CN112158822B - Preparation method of porous carbon microsphere - Google Patents
Preparation method of porous carbon microsphere Download PDFInfo
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- CN112158822B CN112158822B CN202010939933.2A CN202010939933A CN112158822B CN 112158822 B CN112158822 B CN 112158822B CN 202010939933 A CN202010939933 A CN 202010939933A CN 112158822 B CN112158822 B CN 112158822B
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Abstract
The invention discloses a preparation method of porous carbon microspheres, which comprises the following steps: 1) Mixing resin and curing agent to form a uniform phase; 2) Adding deionized water into the resin homogeneous phase, and stirring at high speed to form emulsion; 3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; 4) Heating to solidify the resin, preparing the water-in-resin microcapsule; 5) And (3) placing the filtered, washed and dried resin water-in-resin microcapsule under the protection of inert gas, and performing high-temperature pyrolysis to obtain the porous carbon microsphere. The preparation method provided by the invention has the advantages of simple process, low cost, high coating rate, environmental friendliness and easiness in industrialization.
Description
Technical Field
The invention belongs to the field of porous carbon materials, and particularly relates to a preparation method of porous carbon microspheres.
Background
In recent years, porous carbon materials have become a new and rapidly developed new material system, and applications in various fields, particularly applications in energy-related fields, have been paid attention to. Porous materials have some corresponding superior properties due to their higher porosity in structure. Among the porous materials, the porous carbon material has the characteristics of low cost, light weight, no toxicity, chemical inertness on the surface, high temperature resistance, acid and alkali resistance, high mechanical stability, good conductivity, adsorptivity, large specific surface area, large pore volume and the like, and is used in CO 2 The fields of adsorption, hydrogen storage, catalysis, fuel cells, electrochemical double-layer capacitors and the like show great application potential and are concerned by various fields.
Disclosure of Invention
The invention aims to provide a preparation method of porous carbon microspheres, which has the advantages of wide raw material sources, low price, simple process, low energy consumption, environmental friendliness, high yield of the carbon microspheres and good industrialization prospect.
In the invention, the resin is not compatible with water, when the volume of the resin is larger than the volume of water, the water-in-resin emulsion can be formed under high-speed stirring, the whole emulsion is not compatible with continuous phase silicone oil, the viscosity of the silicone oil is high, and the self-emulsifying effect is achieved, so that when the emulsion is added into the continuous phase, a plurality of emulsion microdroplets can be formed through stirring, and the water is coated in the emulsion microdroplets after the resin in the emulsion microdroplets is solidified, so that the water-in-resin microcapsule can be formed.
The invention provides a preparation method of a novel porous carbon microsphere, which comprises the steps of mixing resin and a curing agent into a whole, adding deionized water, stirring at a high speed to form emulsion, dripping the emulsion into silicone oil, stirring at a high speed to form water-in-resin droplets, heating to cure the resin to form a water-in-resin microcapsule, and carrying out high-temperature pyrolysis carbonization on the water-in-resin microcapsule to finally prepare the porous carbon microsphere.
The preparation method of the porous carbon microsphere specifically comprises the following steps:
(1) Mixing resin and curing agent to form a uniform phase;
(2) Adding deionized water into the resin homogeneous phase, and stirring at high speed to form emulsion;
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion;
(4) Heating the multiphase emulsion to solidify the resin, and preparing the water-in-resin microcapsule;
(5) And (3) placing the filtered, washed and dried resin water-in-resin microcapsule under the protection of inert gas, and performing high-temperature pyrolysis carbonization to finally obtain the porous carbon microsphere.
Further, the resin is one of epoxy resin and phenolic resin.
Further, the curing agent is one of ethylenediamine, diethylenetriamine, triethylenetetramine and p-toluenesulfonic acid.
Further, in the step (1), the mass ratio of the resin to the curing agent is 100:7-100:13.
further, in the step (2), the mass ratio of the resin to the deionized water is 100:50-100:70.
