CN114426278A - Biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres and preparation method thereof - Google Patents
Biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon and a preparation method thereof. The method has simple process and low cost, provides a new channel for high-value utilization of the existing waste biomass tar, and also provides a new technology for optimizing the pore structure of the carbon material.
Description
Technical Field
The invention belongs to the technical field of porous carbon material preparation, and particularly relates to a biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres and a preparation method thereof.
Background
According to the measurement of the International Energy Agency (IEA), the total amount of biomass produced in the world every year is equivalent to 850 hundred million tons of standard coal, and the reserves are abundant. Compared with the traditional fossil energy, the biomass energy is renewable hydrocarbon energy, has the advantage of zero emission of carbon dioxide, and can realize the aims of national and international green low-carbon and sustainable development. Current biomass conversion technologies can be divided into three major categories, physical conversion, chemical conversion, and biological conversion. The thermochemical conversion technology of biomass is to thermally decompose macromolecular organic matters in the biomass into CO and CH4And the like, so as to obtain the biomass oil, the combustible gas and the like. Chemical conversion techniques can be further divided into direct combustion, gasification, liquefaction and pyrolysis. Due to the nature of biomass feedstock, a large amount of biomass tar, an intractable byproduct, is inevitably produced during the thermochemical conversion of biomass. The biomass tar is liquid at normal temperature, is corrosive to equipment and instruments, is easy to block pipelines, can generate carbon particles during combustion, and aggravates dust removal burden. The biomass tar reduces the utilization efficiency of biomass, and seriously restricts the industrial application of biomass indirect liquefaction and biomass gasification technologies.
The components of biomass tar are complex and will vary with the process reaction conditions such as temperature, pressure, and treatment regime. Physical, thermochemical, and plasma methods are currently the methods commonly used to treat biomass tar. The physical method is that the biomass tar is separated by a condensation mode and then physically removed by a dust removal device. Although the operation is simple, the energy of the biomass tar cannot be effectively utilized, and the secondary pollution is large. In the thermochemical treatment process, biomass tar is cracked into small-molecule combustible gas in the presence of a catalyst or at high temperature, the temperature requirement is high, and the pyrolysis catalyst is easy to deactivate. The plasma method is a technology for decomposing macromolecular organic matters in the biomass tar by heating with a plasma torch, has high energy consumption and strict requirements on a reactor, and is difficult to industrially apply. Therefore, the key to solve the problem of biomass tar treatment and accelerate the utilization of biomass energy is to find a treatment method which is efficient, clean, economical and simple in process and can retain the energy and properties of the biomass tar.
The method is an attractive high-valued technical route for converting low-value wastes and the like after biomass energy utilization into high-value-added chemicals, and the biomass tar has excellent plasticity and adjustable denaturation and has great potential in the aspect of preparation of functional solid carbon materials. The porous carbon refers to a carbon material with pore structures of different sizes, and has the advantages of large specific surface area, good stability, high conductivity, developed pore structure and the like. Meanwhile, the raw materials for preparing the porous carbon have rich varieties, wide sources and low price, so the method is applied to various fields. However, the properties of the primary carbon material still have defects, such as poor surface wettability, low activity and the like, and further development of the primary carbon material is limited. By introducing heteroatoms into the carbon atom lattice, the physicochemical properties of the porous carbon material can be significantly improved. Nitrogen atoms have a similar atomic radius as carbon atoms, but a distinct electronic configuration and electronegativity. Therefore, nitrogen atoms are doped in the porous carbon material structure, so that the material performance is improved, and meanwhile, the minimum lattice mismatch is realized.
At present, no relevant method for preparing porous carbon by nitrogen doping of biomass tar base is reported.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the biomass tar-based nitrogen-doped porous carbon modified by the nano carbon spheres and the preparation method thereof, and biomass tar is effectively utilized to produce the biomass tar-based nitrogen-doped porous carbon modified by the nano carbon spheres with developed pore structures.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon, which comprises the following steps:
1) the method comprises the following steps of taking biomass tar as a carbon source, taking strong base or strong base salt as an activating agent, fully dissolving and dispersing the biomass tar, a nitrogen source and the activating agent in water, drying, then pyrolyzing at high temperature in an argon atmosphere, and then cooling, washing and drying to obtain nitrogen-doped porous carbon;
2) grinding and uniformly mixing nitrogen-doped porous carbon and a template agent, then adding biomass tar, uniformly grinding, adding an activating agent, and continuously uniformly grinding to obtain a mixture;
3) and carrying out high-temperature pyrolysis on the mixture in an argon atmosphere, cooling, grinding and washing a pyrolysis product, drying, calcining the dried product at a high temperature in an ammonia atmosphere, and cooling to obtain the biomass tar-based nitrogen-doped porous carbon modified by the carbon nanospheres.
