CN110963479A - Method for microwave-assisted large-scale preparation of nano carbon spheres by lignin - Google Patents
Method for microwave-assisted large-scale preparation of nano carbon spheres by lignin Download PDFInfo
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Abstract
The invention discloses a method for preparing nano carbon spheres by lignin microwave-assisted large-scale preparation, which comprises the steps of firstly, uniformly mixing lignin and silicon carbide, and placing the mixture in a microwave tubular reactor; introducing nitrogen into an inlet of the microwave tubular reactor to exhaust air in a reaction system, wherein the outlet of the microwave tubular reactor is in gas connection with a cold hydrazine system, then introducing the nitrogen into the microwave tubular reactor through dichloromethane to enable the nitrogen to carry dichloromethane, and introducing the nitrogen carrying dichloromethane into the microwave tubular reactor; and under the condition of ensuring that nitrogen carrying dichloromethane is introduced, opening the microwave tubular reactor for reaction, taking out a mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor after the reaction is finished, putting the mixture into water or ethanol, uniformly stirring, standing, taking out the lignin carbon floating on the liquid, and drying to obtain a solid product, namely the nano carbon spheres. The method is beneficial to changing waste lignin resources into valuables and realizing high-value utilization.
Description
Technical Field
The invention belongs to the field of preparation of functional materials from waste resources, and particularly relates to a method for microwave-assisted large-scale preparation of carbon nanospheres from lignin.
Background
The lignin is a byproduct in pulping and papermaking and biomass refining processes (bioethanol), the production amount of the lignin is large, and the lignin is mainly used as a low-value fuel for direct combustion at present. However, the utilization of low added value not only brings environmental pollution problem, but also directly affects the technical economy of pulping and papermaking and biomass refining process. Therefore, the preparation of fuel and high-quality carbon material by using the characteristics of the high carbon content in lignin as a carbon source is an important direction of research. At present, lignin draws much attention in the direction of preparing carbon nanospheres, and the carbon nanospheres can be used in the fields of medicines, wastewater treatment, catalysts and the like. However, currently, the preparation of the carbon nanospheres from lignin needs a series of very complicated degrees such as dissolution of lignin in a solvent, reverse solvent precipitation, dialysis, freeze drying, high-temperature carbonization and the like, the preparation amount is small (gram level), and a preparation period of more than 20 hours is needed, so that the development of lignin in the direction of preparing the carbon nanospheres is restricted, and therefore, a simple and convenient method for converting lignin into a carbon nanosphere material is urgently sought.
Disclosure of Invention
The invention aims to provide a method for preparing carbon nanospheres on a large scale by lignin microwave assistance, which solves the problems of long and complicated steps, poor shape controllability, difficulty in large-scale preparation and the like in the existing method for preparing carbon nanospheres from lignin.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing nano carbon spheres in a large scale by lignin microwave assistance comprises the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of less than 60 meshes and silicon carbide with the particle size of 20-100 meshes, and placing the mixture in a microwave tubular reactor;
step two: introducing nitrogen into an inlet of the microwave tubular reactor to exhaust air in a reaction system, wherein the gas at an outlet of the microwave tubular reactor is connected with a-35 ℃ cold hydrazine system, then introducing the nitrogen into the microwave tubular reactor through dichloromethane to enable the nitrogen to carry dichloromethane, and introducing the nitrogen carrying dichloromethane into the microwave tubular reactor;
step three: starting a microwave tubular reactor under the condition of ensuring that nitrogen carrying dichloromethane is introduced, wherein the microwave frequency is 2.45GHz, the microwave power is 300-500W, heating to 400-500 ℃, and preserving heat for 5-10 minutes;
step four: adjusting the microwave power to 1200-1500W, heating to 800-1200 ℃, and keeping the temperature for 30-60 minutes;
step five: and after the reaction is finished, taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into water or ethanol, uniformly stirring, standing, taking out the lignin carbon floating on the liquid, and drying to obtain a solid product, namely the nano carbon spheres.
Further, the lignin in the first step is one of solvent lignin, sulfate lignin and lignosulfonate.
Furthermore, the mass ratio of the lignin to the silicon carbide in the step one is 1 (0.5-3).
And further, when nitrogen is introduced into the inlet of the microwave tubular reactor in the step two to exhaust air in the reaction system, the nitrogen flow rate corresponding to each kilogram of lignin is 0.5-2L/min, and the nitrogen introduction time is 15 minutes.
And further, in the second step, introducing nitrogen carrying dichloromethane into the microwave tubular reactor for 10 minutes, wherein the mass of dichloromethane carried in each liter of nitrogen is 1-5 g.
And further, carrying out reduced pressure distillation on the condensate collected in the cold hydrazine system at normal temperature, wherein the distillate is dichloromethane, and recycling the dichloromethane in the step two.
