CN112624086B - Controllable preparation method of lignin-based micro-nano carbon spheres - Google Patents
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Abstract
The invention discloses a controllable preparation method of lignin-based micro-nano carbon spheres, which comprises the following steps: mixing a lignin raw material and an organic solvent, and stirring to obtain a lignin solution; adding deionized water into the lignin solution, stirring, and removing the organic solvent to obtain a lignin micro-nanosphere suspension; carrying out hydrothermal reaction on the lignin micro-nano sphere suspension, centrifuging, and freeze-drying to obtain covalently crosslinked lignin micro-nano spheres; carbonizing the covalently crosslinked lignin micro-nano spheres to obtain lignin-based micro-nano carbon spheres. The preparation method can prepare the lignin-based micro-nano carbon spheres with uniform and controllable size, regular appearance and solid structure, realizes the controllable preparation of the lignin-based micro-nano carbon spheres, has the advantages of simple process, mild preparation conditions, low cost and the like, conforms to the green chemical concept, and has higher application value and better application prospect.
Description
Technical Field
The invention relates to a controllable preparation method of lignin-based micro-nano carbon spheres.
Background
The carbon nanospheres have controllable size, high specific surface area and high stability, and are widely used in the fields of electrode materials, catalysis and adsorption. In recent years, the preparation of carbon nanospheres from biomass materials has become a research hotspot. The lignin has the characteristic of high carbon content and is an ideal precursor for developing the nano carbon spheres. However, the existing preparation method of the lignin-based micro-nano carbon spheres has the technical problems that the size and the morphology of the carbon spheres are difficult to control, the use of chemical reagents or the harm to the environment cannot be avoided, and the like. Therefore, a simple and green method is urgently needed to be developed to realize the efficient and controllable preparation of the lignin-based micro-nano carbon spheres, and the method has important significance for further expanding the utilization space of lignin.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method which is simple in process, mild in preparation conditions, low in cost and capable of controllably preparing lignin-based micro-nano carbon spheres with uniform and controllable sizes and regular shapes.
In order to solve the technical problems, the invention adopts the technical scheme that:
a controllable preparation method of lignin-based micro-nano carbon spheres comprises the following steps:
s1, mixing a lignin raw material and an organic solvent, and stirring to obtain a lignin solution;
s2, adding deionized water into the lignin solution obtained in the step S1, stirring, and removing the organic solvent to obtain a lignin micro-nanosphere suspension;
s3, carrying out hydrothermal reaction on the lignin micro-nanosphere suspension obtained in the step S2, centrifuging, and freeze-drying to obtain covalently crosslinked lignin micro-nanospheres;
and S4, carbonizing the covalently crosslinked lignin micro-nano spheres obtained in the step S3 to obtain lignin-based micro-nano carbon spheres.
In the step S1, the ratio of the lignin raw material to the organic solvent is 5 mg-20 mg: 10mL.
In the above controllable preparation method of the lignin-based micro-nano carbon spheres, a further improvement is that in the step S1, the lignin raw material is at least one of alkali lignin, high-boiling alcohol lignin and enzymatic hydrolysis lignin; the organic solvent is at least one of tetrahydrofuran, dioxane and dimethylformamide.
The controllable preparation method of the lignin-based micro-nano carbon spheres is further improved, in the step S1, the stirring speed is 100 rpm-1000 rpm; the stirring time is until the lignin is completely dissolved in the organic solvent.
In the controllable preparation method of the lignin-based micro-nano carbon spheres, the volume ratio of the lignin solution to the deionized water is 1: 4 in the step S2.
In the controllable preparation method of the lignin-based micro-nano carbon spheres, the dropping speed of the deionized water in the step S2 is 2-20 mL/min.
The controllable preparation method of the lignin-based micro-nano carbon spheres is further improved, in the step S2, the stirring speed is 100 rpm-1000 rpm; the stirring time is 5-12 h.
In the controllable preparation method of the lignin-based micro-nano carbon spheres, the hydrothermal reaction temperature is 160-200 ℃ in the step S3; the hydrothermal reaction time is 12h.