Preferably, the nitrogen source is an amine organic substance, the strong base or strong alkali salt is a potassium salt or a sodium salt, and the template agent is magnesium oxide.
More preferably, the amine organic compound is melamine or ethylenediamine.
Further preferably, the potassium salt or sodium salt is KOH, K2CO3、kHCO3NaOH or NaHCO3。
Preferably, in the step 1), the mass ratio of the biomass tar, the activating agent and the nitrogen source is (1-3): 2: 1.
preferably, in the step 1), the temperature of the high-temperature pyrolysis is 350-800 ℃, the high-temperature pyrolysis adopts sectional heating, the temperature is raised from room temperature to 350 ℃ at the speed of 5-6 ℃/min, the temperature is kept for 0.5-1 h, then the temperature is raised from 350 ℃ to 800 ℃ at the speed of 5 ℃/min, and the temperature is kept for 15-20 h.
Preferably, in the step 2), the mass ratio of the nitrogen-doped porous carbon to the biomass tar to the template agent to the activating agent is (1-2) to 1 (6-8): (4-8).
Preferably, in the step 3), the temperature of the high-temperature pyrolysis is 150-900 ℃, the high-temperature pyrolysis adopts sectional heating, the temperature is raised from room temperature to 150 ℃ at the speed of 5 ℃/min, the temperature is kept for 0.5-1 h, then the temperature is raised to 900 ℃ at the speed of 5 ℃/min, and the temperature is kept for 15-20 h.
Preferably, in step 3), the high-temperature calcination temperature is 800 ℃.
The invention also discloses the biomass tar-based nitrogen-doped porous carbon modified by the nano carbon spheres prepared by the preparation method, and the biomass tar-based nitrogen-doped porous carbon modified by the nano carbon spheres has three-dimensional graded porous morphology.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon, which comprises the steps of taking biomass tar as a carbon precursor, utilizing strong base or strong base salt as an activating agent and a pore-making agent, taking an amine organic compound as a nitrogen source, preparing the nitrogen-doped porous carbon by a chemical activation method and in-situ doping, then taking the biomass tar as the carbon precursor, carrying out secondary etching on the nitrogen-doped porous carbon, utilizing magnesium oxide as a template agent and utilizing strong base or strong base salt as an activating agent, namely, combining the activation method and the template method, and preparing the nano carbon sphere modified nitrogen-doped porous carbon material by a post-treatment doping mode. The method has simple process and low cost, provides a new high-value utilization channel for the existing waste biomass tar, and also provides a new technology for optimizing the pore structure of the carbon material.
The nitrogen-doped porous carbon material modified by the carbon nanospheres prepared by the method has the advantages of large specific surface area, high stability, three-dimensional cross-linked porous morphology and developed pore structure, contains abundant micropores, mesopores and mesopores, can be widely applied to the fields such as adsorption and desorption, catalysis, electrodes, energy storage materials and the like, and has good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of a nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon prepared by the method;
FIG. 2 is a scanning electron microscope image of the carbon nanospheres attached to the surface of the porous carbon.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
A preparation method of biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres comprises the following steps:
(1) taking a certain amount of KOH, biomass tar and ethylenediamine according to the mass ratio of 1:2:1, dissolving the sample in a beaker by using deionized water, and fully stirring at room temperature.
(2) Transferring the mixture obtained in the step (1) into a quartz boat, and performing vacuum drying at 80 ℃ for 12 h. And then transferring the mixture to a tubular furnace, carrying out high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 350 ℃ at the speed of 5-6 ℃/min, and keeping the temperature for 0.5-1 h. Then heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, and repeatedly washing with deionized water and a funnel and filtering. The washed product was dried at 60 ℃ using a vacuum drying oven.
(3) Taking a certain amount of the nitrogen-doped porous carbon, the biomass tar, the magnesium oxide and the KOH prepared in the step (1) according to the mass ratio of 1:1:8:8, grinding and mixing the carbon material and the magnesium oxide in a mortar, pouring the ground biomass tar into the mortar, grinding the mixture, and finally adding the KOH for grinding and mixing again.
(4) And (4) transferring the mixture obtained in the step (3) to a quartz boat, placing the quartz boat in a tube furnace, performing high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 150 ℃ at the speed of 5 ℃/min, and keeping the temperature for 0.5-1 h. And then heating to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, washing with dilute hydrochloric acid solution, filtering, washing with a large amount of deionized water, and filtering to neutrality. The washed product was dried at 60 ℃ using a vacuum drying oven.
(5) And (4) placing the product obtained in the step (4) into a tubular furnace, and calcining at high temperature under the condition of 800 ℃ in an ammonia atmosphere. Naturally cooling to room temperature and taking out.