Further, the silicone oil is methyl silicone oil, the viscosity is 100ps-2000ps, and the mass ratio of the resin to the silicone oil is 1:3-1:6.
Further, the stirring speed is 10000-30000r/min.
Further, in the step (4), the heating temperature is 60-150 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-24h.
Further, in the step (5), the drying temperature is 40-80 ℃ and the time is 1-8h.
Further, in the step (5), the inert gas is argon.
Further, in the step (5), the technological conditions of pyrolysis and carbonization are as follows: heat-preserving at 80-90deg.C for 20-40min, then heating to 350-450deg.C, heat-preserving for 50-90min, heating to 600-1000deg.C, heat-preserving for 60-180min, and heating at 1-5deg.C/min.
The invention has the beneficial effects that:
the preparation method of the novel porous carbon microsphere has the advantages of simple process steps, low raw material cost, no pollution, high carbon microsphere yield, low energy consumption, low requirements on the environmental conditions and used equipment of the preparation, and simple, rapid and efficient preparation of the porous carbon microsphere, thereby providing a new way for preparing the porous carbon material.
Drawings
FIG. 1 is an SEM image of carbon microspheres prepared according to example 1 of the invention.
FIG. 2 is a graph showing pore size distribution of carbon microspheres prepared in example 1 of the present invention.
FIG. 3 is a graph showing pore size distribution of carbon microspheres prepared in example 2 of the present invention.
FIG. 4 is a graph showing pore size distribution of carbon microspheres prepared in example 3 of the present invention.
FIG. 5 is a graph showing pore size distribution of carbon microspheres prepared in example 4 of the present invention.
FIG. 6 is a graph showing pore size distribution of carbon microspheres prepared in example 5 of the present invention.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1
The preparation method of the novel porous carbon microsphere mainly comprises the following steps:
(1) Mixing epoxy resin and ethylenediamine as curing agent to form a homogeneous phase; the mass ratio of the epoxy resin to the curing agent is 100:7.
(2) Adding deionized water into the epoxy resin uniform phase, and stirring at a high speed to form emulsion; the mass ratio of the epoxy resin to the deionized water is 100:50.
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the mass ratio of the epoxy resin to the silicone oil is 1:3; the stirring speed is 10000r/min.
(4) Heating to solidify the resin, wherein the heating temperature is 60 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 24 hours; preparing an epoxy resin water-in-water microcapsule;
(5) And (3) filtering, washing, drying (the drying temperature is 40 ℃ for 8 hours), placing the epoxy resin water-in-bag microcapsule under the protection of argon, performing high-temperature pyrolysis carbonization, preserving heat at 80 ℃ for 30min, preserving heat at 400 ℃ for 60min, preserving heat at 800 ℃ for 120min, and heating at a rate of 5 ℃/min.
Fig. 1 is an SEM image of the carbon microsphere prepared in this example.
As can be seen from fig. 1a, the carbon microspheres are spherical, the particle size of the carbon microspheres is distributed between 1 and 100 μm, and a plurality of holes with different sizes are distributed on the surface of the carbon microspheres, wherein a plurality of carbon microspheres with smaller particle sizes are adsorbed in the big holes of the carbon microspheres with larger particle sizes; in FIG. 1b, it can be seen that the carbon microspheres are easily agglomerated under natural conditions, indicating that they have a high surface energy and are easily adsorbed together; fig. 1c is an enlarged view of a portion of fig. 1b, showing the presence of a plurality of micro-holes.
FIG. 2 is a graph showing pore size distribution of the carbon microsphere prepared in this example. As can be seen from FIG. 2, the pores have a pore distribution of 2nm, mesopores of 10 to 50nm and macropores of 50 to 100nm, and a specific surface area of 80.83m 2 /g。
Example 2
The preparation method of the novel porous carbon microsphere mainly comprises the following steps:
(1) Mixing phenolic resin and curing agent p-toluenesulfonic acid to form a uniform phase; the mass ratio of the phenolic resin to the curing agent is 100:10.