Further, the reaction is specifically finished as follows: and closing the microwave tubular reactor, removing the dichloromethane, keeping introducing the nitrogen, stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃, and finishing the reaction.
And further taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor in the fifth step, putting the mixture into water or ethanol, stirring for 5-10 minutes, and standing for 30 minutes.
Further, in the fifth step, the drying temperature is 105 ℃ and the drying time is 4-6 hours.
And further, taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor in the fifth step, putting the mixture into water or ethanol, uniformly stirring, standing, taking out the silicon carbide settled at the bottom of the liquid, drying at 105 ℃ for 2 hours, and circularly using the mixture in the first step.
Compared with the prior art, the invention has the following beneficial technical effects:
1. compared with the traditional process of preparing nanospheres by a solvent method and then carbonizing, the method provided by the invention has the advantages that the lengthy preparation steps are greatly reduced, the reaction period is shortened, and a good technical support is provided for the application of lignin as a nano carbon material. In addition, the silicon carbide used in the invention realizes 100 percent of recycling, the dichloromethane used can realize full recycling, the cost of the whole preparation process is low, and the method is beneficial to industrial-grade production.
2. According to the method, the three synergistic effects of microwave assistance, dichloromethane and distributed heating are combined, so that the high-efficiency and high-yield preparation of the carbon nanospheres by the lignin is realized, the particle size of the prepared carbon nanospheres is 50-250 nm, and the yield of the carbon nanospheres is more than 55%. The microwave-assisted effect is mainly that the 'hot spot' effect generated by microwaves on the contact surface of silicon carbide and lignin (the silicon carbide and the lignin have different dielectric coefficients) is utilized, and as the temperature of the 'hot spot' effect area is higher than that of a non- 'hot spot' effect area, the non- 'hot spot' effect area is subjected to condensation polymerization to generate carbon; the dichloromethane has the function of combining dichloromethane with active groups (hydroxyl, carboxyl and the like) on the surface of lignin during the carbon formation process by utilizing the strong solvent effect of the dichloromethane, and a lignin carbon sphere precursor is generated through the surface tension effect; distributed heating effect: in the first stage, lignin gasification is reduced in a low microwave power stage, and high-yield lignin carbon sphere precursors are generated, and in the second stage, the lignin carbon sphere precursors absorb a large amount of microwaves due to high dielectric coefficient, so that the middle temperature of the lignin carbon sphere precursors is higher than the surface temperature, and the lignin carbon sphere precursors are prevented from being bonded with each other to generate nano carbon spheres quickly. Therefore, the invention ensures the generation of the high-yield carbon nanospheres through the synergistic effect of three aspects of microwave assistance, dichloromethane and distributed temperature rise.
Drawings
FIG. 1 shows a carbon nanosphere (5 ten thousand times) prepared in example 1 of the present invention;
FIG. 2 shows a carbon nanosphere (5 ten thousand times) prepared in example 2 of the present invention;
fig. 3 shows nanocarbon spheres (1 ten thousand times) prepared in example 3 of the present invention.
Detailed Description
Embodiments of the invention are described in further detail below:
a method for preparing nano carbon spheres in a large scale by lignin microwave assistance comprises the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of less than 60 meshes and silicon carbide with the particle size of 20-100 meshes, and placing the mixture in a microwave tubular reactor, wherein the lignin is one of solvent lignin, sulfate lignin and lignosulfonate, and the mass ratio of the lignin to the silicon carbide is 1 (0.5-3).
Step two: introducing nitrogen into an inlet of the microwave tubular reactor to exhaust air in a reaction system, wherein the outlet of the microwave tubular reactor is in gas connection with a-35 ℃ cold hydrazine system, the nitrogen flow corresponding to each kilogram of lignin is 0.5-2L/min, and the nitrogen introduction time is 15 minutes; then, passing nitrogen through a Meng's gas washing bottle filled with dichloromethane to enable the nitrogen to carry the dichloromethane, and introducing the nitrogen carrying the dichloromethane into the microwave tubular reactor for 10 minutes, wherein the mass of the dichloromethane carried in each liter of nitrogen is 1-5 g;
step three: and under the condition of ensuring that nitrogen carrying dichloromethane is introduced, starting the microwave tubular reactor, wherein the microwave frequency is 2.45GHz, the microwave power is 300-500W, heating to 400-500 ℃, and preserving heat for 5-10 minutes.
Step four: adjusting the microwave power to 1200-1500W, heating to 800-1200 ℃, and preserving the heat for 30-60 minutes.
Step five: and closing the microwave tubular reactor, removing the Mene's gas washing bottle filled with dichloromethane, keeping introducing nitrogen, stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃, and finishing the reaction.
