 2 Or then CoCl 2 。
Preferably, the lignin comprises black liquor lignin or clarson lignin.
Wherein, the pyrolysis temperature is 800-900 ℃ after the transition metal salt is loaded on lignin by an excessive impregnation method, and the pyrolysis temperature is treated for 2-3 hours at constant temperature.
Wherein the calcination is preferably a muffle furnace at 400 ℃ for 2 hours.
Preferably, the gaseous carbon source is ethylene or methane.
Preferably, the gaseous carbon source and nitrogen gas are introduced into the reactor, and the reaction is carried out at a high temperature for 1-1.5h at 700-900 ℃.
More preferably, the introduced gaseous carbon source is ethylene, the ethylene flow is 10ml/min, the nitrogen flow is 100ml/min (and the whole process is introduced), the target temperature is 700-900 ℃, and the heating rate is 10 ℃/min. Keeping the temperature for 1 hour after the temperature reaches the target temperature, introducing ethylene at a rate of 10ml/min in the first half hour, and stopping introducing ethylene in the second half hour.
Wherein the lignin thermal reconstruction assembly carbon nanomaterial grows as a top growth under the catalysis of transition metal particles.
The lignin thermal reconstruction assembly carbon nanomaterial prepared by the preparation method of the lignin thermal reconstruction assembly carbon nanomaterial.
Wherein, the lignin thermal reconstruction assembly carbon nano material is a multi-wall carbon nano tube and the tube diameter is 20nm-120nm.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
according to the preparation method of the lignin thermal reconstruction assembled carbon nanomaterial, the low-value lignin carbon material is converted into the high-value carbon nanomaterial, so that the market demand for the high-value carbon material is met; low cost, wide application material range, environmental protection, and realization of resource reutilization and energy conservation.
According to the invention, the blending material (the blending material refers to an introduced gaseous carbon source, ethylene or a mixture of methane and nitrogen) is introduced in the lignin pyrolysis process, so that the decomposition of lignin can be deepened, the secondary polycondensation of tar is reduced, the structural deoxidization of lignin is promoted, and a purer carbon product is obtained. The pure carbon product is an excellent raw material for preparing the high-performance carbon nano material under the guiding and specific working conditions of the catalyst.
The invention has the advantages of simple and easily obtained raw materials, controllable preparation conditions and wide application range, successfully develops and utilizes the lignin which is a low-value renewable resource, has great significance on resource utilization and environmental protection, and has popularization and application values.
Drawings
FIG. 1 is an SEM image of lignin-based carbon material of example 1;
FIG. 2 is an SEM image of the carbon nanomaterial obtained in example 1;
FIG. 3 is a TEM transmission electron micrograph of the carbon nanomaterial obtained in example 1;
fig. 4 is a TEM transmission electron micrograph of the carbon nanomaterial obtained in example 1.
Detailed Description
The invention will be further illustrated with reference to examples.
Example 1
A preparation method of lignin thermal reconstruction assembled carbon nanomaterial comprises the following specific steps:
2.377g of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O), dissolving in 50mL distilled water; 10g of clarson lignin was weighed into a 100mL beaker, to which 50mL of Ni solution was transferred, and stirred in a water bath at 60℃for 2 hours. After stirring, the mixture was taken out, transferred to an oven, and dried at 105℃for 12 hours. Weigh 2g of sampleSetting target pyrolysis temperature at 800 deg.c, holding temperature for 3 hr, heating rate at 10 deg.c/min and N 2 As a shielding gas (flow rate 100 mL/min), a lignin-based carbon material was prepared. 0.1g lignin-based carbon material is weighed, N2 is used as a protective gas (the flow is 100 mL/min), the target pyrolysis temperature is set at 800 ℃, and the heating rate is 10 ℃/min. When the fixed bed temperature reaches 800 ℃, keeping the constant temperature for 1 hour, introducing ethylene at the speed of 10ml/min for the first 0.5 hour, and stopping introducing ethylene for the last 0.5 hour, so that the carbon nano material grows completely.
Performance test: and (3) performing Scanning Electron Microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Transmission Electron Microscopy (TEM) characterization analysis on the obtained lignin-based carbon material and carbon nano material.
Scanning electron microscope diagrams of the lignin-based carbon material and the carbon nanomaterial obtained in the embodiment are shown in fig. 1 and 2, and transmission electron microscope diagrams of the carbon nanomaterial are shown in fig. 3 and 4. The synthesized carbon nano material is a hollow multi-wall tubular structure, the wall thickness of the tube is about 10nm, the interlayer distance is 0.3-0.4nm, the diameter is 20-70nm, the length is 800-1800nm, and the synthesized carbon nano material can be determined to be a multi-wall carbon nano tube. The nickel particles are attached to the top ends of the carbon nano-tubes, so that the growth process of the carbon nano-tubes accords with the mechanism of top end growth, namely, the carbon nano-tubes are separated out from the lower parts of the nickel particles, and the nickel particles are always positioned at the top ends of the carbon nano-tubes. According to both the figures 2 and 3, the carbon nanotubes and other carbon materials are uniformly mixed, so that the preparation of the carbon material mixture containing the carbon nanomaterial is realized, and the high-value utilization of biomass solid waste to the carbon nanomaterial is realized.
Example 2
A preparation method of lignin thermal reconstruction assembled carbon nanomaterial comprises the following specific steps:
1.189g of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O), dissolving in 50mL distilled water; 10g of clarson lignin was weighed into a 100mL beaker, to which 50mL of Ni solution was transferred, and stirred in a water bath at 60℃for 2 hours. After stirring, the mixture was taken out, transferred to an oven, and dried at 105℃for 12 hours. Weighing 2g of sample, setting target pyrolysis temperature to 800 ℃, keeping constant temperature for 3 hours, and heatingAt a rate of 10 ℃/min, with N 2 As a shielding gas (flow rate 100 mL/min), a lignin-based carbon material was prepared. 0.1g of lignin-based carbon material is weighed and placed, N2 is used as protective gas (the flow is 100 mL/min), the target pyrolysis temperature is set to 900 ℃, and the heating rate is 10 ℃/min. And when the temperature of the fixed bed reaches 900 ℃, keeping the constant temperature for 1 hour, introducing ethylene at the speed of 10ml/min for the first 0.5 hour, and stopping introducing ethylene for the last 0.5 hour, so that the carbon nano material grows completely.
And carrying out characterization analysis on the obtained lignin-based carbon material and the carbon nano material. The obtained carbon nano material is a multi-wall carbon nano tube with the tube diameter of 30-80nm.
Example 3
A preparation method of lignin thermal reconstruction assembled carbon nanomaterial comprises the following specific steps:
1.189g of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O), dissolving in 50mL distilled water; 10g of clarson lignin was weighed into a 100mL beaker, to which 50mL of Ni solution was transferred, and stirred in a water bath at 60℃for 2 hours. After stirring, the mixture was taken out, transferred to an oven, and dried at 105℃for 12 hours. 2g of sample is weighed, the target pyrolysis temperature is set to 800 ℃, the constant temperature time is set to 3 hours, the heating rate is set to 10 ℃/min, N2 is used as protective gas (the flow is 100 mL/min), and then the sample is put into a muffle furnace to be calcined for 2 hours at 400 ℃ to prepare the lignin-based carbon material. 0.1g lignin-based carbon material is weighed, N2 is used as a protective gas (the flow is 100 mL/min), the target pyrolysis temperature is set to 900 ℃, and the heating rate is 10 ℃/min. When the temperature of the fixed bed reaches 900 ℃, keeping the temperature for 1.5 hours, introducing ethylene at the speed of 10ml/min in the first 1 hour, and stopping introducing ethylene in the last 0.5 hour, so that the carbon nano material grows completely.
And carrying out characterization analysis on the obtained lignin-based carbon material and the carbon nano material. The obtained carbon nano material is a multi-wall carbon nano tube with the tube diameter of 60-120nm.
Example 4
Example 4 was prepared in the same manner as example 1, except that: the transition metal salt is Ni (NO) 3 ) 2 The lignin is clarson lignin, the pyrolysis temperature is 900 ℃, the heating rate is 10 ℃/min, and the pyrolysis is constantTreating for 2h; the gaseous carbon source is methane, and the gaseous carbon source is introduced to react for 1.5 hours at 700 ℃.
Example 5
Example 5 was prepared in the same manner as in example 1, except that: the transition metal salt is FeCl 3 Lignin is black liquor lignin, the pyrolysis temperature is 850 ℃, the heating rate is 10 ℃/min, and the pyrolysis is carried out for 2.5 hours at constant temperature; the gaseous carbon source is ethylene which is reacted at 900 ℃ for 1h.