(2) Adding deionized water into the phenolic resin homogeneous phase, and stirring at high speed to form emulsion; the mass ratio of the phenolic resin to the deionized water is 100:60.
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the mass ratio of the phenolic resin to the silicone oil is 1:4; the stirring speed is 10000r/min.
(4) Heating to solidify the resin, wherein the heating temperature is 120 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 1h, so as to prepare the phenolic resin water-in-package microcapsule;
(5) Filtering, washing, drying (the drying temperature is 50 ℃ for 6 hours), placing the water-in-phenol-formaldehyde resin microcapsule under the protection of argon, performing high-temperature pyrolysis carbonization, preserving heat at 90 ℃ for 40min, preserving heat at 450 ℃ for 50min, preserving heat at 900 ℃ for 90min, and heating up at a rate of 5 ℃/min.
FIG. 3 is a graph showing pore size distribution of the carbon microsphere prepared in this example. As can be seen from FIG. 3, micropores whose pore distribution is mainly 1nm, and additionally small amounts of mesopores of 20 to 50nm and macropores of 50 to 100nm, whose specific surface area is 277.3m, are present 2 /g。
Example 3
The preparation method of the novel porous carbon microsphere mainly comprises the following steps:
(1) Mixing phenolic resin and curing agent p-toluenesulfonic acid to form a uniform phase; the mass ratio of the phenolic resin to the curing agent is 100:11.
(2) Adding deionized water into the phenolic resin homogeneous phase, and stirring at high speed to form emulsion; the mass ratio of the phenolic resin to the deionized water is 100:55.
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the mass ratio of the phenolic resin to the silicone oil is 1:5; the stirring speed was 15000r/min.
(4) Heating to solidify the resin, wherein the heating temperature is 150 ℃, the heating rate is 4 ℃/min, and the heat preservation time is 1h; preparing a phenolic resin water-in-water microcapsule;
(5) Filtering, washing, drying (the drying temperature is 70 ℃ for 4 hours), placing the water-in-phenol-formaldehyde resin microcapsule under the protection of argon, performing high-temperature pyrolysis carbonization, preserving heat at 85 ℃ for 30min, preserving heat at 300 ℃ for 80min, preserving heat at 750 ℃ for 120min, and heating up at a rate of 5 ℃/min.
FIG. 4 is a graph showing pore size distribution of the carbon microsphere prepared in this example. As can be seen from FIG. 4, the pore distribution is 1-2nm micropores, and mainly 1nm micropores, 5-50nm mesopores and 50-100nm macropores, and the specific surface area is 124.97m 2 /g。
Example 4
The preparation method of the novel porous carbon microsphere mainly comprises the following steps:
(1) Mixing phenolic resin and curing agent p-toluenesulfonic acid to form a uniform phase; the mass ratio of the phenolic resin to the curing agent is 100:9.
(2) Adding deionized water into the phenolic resin homogeneous phase, and stirring at high speed to form emulsion; the mass ratio of the phenolic resin to the deionized water is 100:65.
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the mass ratio of the phenolic resin to the silicone oil is 1:4.5; the stirring speed is 20000r/min.
(4) Heating to solidify the resin, wherein the heating temperature is 140 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 2.5h; preparing a phenolic resin water-in-water microcapsule;
(5) Filtering, washing, drying (the drying temperature is 60 ℃ for 8 hours), placing the water-in-phenol-formaldehyde resin microcapsule under the protection of argon, performing high-temperature pyrolysis carbonization, preserving heat for 20min at 80 ℃, preserving heat for 70min at 450 ℃, preserving heat for 100min at 800 ℃, and heating up at a rate of 3 ℃/min.
FIG. 5 is a graph showing pore size distribution of the carbon microsphere prepared in this example. As can be seen from FIG. 5, the pores have a pore distribution of 1-2nm, mainly 1.5nm, a small amount of 15-50nm mesopores and 50-100nm macropores, and a specific surface area of 244.08m 2 /g。
Example 5
The preparation method of the novel porous carbon microsphere mainly comprises the following steps:
(1) Mixing epoxy resin and curing agent diethylenetriamine to form a uniform phase; the mass ratio of the epoxy resin to the curing agent is 100:8.
