CN112225215A - High-specific-surface-area and multi-stage-hole hollow carbon microsphere taking lignin as raw material and preparation method thereof - Google Patents
High-specific-surface-area and multi-stage-hole hollow carbon microsphere taking lignin as raw material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-specific-surface-area and multi-level-hole hollow carbon microsphere taking lignin as a raw material and a preparation method thereof. The method comprises the following steps: the preparation method comprises the steps of carrying out spray drying on a mixed solution of lignin and sulfite to obtain lignin microspheres, carbonizing the lignin microspheres in inert gas to obtain carbonized microspheres, mixing the carbonized microspheres with an activating agent, drying and activating to finally obtain the hollow carbon microspheres with intact spherical structures, high specific surface areas, large pore volumes, rich surface activities and multi-layer pore structures. The specific surface area of the hollow carbon microsphere can reach 3406m2The pore volume can reach 2.46cm3The surface oxygen content can reach 9.59 at%, and the excellent pore structure and surface chemical property can be widely applied to the industries of electronics, chemical engineering, environmental protection and the like. Moreover, the invention has simple preparation process, convenient operation, low cost and good industrial applicationThe use value is high.
Description
Technical Field
The invention belongs to the technical field of biomass carbon materials, and particularly relates to a high-specific-surface-area and multi-level-hole hollow carbon microsphere taking lignin as a raw material and a preparation method thereof.
Background
With the development of industry and the increase of population, the consumption of fossil fuel is rapidly increased, and the energy and environmental problems caused by the consumption of fossil fuel are becoming more and more serious. Therefore, there is an urgent need to find a green and sustainable raw material for producing new energy and high performance materials. The wood fiber biomass is expected to replace fossil raw materials as a natural, rich and renewable resource. Lignin is an important constituent of plant cell walls, second only to the second largest natural high molecular polymers of cellulose. The advantages of high carbon content, good thermal stability, special benzene ring structure, biodegradability and the like make the application of the material in energy, materials, environment and the like have great potential. However, only about 2% of the lignin produced annually from pulp and paper mills is highly valued and mostly incinerated as low-grade fuel. This is not only a waste of biomass resources, but also environmental pollution. Therefore, how to utilize lignin efficiently is of great significance.
Biomass nanoporous carbon materials are rapidly developed and widely studied due to high specific surface area, large pore volume, excellent thermal stability, low production cost, and rich renewable preparation raw materials. At present, the biomass porous carbon material is widely applied to the aspects of air purification, water treatment, catalysts, energy storage and the like. One of the important production methods is to mix biomass with high carbon content with an activating agent (water vapor, potassium hydroxide, phosphoric acid, etc.) and then obtain the biomass through high-temperature treatment. The method is simple to operate and the conditions are easy to control. Researchers successfully convert lignin into a carbon material with high porosity by using the method, and high-value utilization of the lignin is realized. Patent CN108715446A discloses a method for preparing high and medium porosity activated carbon by taking alkali lignin as raw materialThe method comprises extracting alkali lignin from black liquor, carbonizing at high temperature, and steaming with water vapor or ZnCl2And activating to finally obtain the lignin-based activated carbon with high specific surface area. In patent application publication No. CN110894071A, a method for preparing a carbon material by using alkali lignin as a raw material and ammonium polyphosphate powder as an activating agent is disclosed, and a lignin-based carbon material with high phosphorus content is obtained by activating the alkali lignin with high-temperature ammonium polyphosphate. The material has good adsorption capacity on dye in wastewater.
Currently, the preparation of lignin-based carbon materials is extensively developed and studied. But the lignin-based carbon material obtained is mostly in irregular block and powder form; and the pore size distribution is relatively single. Therefore, a strategy for effectively preparing the lignin-based carbon material with high specific surface area, proper pore size distribution and regular appearance is urgently needed.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-specific-surface-area and multi-stage-hole hollow carbon microsphere taking lignin as a raw material and a preparation method thereof.