Fig. 1 and 2 are scanning electron micrographs of example 1, and it can be clearly seen from fig. 1 that the porous carbon prepared by the invention has a three-dimensional cross-linked pore morphology and a rich pore structure. From fig. 2, it can be clearly seen that the carbon nanospheres are attached to the surface of the porous carbon, and further optimization of the carbon material structure is realized.
Example 2
A preparation method of biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres comprises the following steps:
(1) taking a certain amount of KHCO according to the mass ratio of 2:2:13And the biomass tar and the melamine are dissolved in a beaker by using deionized water, and the mixture is fully stirred at room temperature.
(2) Transferring the mixture obtained in the step (1) into a quartz boat, and performing vacuum drying at 80 ℃ for 12 h. And then transferring the mixture to a tubular furnace, carrying out high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 350 ℃ at the speed of 5-6 ℃/min, and keeping the temperature for 0.5-1 h. Then heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, and repeatedly washing with deionized water and a funnel and filtering. The washed product was dried at 60 ℃ using a vacuum drying oven.
(3) By massTaking a certain amount of nitrogen-doped porous carbon, biomass tar, magnesium oxide and KHCO prepared in the step (1) according to the ratio of 1:1:6:83Firstly, grinding and mixing a carbon material and magnesium oxide in a mortar, then pouring biomass tar for grinding, and finally adding KOH for grinding and mixing again.
(4) And (4) transferring the mixture obtained in the step (3) to a quartz boat, placing the quartz boat in a tube furnace, performing high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 150 ℃ at the speed of 5 ℃/min, and keeping the temperature for 0.5-1 h. And then heating to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, washing with dilute hydrochloric acid solution, filtering, washing with a large amount of deionized water, and filtering to neutrality. The washed product was dried at 60 ℃ using a vacuum drying oven.
(5) And (4) placing the product obtained in the step (4) into a tubular furnace, and calcining at high temperature under the condition of 800 ℃ in an ammonia atmosphere. Naturally cooling to room temperature and taking out
Example 3
A preparation method of biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres comprises the following steps:
(1) taking a certain amount of NaOH, biomass tar and ethylenediamine according to the mass ratio of 2:2:1, dissolving the sample in a beaker by using deionized water, and fully stirring at room temperature.
(2) Transferring the mixture obtained in the step (1) into a quartz boat, and performing vacuum drying at 80 ℃ for 12 h. And then transferring the mixture to a tubular furnace, carrying out high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 350 ℃ at the speed of 5-6 ℃/min, and keeping the temperature for 0.5-1 h. Then heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, and repeatedly washing with deionized water and a funnel and filtering. And drying the washed product at 60 ℃ by using a vacuum drying oven.
(3) Taking a certain amount of the nitrogen-doped porous carbon, the biomass tar, the magnesium oxide and the NaOH prepared in the step (1) according to the mass ratio of 1:1:8:4, grinding and mixing the carbon material and the magnesium oxide in a mortar, pouring the ground biomass tar into the mortar, grinding the mixture, and finally adding KOH for grinding and mixing again.
(4) And (4) transferring the mixture obtained in the step (3) to a quartz boat, placing the quartz boat in a tube furnace, performing high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 150 ℃ at a speed of 5 ℃/min, and keeping the temperature for 0.5-1 h. And then heating to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, washing with dilute hydrochloric acid solution, filtering, washing with a large amount of deionized water, and filtering to neutrality. The washed product was dried at 60 ℃ using a vacuum drying oven.
(5) And (4) placing the product obtained in the step (4) into a tubular furnace, and calcining at high temperature under the condition of 800 ℃ in an ammonia atmosphere. Naturally cooling to room temperature and taking out.
Example 4
A preparation method of biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres comprises the following steps:
(3) taking a certain amount of NaHCO according to the mass ratio of 3:2:13And the biomass tar and the melamine are dissolved in a beaker by using deionized water, and the mixture is fully stirred at room temperature.
(4) Transferring the mixture obtained in the step (1) into a quartz boat, and performing vacuum drying at 80 ℃ for 12 h. And then transferring the mixture to a tubular furnace, carrying out high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 350 ℃ at the speed of 5-6 ℃/min, and keeping the temperature for 0.5-1 h. Then heating to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, and repeatedly washing with deionized water and a funnel and filtering. And drying the washed product at 60 ℃ by using a vacuum drying oven.
(3) Taking a certain amount of nitrogen-doped porous carbon, biomass tar, magnesium oxide and NaHCO prepared in the step (1) according to the mass ratio of 1:1:8:63Firstly, grinding and mixing a carbon material and magnesium oxide in a mortar, then pouring biomass tar for grinding, and finally adding KOH for grinding and mixing again.