In the above controllable preparation method of the lignin-based micro-nano carbon spheres, the carbonization is performed in an inert atmosphere in step S4; controlling the heating rate to be 3-8 ℃/min in the carbonization process; the carbonization temperature is 700-900 ℃; the carbonization time is 2h.
The controllable preparation method of the lignin-based micro-nano carbon spheres is further improved, and the inert atmosphere is nitrogen atmosphere.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a controllable preparation method of lignin-based micro-nano carbon spheres, which comprises the steps of preparing lignin micro-nano spheres with uniform size and regular structure by a solvent-anti-solvent method through self-assembly, then crosslinking and polymerizing lignin molecules in the micro-nano spheres through hydrothermal treatment, improving the structural strength and the thermal stability of the micro-nano spheres, and finally cracking the micro-nano spheres through carbonization treatment to obtain the micro-nano carbon spheres. In the preparation process, the controllable preparation of the micro-nano spheres can be realized by regulating and controlling the initial concentration of lignin in an organic solvent, the dropping speed of deionized water and the stirring speed, so that the regulation and control of the micro-nano carbon spheres are realized; the hydrothermal treatment mainly improves the structural strength of the micro-nano spheres, so that the micro-nano spheres can not collapse in the carbonization process, the lignin-based micro-nano carbon spheres with uniform and controllable size, regular appearance and solid structure are prepared, and the controllable preparation of the lignin-based micro-nano carbon spheres is realized. The preparation method has the advantages of simple process, mild preparation conditions, low cost and the like, conforms to the green chemical concept, and has higher application value and better application prospect.
(2) According to the invention, the ratio of the lignin raw material to the organic solvent is optimized to be 5-20 mg: 10mL, so that the lignin can be ensured to have better solubility in the organic solvent, and the lignin micro-nanospheres with adjustable and uniform particle sizes can be obtained; meanwhile, the volume ratio of the lignin raw material to the deionized water is optimized to be 1: 4, the lignin molecules can be ensured to completely participate in the formation of the micro-nanospheres, and the concentration is moderate.
(3) In the invention, the dropping speed of the deionized water is optimized to be 2-20 mL/min, so that the particle size of the lignin micro-nanospheres can be conveniently regulated.
(4) According to the invention, the hydrothermal reaction temperature is optimized to be 160-200 ℃, the time is 12h, the formation of a cross-linked network by lignin molecules in the lignin micro-nanospheres can be ensured, and the structural collapse can not occur in the carbonization process.
(5) According to the invention, the temperature rise rate is controlled to be 3-8 ℃/min, the carbonization temperature is 700-900 ℃, and the carbonization time is 2h in the carbonization process, so that the higher carbonization rate can be ensured, and the preparation of the lignin-based micro-nano carbon spheres with higher carbon content is facilitated.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, 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.
Fig. 1 is an SEM image of lignin-based micro-nano carbon spheres prepared in example 1 of the present invention.
Fig. 2 is a TEM image of the lignin-based micro-nano carbon spheres prepared in embodiment 1 of the present invention.
Fig. 3 is a particle size distribution diagram of the lignin-based micro-nano carbon spheres prepared in embodiment 1 of the present invention.
Fig. 4 is an SEM image of the lignin-based carbon material prepared in comparative example 1.
Fig. 5 is an SEM image of the lignin-based carbon material prepared in comparative example 2.
Detailed Description
The invention is further described below with reference to the drawings and the specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1
A preparation method of lignin-based micro-nano carbon spheres comprises the following steps:
(1) And (3) placing 20mg of enzymatic hydrolysis lignin in a 250mL beaker, adding 10mL of tetrahydrofuran, and stirring at 800rpm until the enzymatic hydrolysis lignin is dissolved to obtain a lignin solution.