Claims (6)

1. The preparation method of the lignin thermal reconstruction assembled carbon nanomaterial is characterized by comprising the following steps of: loading transition metal salt onto lignin by an excessive impregnation method, and obtaining a lignin-based carbon material rich in nano transition metal oxide particles after pyrolysis and calcination; introducing a gaseous carbon source and nitrogen mixed gas into the lignin-based carbon material, reacting at a high temperature, and finally collecting to obtain a carbon nanotube-lignin-based carbon material mixture after thermal reconstruction, namely the lignin thermal reconstruction assembled carbon nanomaterial;
loading transition metal salt on lignin by an excessive impregnation method, and then carrying out constant-temperature treatment for 2-3 hours at the pyrolysis temperature of 800-900 ℃; introducing a gaseous carbon source and nitrogen mixed gas, and reacting at a high temperature to 700-900 ℃ for 1-1.5h; the transition metal salt is NiCl 2 。
2. The method of preparing a lignin thermal reconfiguration assembled carbon nanomaterial of claim 1, wherein the lignin comprises black liquor lignin or clarson lignin.
3. The method for preparing lignin thermal reconstruction assembly carbon nanomaterial according to claim 1, wherein the gaseous carbon source is ethylene or methane.
4. The method for preparing the lignin thermal reconstruction assembly carbon nanomaterial according to claim 1, wherein the lignin thermal reconstruction assembly carbon nanomaterial is grown on top under the catalysis of transition metal particles.
5. A lignin thermal-reconstruction-assembled carbon nanomaterial prepared by the method for preparing a lignin thermal-reconstruction-assembled carbon nanomaterial of claim 1.
6. The lignin thermal reconstruction assembly carbon nanomaterial of claim 5, wherein the lignin thermal reconstruction assembly carbon nanomaterial is a multi-walled carbon nanotube and has a tube diameter of 20nm to 120nm.
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CN111170402B (en) * 2020-02-12 2021-07-02 东华大学 Method for removing perfluorooctanoic acid in water body by using lignin-based carbon nano tube
CN111634902B (en) * 2020-06-01 2023-03-28 南京博岭节能环保研究院有限公司 Method for preparing carbon nano tube by secondary catalytic reforming of lignin pyrolysis gas
CN112265981B (en) * 2020-10-23 2022-08-26 中南林业科技大学 Method for preparing carbon nano tube by lignin nano micelle
CN112973625B (en) * 2021-02-05 2022-05-10 中南林业科技大学 Lignin-based carbon nanotube and preparation method and application thereof

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