The invention aims to provide a method for preparing a high-specific surface area and multi-level hole hollow carbon microsphere by taking lignin as a raw material, which has the advantages of simple process and low cost.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a method for preparing a high-specific surface area and multi-level hole hollow carbon microsphere by taking lignin as a raw material, which comprises the following steps:
(1) adding lignin and sulfite into water, heating, stirring to obtain a mixed solution, adjusting the pH of the mixed solution to 7.0-9.0 by using an acid solution, carbon dioxide gas or sulfite, and drying in a spray dryer to obtain lignin microspheres;
(2) heating the lignin microspheres obtained in the step (1) in a high-temperature furnace in an inert atmosphere for carbonization treatment, and naturally cooling to room temperature to obtain carbonized microspheres;
(3) mixing the carbonized microspheres and the activating agent in the step (2), adding the mixture into ultrapure water, uniformly oscillating and mixing, standing, and drying to obtain a solid mixture of the carbonized microspheres and the activating agent;
(4) and (3) heating the solid mixture of the carbonized microspheres and the activating agent in the step (3) in a high-temperature furnace in an inert atmosphere to carry out activation treatment to obtain activated carbon microspheres, then washing with water until the filtrate is neutral, and drying to obtain the hollow carbon microspheres with high specific surface area and hierarchical pores.
Further, the lignin in the step (1) is more than one of sodium lignosulphonate and alkali lignin; the sulfite is more than one of sodium sulfite and potassium sulfite; the mass ratio of the lignin to the sulfite is 5:1-1: 1; in the mixed solution, the total solid content of lignin and sulfite is 30-36%.
Further, the temperature of the stirring treatment in the step (1) is 120-220 ℃, and the time of the stirring treatment is 2-6 h.
Further, the drying mode in the step (1) is spray drying; the temperature of the air inlet of the spray drying is 250-350 ℃, the temperature of the air outlet is 100-150 ℃, and the evaporation amount of water per hour is 1.5-2.5 tons; the water content of the lignin microspheres is less than 6%.
Further, the temperature rising rate of the step (2) is 5-10 ℃/min; the temperature of the carbonization treatment is 400-500 ℃, and the time of the carbonization treatment is 50-80 min.
Further, the activating agent in the step (3) is more than one of potassium hydroxide and potassium carbonate solid; according to the dry weight, the mass ratio of the carbonized microspheres to the activating agent is 1:1-1: 4.
Preferably, the mass ratio of the carbonized microspheres to the aqueous solution of the activating agent is 1:2-1:3 in terms of dry weight.
Further, the standing time in the step (3) is 2-4 h.
Further, the heating rate in the step (4) is 5-20 ℃/min; the temperature of the activation treatment is 700-900 ℃, and the time of the activation treatment is 40-100 min.
Further, the inert atmosphere in the step (2) and the step (4) is nitrogen, argon or a mixed gas of the nitrogen and the argon. The flow rate of the inert atmosphere is 200-500 ml/min.
The invention provides a high-specific surface area and hierarchical pore hollow carbon microsphere prepared by the preparation method.
A large number of tests and results show that in the preparation method provided by the invention, the carbonization temperature, the activation time and the activation temperature of the lignin microspheres during carbonization and the mass ratio of the carbonization microspheres to the activating agent are all key influence factors of the specific surface area, the pore volume and the pore size distribution of the hollow carbon microspheres. The specific surface area and the pore volume of the hollow carbon microsphere can be improved and the pore size distribution of the hollow carbon microsphere can be expanded by prolonging the activation time, increasing the carbonization temperature and the activation temperature and increasing the mass ratio of the carbonized microsphere to the activating agent; however, too long an activation time, too high a carbonization temperature, an activation temperature, and a mass ratio of the carbonized microspheres to the activator cause collapse of the pore skeleton of the carbon microspheres and loss of ignition resulting in a decrease in specific surface area, pore volume, and destruction of the shape of the carbon microspheres.
By regulating and controlling the above influencing factors, the maximum specific surface area of the prepared hollow carbon microsphere reaches 3406m2The total pore volume can reach 2.19cm3(g) a multi-level pore structure with interconnected micropores-hollows-macropores, and surface oxygen content as high as 9.59 at%, which are far superior to the performance of hollow carbon spheres prepared by the prior art and the performance of activated carbon on the existing market (700 m)2/g<Specific surface area<1600m2/g)。
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the hollow carbon microsphere prepared by the method has a developed hierarchical pore structure and a high specific surface area (1799-3406 m)2G) large pore volume (1.02-2.46 cm)3The method can adjust and control the proportion of micropores, hollows and macropores of the hollow carbon microspheres by changing the carbonization temperature, the mass ratio of the carbonized microspheres to the activating agent and the activation temperature.