(2) Adding 40mL of deionized water into the lignin solution obtained in the step (1) at a dropping speed of 4mL/min, and continuously stirring at 800rpm for 5 hours to completely volatilize tetrahydrofuran in the solution to obtain a lignin micro-nanosphere suspension;
(3) And (3) placing 40mL of the lignin nanosphere suspension obtained in the step (2) into a 100mL hydrothermal reaction kettle, treating for 12h at 160 ℃, centrifuging, and freeze-drying to obtain covalently crosslinked lignin nanosphere solid powder.
(4) Putting a certain amount of the co-crosslinked lignin micro-nano sphere solid powder obtained in the step (3) into a corundum ark/tube furnace, and carrying out heating treatment at 3 ℃ for min in a nitrogen atmosphere -1 The temperature is raised to 700 ℃ at the heating rate and carbonized for 2 hours to obtain the lignin-based micro-nano carbon spheres.
Fig. 1 is an SEM image of lignin-based micro-nano carbon spheres prepared in example 1 of the present invention. Fig. 2 is a TEM image of the lignin-based micro-nano carbon spheres prepared in example 1 of the present invention. Fig. 3 is a particle size distribution diagram of the lignin-based micro-nano carbon spheres prepared in embodiment 1 of the present invention. As can be seen from the figures 1 and 2, the lignin-based micro-nano carbon spheres prepared by the method are uniform in size, regular in morphology and solid in structure. As can be seen from the figure 3, the average particle size of the lignin-based micro-nano carbon spheres prepared by the method is 396.98nm.
Example 2
A controllable preparation method of lignin-based micro-nano carbon spheres is basically the same as the preparation method in the embodiment 1, and the differences are only that: the temperature for carbonization in example 2 was 800 ℃.
Tests prove that the lignin-based micro-nano carbon spheres prepared in the embodiment 2 are uniform in size, regular in morphology, solid in structure and 401.46nm in average particle size, and have no obvious change compared with the embodiment 1.
Example 3
A controllable preparation method of lignin-based micro-nano carbon spheres is basically the same as the preparation method in the embodiment 1, and the differences are only that: the temperature for carbonization in example 3 was 900 ℃.
Tests prove that the lignin-based micro-nano carbon spheres prepared in the embodiment 3 have uniform size, regular morphology, solid structure and average particle size of 404.30nm, and are not obviously changed compared with the embodiments 1 and 2.
Example 4
A controllable preparation method of lignin-based micro-nano carbon spheres is basically the same as the preparation method in the embodiment 1, and the differences are only that: in example 4, the amount of the enzymatic hydrolysis lignin was 5mg, and the carbonization temperature was 800 ℃.
Tests prove that the lignin-based micro-nano carbon spheres prepared in the embodiment 4 have uniform size, regular appearance and solid structure, have the average particle size of 266.61nm, and are reduced compared with the embodiment 1, because the lignin consumption is reduced, the lignin molecules dissolved in the solution are reduced, the lignin molecules participating in the formation of each nanosphere are reduced, and the particle size of the lignin micro-nano spheres obtained by self-assembly is reduced.
Comparative example 1
A method for preparing a lignin-based carbon material, comprising the steps of:
1) Putting 20mg of enzymatic hydrolysis lignin in a 250mL beaker, adding 10mL of tetrahydrofuran, stirring at 800rpm until the enzymatic hydrolysis lignin is dissolved, then titrating 40mL of deionized water at the speed of 4mL/min, continuously stirring at 800rpm for 5 hours to completely volatilize the tetrahydrofuran in the solution to obtain lignin micro/nanosphere suspension, and finally centrifuging and freeze-drying the lignin nanosphere suspension to obtain lignin nanosphere solid powder.
2) Putting a certain amount of lignin micro-nano sphere solid powder into a corundum ark/tube furnaceAt 3 deg.C for min under nitrogen atmosphere -1 The temperature is raised to 700 ℃ at the heating rate and carbonized for 2 hours to obtain the lignin-based carbon material.