(4) And (4) transferring the mixture obtained in the step (3) to a quartz boat, placing the quartz boat in a tube furnace, performing high-temperature pyrolysis in an argon atmosphere by adopting a segmented heating mode, heating from room temperature to 150 ℃ at the speed of 5 ℃/min, and keeping the temperature for 0.5-1 h. And then heating to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 15-20 h. Naturally cooling to room temperature, transferring into a mortar, grinding, washing with dilute hydrochloric acid solution, filtering, washing with a large amount of deionized water, and filtering to neutrality. The washed product was dried at 60 ℃ using a vacuum drying oven.
(5) And (4) placing the product obtained in the step (4) into a tubular furnace, and calcining at high temperature under the condition of 800 ℃ in an ammonia atmosphere. Naturally cooling to room temperature and taking out.
In summary, the invention uses cheap biomass tar as a carbon source, firstly uses a chemical activation method to obtain the nitrogen-doped porous carbon material, and then uses the chemical activation method and a template method to combine, and attaches carbon nanospheres on the pore wall to further increase the specific surface area, thereby obtaining the nitrogen-doped porous carbon material modified by the carbon nanospheres. The prepared porous carbon material has the advantages of large specific surface area, high stability, three-dimensional cross-linked porous morphology, developed pore structure and good application prospect.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of biomass tar-based nitrogen-doped porous carbon modified by carbon nanospheres is characterized by comprising the following steps:
1) the method comprises the following steps of taking biomass tar as a carbon source, taking strong base or strong base salt as an activating agent, fully dissolving and dispersing the biomass tar, a nitrogen source and the activating agent in water, drying, then pyrolyzing at high temperature in an argon atmosphere, and then cooling, washing and drying to obtain nitrogen-doped porous carbon;
2) grinding and uniformly mixing nitrogen-doped porous carbon and a template agent, then adding biomass tar, uniformly grinding, adding an activating agent, and continuously uniformly grinding to obtain a mixture;
3) and (3) carrying out high-temperature pyrolysis on the mixture in an argon atmosphere, cooling, grinding and washing a pyrolysis product, drying, calcining the dried product at a high temperature in an ammonia atmosphere, and cooling to obtain the biomass tar-based nitrogen-doped porous carbon modified by the carbon nanospheres.
2. The method for preparing the nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon as claimed in claim 1, wherein the nitrogen source is an amine organic matter, the alkali or strong alkali salt is potassium salt or sodium salt, and the template agent is magnesium oxide.
3. The preparation method of the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon according to claim 2, wherein the amine organic substance is melamine or ethylenediamine.
4. The preparation method of the carbon nanosphere-modified biomass tar-based nitrogen-doped porous carbon as claimed in claim 2, wherein the potassium salt or sodium salt is KOH or K2CO3、kHCO3NaOH or NaHCO3。
5. The preparation method of the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon according to claim 1, wherein in the step 1), the mass ratio of the biomass tar to the activating agent to the nitrogen source is (1-3): 2: 1.
6. the preparation method of the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon according to claim 1, characterized in that in the step 1), the high-temperature pyrolysis temperature is 350-800 ℃, the high-temperature pyrolysis adopts sectional heating, the temperature is raised from room temperature to 350 ℃ at a speed of 5-6 ℃/min, the temperature is kept for 0.5-1 h, and then the temperature is raised from 350 ℃ to 800 ℃ at a speed of 5 ℃/min and is kept for 15-20 h.
7. The preparation method of the nano carbon sphere modified biomass tar-based nitrogen-doped porous carbon according to claim 1, wherein in the step 2), the mass ratio of the nitrogen-doped porous carbon to the biomass tar to the template to the activator is (1-2): 1 (6-8): (4-8).
8. The preparation method of the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon according to claim 1, wherein in the step 3), the high-temperature pyrolysis temperature is 150-900 ℃, the high-temperature pyrolysis adopts sectional heating, the temperature is raised from room temperature to 150 ℃ at a speed of 5 ℃/min, the temperature is kept for 0.5-1 h, then the temperature is raised to 900 ℃ at a speed of 5 ℃/min, and the temperature is kept for 15-20 h.
9. The preparation method of the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon as claimed in claim 1, wherein in the step 3), the high-temperature calcination temperature is 800 ℃.
10. The nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon prepared by the preparation method of any one of claims 1 to 9 is characterized in that the nanocarbon sphere modified biomass tar-based nitrogen-doped porous carbon has a three-dimensional hierarchical porous morphology.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115215338A (en) * | 2022-07-26 | 2022-10-21 | 西安交通大学 | Process system and method for preparing porous carbon through carbonization and activation of biomass tar |
| CN115228435A (en) * | 2022-07-29 | 2022-10-25 | 山东省科学院能源研究所 | Method for circularly and continuously preparing and regenerating activated carbon adsorbent |
| CN116272942A (en) * | 2023-03-24 | 2023-06-23 | 西安交通大学 | Method for functionalizing biomass tar derived carbon-based material |
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