(2) The diameter of the hollow carbon microsphere prepared by the method is 40.26-72.21 microns, and the diameter of the hollow carbon microsphere can be regulated and controlled by the mass ratio of the carbonized microsphere to the activating agent and the drying condition of a spray dryer.
(3) The method can ensure that the shape of the carbon microsphere is not damaged in the processes of dipping and activating by the activating agent through the step of carbonizing the lignin microsphere; during activation, the interior of the carbon microsphere is thermally degraded and released from the pore structure on the carbon shell, thereby forming a hollow structure.
(4) According to the invention, the high-performance hollow carbon microspheres are successfully prepared by using lignin extracted from pulping waste liquid as a raw material, the high-valued utilization of the lignin is realized, the concept of changing waste into valuable is fully considered, the production cost of the hollow carbon microspheres is reduced, and the method has an important significance for realizing the sustainable development of the carbon material.
(5) The hollow carbon microsphere prepared by the invention can be widely applied to the fields of environmental protection, electronics, chemical engineering and the like with excellent surface chemical properties and developed pore structures.
(6) The preparation method disclosed by the invention is simple to operate, easy to control conditions, low in cost, environment-friendly and easy to realize industrial production.
Drawings
Fig. 1 is a scanning electron microscope image of lignin microspheres prepared in example 1.
Fig. 2 is a scanning electron microscope image of the hollow carbon microsphere prepared in example 1.
Fig. 3 is a nitrogen adsorption/desorption isotherm diagram of the hollow carbon microspheres prepared in examples 1 to 5.
FIG. 4 is a graph showing the pore size distribution of hollow carbon microspheres prepared in examples 1 to 3.
FIG. 5 is a graph showing the pore size distribution of hollow carbon microspheres prepared in examples 4 to 5.
FIG. 6 is an X-ray photoelectron spectrum of hollow carbon microspheres prepared according to examples 1 to 5.
Fig. 7 is a constant current charge and discharge graph of hollow carbon microspheres prepared according to examples 1-5.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
Firstly, mixing needle leaf alkali lignin and sodium sulfite according to a mass ratio of 5:1, adding the mixture into water, stirring and reacting for 6 hours at 120 ℃, adjusting the pH of an aqueous solution to 7.0 by using carbon dioxide gas and sodium sulfite, wherein the total solid content of the needle leaf alkali lignin and the sodium sulfite in the solution is 30%, and finally, putting the aqueous solution into a centrifugal spray dryer for drying, wherein the air inlet temperature of the spray dryer is 250 ℃, the air outlet temperature of the spray dryer is 100 ℃, and the evaporation capacity of water per hour is 1.5 tons; and obtaining the lignin microspheres, wherein the water content of the lignin microspheres is less than 6%.
And secondly, placing the obtained lignin carbon microspheres in a tube furnace, introducing argon at the flow rate of 200ml/min, heating to 450 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 50min, and naturally cooling to room temperature to obtain the lignin carbonized microspheres.
And thirdly, blending the lignin carbonized sphere and potassium hydroxide according to the mass ratio of 1:3, adding the mixture into ultrapure water, oscillating for 5min, uniformly mixing, standing for 2h, and then placing the mixture into an oven for drying to obtain a solid mixture of the lignin carbonized sphere and the potassium hydroxide.
And fourthly, placing the obtained mixture in a tubular furnace, introducing argon at the flow rate of 200ml/min, raising the temperature to 800 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 40min, naturally cooling to room temperature, filtering and washing with ultrapure water until the filtrate is neutral, placing the obtained solid in an oven, and drying to be completely dry to obtain the high-specific-surface-area and multi-level-hole hollow carbon microsphere marked as HPAC-1.