Fig. 4 is an SEM image of the lignin-based carbon material prepared in comparative example 1. As can be seen from fig. 4, compared with example 1, the lignin micro/nanospheres prepared by self-assembly can not form spherical structures by direct carbonization, which indicates that lignin-based micro/nano carbon spheres with uniform size and regular morphology can not be prepared under the condition of omitting hydrothermal treatment because the lignin raw material is a random blocky structure, and the morphology of the lignin-based micro/nano carbon spheres can not be changed during direct carbonization, so that spherical structures can not be formed.
Comparative example 2
A method for preparing a lignin-based carbon material, comprising the steps of:
1) 20mg of enzymatic hydrolysis lignin is placed in a 100mL hydrothermal reaction kettle, treated for 12 hours at 160 ℃, and then centrifuged and freeze-dried to obtain solid powder.
2) Placing a certain amount of solid powder in a corundum ark/tube furnace, and heating at 3 deg.C for min under nitrogen atmosphere -1 The temperature is raised to 700 ℃ at the heating rate and carbonized for 2 hours to obtain the lignin-based carbon material.
Fig. 5 is an SEM image of the lignin-based carbon material prepared in comparative example 2. As can be seen from fig. 5, compared with example 1, a spherical structure cannot be formed by directly carbonizing lignin subjected to hydrothermal treatment, which indicates that lignin-based micro-nano carbon spheres with uniform size and regular morphology cannot be prepared without controllable preparation of lignin micro-nano spheres, because the hydrothermal treatment process only provides conditions for condensation reaction of lignin molecules in the lignin nano spheres, and the change of the morphology is difficult to control.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (5)
1. A controllable preparation method of lignin-based micro-nano carbon spheres is characterized by comprising the following steps:
s1, mixing a lignin raw material and an organic solvent, and stirring to obtain a lignin solution; the ratio of the lignin raw material to the organic solvent is 20 mg: 10mL;
s2, adding deionized water into the lignin solution obtained in the step S1, stirring, and removing the organic solvent to obtain a lignin micro-nanosphere suspension; the volume ratio of the lignin solution to the deionized water is 1: 4; the dropping speed of the deionized water is 2mL/min to 20mL/min; the rotating speed of the stirring is 100 rpm-1000 rpm; the stirring time is 5-12 h;
s3, carrying out hydrothermal reaction on the lignin micro-nanosphere suspension obtained in the step S2, centrifuging, and freeze-drying to obtain covalently crosslinked lignin micro-nanospheres; the temperature of the hydrothermal reaction is 160-200 ℃; the time of the hydrothermal reaction is 12 hours;
and S4, carbonizing the covalently crosslinked lignin micro-nano spheres obtained in the step S3 to obtain lignin-based micro-nano carbon spheres.
2. The controllable preparation method of lignin-based micro-nano carbon spheres according to claim 1, wherein in step S1, the lignin raw material is at least one of alkali lignin, high boiling alcohol lignin and enzymatic hydrolysis lignin; the organic solvent is at least one of tetrahydrofuran, dioxane and dimethylformamide.
3. The controllable preparation method of the lignin-based micro-nano carbon spheres according to claim 1, wherein in the step S1, the stirring speed is 100rpm to 1000rpm; the stirring time is until the lignin is completely dissolved in the organic solvent.
4. The controllable preparation method of the lignin-based micro-nano carbon spheres according to any one of claims 1 to 3, wherein in the step S4, the carbonization is performed in an inert atmosphere; controlling the heating rate to be 3-8 ℃/min in the carbonization process; the carbonization temperature is 700-900 ℃; the carbonization time is 2h.
5. The controllable preparation method of lignin-based micro-nano carbon spheres according to claim 4, wherein the inert atmosphere is a nitrogen atmosphere.
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| EP3053929A1 (en) * | 2015-02-06 | 2016-08-10 | Valmet Technologies Oy | Method for treating lignin-based material |
| CN106276848A (en) * | 2016-07-19 | 2017-01-04 | 华南理工大学 | A kind of with lignin for raw material nitrogen-doped carbon ball and preparation method and application |
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| CN110479309A (en) * | 2019-08-27 | 2019-11-22 | 大连工业大学 | It is a kind of using lignin as nanometer spherical carbon-based solid acid of raw material and its preparation method and application |
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