(2) Adding deionized water into the epoxy resin uniform phase, and stirring at a high speed to form emulsion; the mass ratio of the epoxy resin to the deionized water is 100:55.
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the mass ratio of the epoxy resin to the silicone oil is 1:5; the stirring speed is 30000r/min.
(4) Heating to solidify the resin, wherein the heating temperature is 60 ℃, the heating rate is 3 ℃/min, and the heat preservation time is 18h; preparing an epoxy resin water-in-water microcapsule;
(5) And (3) filtering, washing, drying (the drying temperature is 50 ℃ for 6 hours), placing the epoxy resin water-in-bag microcapsule under the protection of argon, performing high-temperature pyrolysis carbonization, preserving heat at 80 ℃ for 30min, preserving heat at 350 ℃ for 80min, preserving heat at 800 ℃ for 120min, and heating at a rate of 1 ℃/min.
FIG. 6 is a graph showing pore size distribution of the carbon microsphere prepared in this example. As can be seen from FIG. 6, the pores are distributed in 1-2nm and mainly in 2nm, and a large number of 5-50nm mesopores and 50-100nm macropores are present, and the specific surface area is 69.97m 2 /g。
Claims (4)
1. A preparation method of porous carbon microspheres is characterized in that: mixing resin and a curing agent into a whole, adding deionized water, stirring at a high speed to form emulsion, adding the emulsion into silicone oil, stirring at a high speed to form water-in-resin microdroplets, heating to cure the resin to form water-in-resin microcapsules, and performing high-temperature pyrolysis carbonization on the water-in-resin microcapsules to finally prepare the porous carbon microspheres;
the preparation method of the porous carbon microsphere comprises the following steps:
(1) Mixing resin and curing agent to form a uniform phase; the resin is one of epoxy resin and phenolic resin; the curing agent is one of ethylenediamine, diethylenetriamine, triethylenetetramine and p-toluenesulfonic acid; the mass ratio of the resin to the curing agent is 100:7-100:13;
(2) Adding deionized water into the resin homogeneous phase, and stirring at high speed to form emulsion;
(3) Dripping the emulsion into silicone oil, and stirring at high speed to form a complex phase emulsion; the silicone oil is methyl silicone oil;
(4) Heating the multiphase emulsion to solidify the resin, and preparing the water-in-resin microcapsule;
(5) Placing the filtered, washed and dried resin water-in-resin microcapsule under the protection of inert gas, and performing high-temperature pyrolysis carbonization to finally obtain the porous carbon microsphere; the technological conditions of the high-temperature pyrolysis carbonization are as follows: heat-preserving at 80-90deg.C for 20-40min, then heating to 350-450deg.C, heat-preserving for 50-90min, heating to 600-1000deg.C, heat-preserving for 60-180min, and heating at 1-5deg.C/min;
the methyl silicone oil has the viscosity of 100ps-2000ps and the mass ratio of the resin to the silicone oil of 1:3-1:6;
in the step (2), the mass ratio of the resin to the deionized water is 100:50-100:70.
2. The method for preparing the porous carbon microsphere according to claim 1, wherein: in the step (4), the heating temperature is 60-150 ℃, the heating rate is 1-5 ℃/min, and the heat preservation time is 1-24h.
3. The method for preparing the porous carbon microsphere according to claim 1, wherein: in the step (5), the drying temperature is 40-80 ℃ and the time is 1-8h.
4. The method for preparing the porous carbon microsphere according to claim 1, wherein: in the step (5), the inert gas is argon.
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| JP3628935B2 (en) * | 2000-04-28 | 2005-03-16 | 東レ・ダウコーニング・シリコーン株式会社 | Silicone rubber sponge-forming composition, silicone rubber sponge and method for producing them |
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