Fig. 1 is a scanning electron microscope picture of the lignin microspheres obtained in the first step, which shows that the lignin microspheres have excellent spherical morphology. FIG. 2 is a scanning electron microscope image of the obtained high specific surface area, multi-stage pore hollow carbon microsphereThe sheet shows that the lignin-based hollow carbon microspheres still keep complete spherical shapes after carbonization and activation treatment. FIG. 3 shows the nitrogen adsorption/desorption isotherm plot of HPAC-1, which can be seen in FIG. 3 in the low pressure region (0)<p/p0<0.1) and a neutral pressure zone (0.1)<p/p0<0.6) all had large nitrogen adsorption amounts, indicating that HPAC-1 had abundant meso-micropores, and the specific surface area of HPAC-1 was 3406m by calculation2Per g, pore volume 2.29cm3(ii) in terms of/g. It can be seen in the pore size distribution plot of fig. 4 that HPAC-1 possesses a hierarchical pore structure. FIG. 6 shows an X-ray photoelectron spectrum of HPAC-1, indicating that the surface of HPAC-1 has abundant oxygen-containing functional groups. At 6 mol. L-1In KOH aqueous electrolyte, HPAC-1 is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as a counter electrode, and the current density is 10 A.g-1The constant current charge-discharge curve of HPAC-1 obtained under the working conditions is shown in figure 7, and from figure 7, the constant current charge-discharge curve of HPAC-1 presents a nearly linear triangular shape and almost negligible micro deformation, which means that the constant current charge-discharge curve has excellent electrochemical reversibility and high coulombic efficiency, and the specific capacitance of HPAC-1 is 320F g obtained by calculation-1。
Example 2
Mixing needle leaf alkali lignin and sodium sulfite according to a mass ratio of 3:1, adding the mixture into water, stirring and reacting for 4 hours at 150 ℃, adjusting the pH of the aqueous solution to 8.0 by using carbon dioxide gas and sodium sulfite, wherein the total solid content of the needle leaf alkali lignin and the sodium sulfite in the solution is 32%, and finally, putting the aqueous solution into a centrifugal spray dryer for drying, wherein the temperature of an air inlet of the spray dryer is 300 ℃, the temperature of an air outlet of the spray dryer is 120 ℃, and the evaporation capacity of water per hour is 2 tons, so that lignin microspheres can be obtained, and the water content of the lignin microspheres is less than 6%; placing the obtained lignin carbon microspheres in a tube furnace, introducing argon at the flow rate of 300ml/min, heating to 400 ℃ at the heating rate of 8 ℃/min, preserving the heat for 60min, and naturally cooling to room temperature to obtain lignin carbonized microspheres; blending the obtained lignin carbonized microspheres and potassium hydroxide according to the mass ratio of 1:3, adding the blended mixture into ultrapure water, oscillating for 1min, uniformly mixing, standing for 3h, and then placing the mixture into an oven for drying to obtain a mixture of lignin carbonized spheres and potassium hydroxide; and placing the obtained mixture in a tubular furnace, introducing argon at the flow rate of 300ml/min, heating to 700 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 60min, naturally cooling to room temperature, filtering and washing with ultrapure water until the filtrate is neutral, taking a black solid, placing the black solid in an oven, and drying to be absolutely dry to obtain the high-specific surface area and multi-level hole hollow carbon microsphere, which is recorded as HPAC-2.
FIG. 3 shows a nitrogen adsorption/desorption isotherm diagram of HPAC-2, calculated to give HPAC-2 a specific surface area of 2292m2G, pore volume of 1.10cm3(ii) in terms of/g. It can be seen in the pore size distribution plot of FIG. 4 that HPAC-2 possesses peaks at pore sizes 0.5-2nm and 2-10nm, indicating the hierarchical pore structure of HPAC-2. The X-ray photoelectron spectrum of fig. 6 shows that the surface of HPAC-2 has abundant oxygen-containing functional groups. At 6 mol. L-1In KOH aqueous electrolyte, HPAC-2 is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as a counter electrode, and the current density is 10 A.g-1The constant current charge-discharge curve of HPAC-2 obtained under the working conditions is shown in FIG. 7, and the specific capacitance of HPAC-2 is 161F g by calculation-1。
Example 3
Mixing needle leaf alkali lignin and sodium sulfite according to a mass ratio of 1:1, adding the mixture into water, stirring and reacting for 2 hours at 220 ℃, adjusting the pH of an aqueous solution to 9 by using carbon dioxide gas and sodium sulfite, wherein the total solid content of the needle leaf alkali lignin and the sodium sulfite in the solution is 36%, finally, putting the aqueous solution into a centrifugal spray dryer for drying, wherein the temperature of an air inlet of the spray dryer is 300 ℃, the temperature of an air outlet of the spray dryer is 120 ℃, and the evaporation capacity of water per hour is 2 tons, so that lignin microspheres can be obtained, and the water content of the lignin microspheres is less than 6%; placing the obtained lignin carbon microspheres in a tube furnace, introducing argon at the flow rate of 300ml/min, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 80min, and naturally cooling to room temperature to obtain lignin carbonized microspheres; blending the obtained lignin carbonized microspheres and potassium hydroxide according to the mass ratio of 1:3, adding a proper amount of ultrapure water, oscillating, uniformly mixing, standing for 4 hours, and then placing in an oven for drying to obtain a mixture of lignin carbonized spheres and potassium hydroxide; and placing the obtained mixture in a tubular furnace, introducing argon at the flow rate of 500ml/min, heating to 900 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 100min, naturally cooling to room temperature, filtering and washing with ultrapure water until the filtrate is neutral, placing black solids in an oven, and drying to be absolutely dry to obtain the high-specific surface area and multi-level hole hollow carbon microsphere, which is recorded as HPAC-3.