Step six: and (4) carrying out reduced pressure distillation on the condensate collected in the cold hydrazine system at normal temperature, wherein the distillate is dichloromethane, and recycling the dichloromethane in the step two.
Step seven: and taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into water or ethanol, stirring for 5-10 minutes, standing for 30 minutes, taking out the lignin carbon floating on the liquid, and drying at 105 ℃ for 4-6 hours to obtain a solid product, namely the nano carbon spheres. And taking out the silicon carbide which is settled at the bottom of the liquid, drying the silicon carbide at 105 ℃ for 2h, and recycling the silicon carbide for the first step.
The present invention is described in further detail below with reference to examples:
example 1
Uniformly mixing 5kg of alcoholysis lignin with the particle size of 60-80 meshes and 2.5kg of silicon carbide with the particle size of 20-60 meshes, putting the mixture in a microwave tubular reactor, introducing nitrogen with the flow rate of 2.5L/min for 15 minutes, then passing the nitrogen through a Meng gas washing bottle filled with dichloromethane to enable the nitrogen to carry dichloromethane with the carrying amount of 2.5g/min, introducing the nitrogen carrying dichloromethane into the microwave tubular reactor for 10 minutes, starting the microwave tubular reactor, keeping the microwave frequency at 2.45GHz and the microwave power at 300W, heating to 400 ℃, and keeping the temperature for 10 minutes; then the microwave power is adjusted to 1200W, the temperature is raised to 800 ℃, and the temperature is kept for 60 minutes. And closing the microwave tubular reactor, removing the Mene's gas washing bottle filled with dichloromethane, keeping introducing the nitrogen, and stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃. And (3) carrying out reduced pressure distillation on the condensate collected in the cold hydrazine system at normal temperature, and recycling the distillate into the Meng gas washing bottle in the experiment. And taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into water, stirring the mixture for 5 minutes, standing the mixture for 30 minutes, taking out the lignin carbon floating on the liquid, and drying the lignin carbon at 105 ℃ for 4 hours to obtain a solid product, namely the nano carbon spheres. Will sink inAnd taking out the silicon carbide at the bottom of the liquid, drying at 105 ℃ for 2h, and recycling the silicon carbide in the microwave tubular reactor. The yield of the nano carbon spheres obtained by the reaction is 68.4 percent, the particle size of the nano carbon spheres is 180-250 nm, and the specific surface area is 462m2/g。
Example 2
Uniformly mixing 20kg of kraft lignin with the particle size of 80-100 meshes and 60kg of silicon carbide with the particle size of 80-100 meshes, placing the mixture in a microwave tubular reactor, introducing nitrogen with the flow rate of 40L/min for 15 minutes, then passing the nitrogen through a Mene's gas washing bottle filled with dichloromethane to enable the nitrogen to carry dichloromethane with the carrying amount of 200g/min, introducing the nitrogen carrying dichloromethane into the microwave tubular reactor for 10 minutes, starting the microwave tubular reactor, wherein the microwave frequency is 2.45GHz, the microwave power is 500W, heating to 500 ℃, and preserving the heat for 5 minutes; then the microwave power is adjusted to 1500W, the temperature is raised to 1200 ℃, and the temperature is kept for 30 minutes. And closing the microwave tubular reactor, removing the Mene's gas washing bottle filled with dichloromethane, keeping introducing the nitrogen, and stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃. And (3) carrying out reduced pressure distillation on the condensate collected in the cold hydrazine system at normal temperature, and recycling the distillate into the Meng gas washing bottle in the experiment. And taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into ethanol, stirring the mixture for 10 minutes, standing the mixture for 30 minutes, taking out the lignin carbon floating on the liquid, and drying the lignin carbon at 105 ℃ for 6 hours to obtain a solid product, namely the nano carbon spheres. The silicon carbide settled at the bottom of the liquid was taken out, dried at 105 ℃ for 2h and recycled to the microwave tubular reactor. The yield of the nano carbon spheres obtained by the reaction is 56.9 percent, the particle size of the nano carbon spheres is 50-160 nm, and the specific surface area is 687m2/g。
Example 3
Uniformly mixing 10kg of lignosulfonate with the particle size of 80-120 meshes and 20kg of silicon carbide with the particle size of 40-80 meshes, placing the mixture in a microwave tubular reactor, introducing nitrogen with the flow rate of 10L/min for 15 minutes, then passing the nitrogen through a Mene's gas washing bottle filled with dichloromethane to enable the nitrogen to carry the dichloromethane with the carrying amount of 30g/min, introducing the nitrogen carrying the dichloromethane into the microwave tubular reactor for 10 minutes, and then opening the microwave tubular reactorHeating the reactor to 450 ℃ with the microwave frequency of 2.45GHz and the microwave power of 400W, and keeping the temperature for 8 minutes; then the microwave power is adjusted to 1300W, the temperature is raised to 1000 ℃, and the temperature is preserved for 40 minutes. And closing the microwave tubular reactor, removing the Mene's gas washing bottle filled with dichloromethane, keeping introducing the nitrogen, and stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃. And (3) carrying out reduced pressure distillation on the condensate collected in the cold hydrazine system at normal temperature, and recycling the distillate into the Meng gas washing bottle in the experiment. And taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into ethanol, stirring for 7 minutes, standing for 30 minutes, taking out the lignin carbon floating on the liquid, and drying at 105 ℃ for 5 hours to obtain a solid product, namely the nano carbon spheres. The silicon carbide settled at the bottom of the liquid was taken out, dried at 105 ℃ for 2h and recycled to the microwave tubular reactor. The yield of the nano carbon spheres obtained by the reaction is 60.2 percent, the particle size of the nano carbon spheres is 120-200 nm, and the specific surface area is 514m2/g。
Claims (10)
1. A method for preparing carbon nanospheres on a large scale by lignin microwave assistance is characterized by comprising the following steps:
the method comprises the following steps: uniformly mixing lignin with the particle size of less than 60 meshes and silicon carbide with the particle size of 20-100 meshes, and placing the mixture in a microwave tubular reactor;
step two: introducing nitrogen into an inlet of the microwave tubular reactor to exhaust air in a reaction system, wherein the gas at an outlet of the microwave tubular reactor is connected with a-35 ℃ cold hydrazine system, then introducing the nitrogen into the microwave tubular reactor through dichloromethane to enable the nitrogen to carry dichloromethane, and introducing the nitrogen carrying dichloromethane into the microwave tubular reactor;
step three: starting a microwave tubular reactor under the condition of ensuring that nitrogen carrying dichloromethane is introduced, wherein the microwave frequency is 2.45GHz, the microwave power is 300-500W, heating to 400-500 ℃, and preserving heat for 5-10 minutes;
step four: adjusting the microwave power to 1200-1500W, heating to 800-1200 ℃, and keeping the temperature for 30-60 minutes;
step five: and after the reaction is finished, taking out the mixture of the lignin carbon and the silicon carbide from the microwave tubular reactor, putting the mixture into water or ethanol, uniformly stirring, standing, taking out the lignin carbon floating on the liquid, and drying to obtain a solid product, namely the nano carbon spheres.
2. The method for microwave-assisted mass production of nanocarbon spheres by lignin according to claim 1, wherein the lignin in the first step is one of solvent lignin, kraft lignin and lignosulfonate.
3. The method for microwave-assisted large-scale preparation of carbon nanospheres by lignin according to claim 1, wherein the mass ratio of lignin to silicon carbide in the first step is 1 (0.5-3).
4. The microwave-assisted large-scale preparation method of carbon nanospheres by lignin according to claim 1, wherein in the second step, when nitrogen is introduced into the inlet of the microwave tubular reactor to exhaust air in the reaction system, the nitrogen flow rate corresponding to each kilogram of lignin is 0.5-2L/min, and the nitrogen introduction time is 15 minutes.
5. The microwave-assisted large-scale preparation method of carbon nanospheres by lignin according to claim 1, wherein in the second step, nitrogen carrying dichloromethane is introduced into the microwave tube reactor for 10 minutes, and the mass of dichloromethane carried in each liter of nitrogen is 1-5 g.
6. The microwave-assisted large-scale preparation method of carbon nanospheres from lignin according to claim 1, wherein the condensate collected in the cold hydrazine system is subjected to reduced pressure distillation at normal temperature, and the distillate is dichloromethane and is recycled in step two.
7. The method for microwave-assisted large-scale preparation of carbon nanospheres by lignin according to claim 1, wherein the reaction is specifically completed by: and closing the microwave tubular reactor, removing the dichloromethane, keeping introducing the nitrogen, stopping introducing the nitrogen when the temperature in the microwave tubular reactor is reduced to be below 120 ℃, and finishing the reaction.
8. The microwave-assisted large-scale preparation method of carbon nanospheres from lignin according to claim 1, wherein in step five, the mixture of lignin carbon and silicon carbide is taken out from the microwave tubular reactor, stirred in water or ethanol for 5-10 minutes, and left to stand for 30 minutes.
9. The method for microwave-assisted large-scale preparation of carbon nanospheres by lignin according to claim 1, wherein the drying temperature in step five is 105 ℃ and the drying time is 4-6 hours.
10. The method for microwave-assisted large-scale preparation of nanocarbon spheres by lignin according to claim 1, wherein in the fifth step, the mixture of lignin carbon and silicon carbide is taken out from the microwave tubular reactor, put into water or ethanol, stirred uniformly, then kept stand, the silicon carbide settled at the bottom of the liquid is taken out, dried at 105 ℃ for 2h, and recycled in the first step.
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