FIG. 3 shows a nitrogen adsorption/desorption isotherm diagram of HPAC-3, which was calculated to give a specific surface area of 3187m for HPAC-32Per g, pore volume of 2.46cm3(ii) in terms of/g. The pore size distribution diagram of FIG. 4 shows the hierarchical pore structure of HPAC-3. The X-ray photoelectron spectrum of fig. 6 shows that the surface of HPAC-3 has abundant oxygen-containing functional groups. At 6 mol. L-1In KOH aqueous electrolyte, HPAC-3 is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as a counter electrode, and the current density is 10 A.g-1The constant current charge-discharge curve of HPAC-2 obtained under the working conditions is shown in FIG. 7, and the specific capacitance of HPAC-3 is 283F g-1。
Example 4
Lignin microspheres were obtained by the method of the first step of example 1; placing the obtained lignin microspheres in a tube furnace, introducing nitrogen at the flow rate of 300ml/min, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, and naturally cooling to room temperature to obtain lignin carbonized microspheres; mixing the obtained lignin carbonized microspheres and potassium hydroxide according to the mass ratio of 1:1, adding a proper amount of deionized water, oscillating, uniformly mixing, standing for 2 hours, and drying to obtain a mixture of the lignin carbonized microspheres and the potassium hydroxide; and placing the obtained mixture in a tubular furnace, introducing argon at the flow rate of 350ml/min, heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 40min, naturally cooling to room temperature, filtering and washing with ultrapure water until the filtrate is neutral, taking filter residue, and finally placing in an oven to dry for 12h at the temperature of 120 ℃ to obtain the high-specific surface area and multi-level hole hollow carbon microsphere which is marked as HPAC-4.
FIG. 3 showsThe nitrogen adsorption/desorption isotherm diagram of HPAC-4 was determined, and the specific surface area of HPAC-4 was 3006m by calculation2Per g, pore volume of 2.14cm3(ii) in terms of/g. The hierarchical pore structure of HPAC-4 can be seen in the pore size distribution plot of FIG. 5. The X-ray photoelectron spectrum of fig. 6 shows that the surface of HPAC-4 has abundant oxygen-containing functional groups. At 6 mol. L-1In KOH aqueous electrolyte, HPAC-4 is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as a counter electrode, and the current density is 10 A.g-1The constant current charge-discharge curve of HPAC-4 obtained under the working conditions is shown in FIG. 7, and the specific capacitance of HPAC-4 is 231F g-1。
Example 5
Lignin microspheres were obtained by the method of the first step of example 1; placing the obtained lignin microspheres in a tubular furnace, introducing nitrogen at the flow rate of 350ml/min, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, and naturally cooling to room temperature to obtain lignin carbonized microspheres; mixing the obtained lignin carbonized microspheres and potassium hydroxide according to the mass ratio of 1:4, adding deionized water, oscillating, uniformly mixing, standing for 2 hours, and drying to obtain a mixture of the lignin carbonized microspheres and the potassium hydroxide; and placing the obtained mixture in a tubular furnace, introducing argon at the flow rate of 300ml/min, heating to 800 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 40min, naturally cooling to room temperature, filtering and washing with ultrapure water until the filtrate is neutral, taking filter residue, and finally placing in an oven to dry for 12h at the temperature of 120 ℃ to obtain the high-specific surface area and multi-level hole hollow carbon microsphere, which is marked as HPAC-5.
FIG. 3 shows a nitrogen adsorption/desorption isotherm diagram of HPAC-5, which was calculated to give HPAC-5 a specific surface area of 2292m2G, pore volume of 1.10cm3(ii) in terms of/g. The hierarchical pore structure of HPAC-5 can be seen in the pore size distribution plot of FIG. 5. The X-ray photoelectron spectrum of fig. 6 shows that the surface of HPAC-5 has high oxygen-containing functional groups. At 6 mol. L-1In KOH aqueous electrolyte, HPAC-5 is used as a working electrode, Hg/HgO is used as a reference electrode, a platinum sheet is used as a counter electrode, and the current density is 10 A.g-1Obtaining the constant current charge and discharge of HPAC-5 under the working conditionThe electrical curve is shown in FIG. 7, and the specific capacitance of HPAC-5 is calculated to be 166F g-1。
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing a high-specific surface area and hierarchical pore hollow carbon microsphere by taking lignin as a raw material is characterized by comprising the following steps:
(1) adding lignin and sulfite into water, heating and stirring to obtain a mixed solution, adjusting the pH of the mixed solution to 7.0-9.0 by using an acid solution, carbon dioxide gas or sulfite, and drying to obtain lignin microspheres;
(2) heating the lignin microspheres obtained in the step (1) in an inert atmosphere to carry out carbonization treatment to obtain carbonized microspheres;
(3) mixing the carbonized microspheres in the step (2) with an activating agent, adding the mixture into water, oscillating and uniformly mixing, standing, and drying to obtain a solid mixture of the carbonized microspheres and the activating agent;
(4) and (3) heating the solid mixture of the carbonized microspheres and the activating agent in the step (3) under an inert atmosphere to carry out activation treatment to obtain activated carbon microspheres, then washing with water until the filtrate is neutral, and drying to obtain the high-specific surface area and multi-level hole hollow carbon microspheres.
2. The method for preparing the high-specific-surface-area, multi-stage-hole hollow carbon microspheres from lignin as a raw material according to claim 1, wherein the lignin in the step (1) is one or more of sodium lignosulfonate and alkali lignin; the sulfite is more than one of sodium sulfite and potassium sulfite; the mass ratio of the lignin to the sulfite is 5:1-1: 1; in the mixed solution, the total solid content of lignin and sulfite is 30-36%.
3. The method for preparing the high specific surface area, multi-stage pore hollow carbon microsphere by using the lignin as the raw material as claimed in claim 1, wherein the temperature of the stirring treatment in the step (1) is 120-220 ℃, and the time of the stirring treatment is 2-6 h.
4. The method for preparing the high specific surface area, multi-stage pore hollow carbon microspheres by using the lignin as the raw material according to claim 1, wherein the drying manner in the step (1) is spray drying; the temperature of the air inlet of the spray drying is 250-350 ℃, the temperature of the air outlet is 100-150 ℃, and the evaporation amount of water per hour is 1.5-2.5 tons; the water content of the lignin microspheres is less than 6%.
5. The method for preparing the high-specific-surface-area, multi-pore hollow carbon microspheres from lignin as a raw material according to claim 1, wherein the temperature rise rate in the step (2) is 5-10 ℃/min; the temperature of the carbonization treatment is 400-500 ℃, and the time of the carbonization treatment is 50-80 min.
6. The method for preparing the high-specific-surface-area and multi-stage-hole hollow carbon microspheres by using lignin as a raw material according to claim 1, wherein the activating agent in the step (3) is more than one of potassium hydroxide and potassium carbonate solid; according to the dry weight, the mass ratio of the carbonized microspheres to the activating agent is 1:1-1: 4.
7. The method for preparing the high specific surface area, multi-stage pore hollow carbon microspheres from lignin as a raw material according to claim 1, wherein the standing time in the step (3) is 2-4 h.
8. The method for preparing the high-specific-surface-area, multi-pore hollow carbon microspheres from lignin as a raw material according to claim 1, wherein the temperature rise rate in the step (4) is 5-20 ℃/min; the temperature of the activation treatment is 700-900 ℃, and the time of the activation treatment is 40-100 min.
9. The method for preparing the high specific surface area, multi-stage pore hollow carbon microsphere by using the lignin as the raw material according to claim 1, wherein the inert atmosphere in the steps (2) and (4) is nitrogen, argon or a mixed gas of the nitrogen and the argon; the flow rate of the inert atmosphere is 200-500 ml/min.
10. A high specific surface area, multi-stage pore hollow carbon microsphere produced by the production method according to any one of claims 1 to 9.
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