CN114380283A - Preparation method of porous carbon and porous carbon prepared by preparation method - Google Patents
Preparation method of porous carbon and porous carbon prepared by preparation method Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000839 emulsion Substances 0.000 claims abstract description 40
- 239000007833 carbon precursor Substances 0.000 claims abstract description 29
- 238000001694 spray drying Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 26
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- 238000007865 diluting Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012798 spherical particle Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 catalysis Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
- B01J2/04—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a gaseous medium
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Abstract
The invention provides a preparation method of porous carbon, which comprises the following steps: and mixing the template emulsion with a carbon source, and then spray-drying to obtain a porous carbon precursor, and carbonizing the porous carbon precursor to obtain the porous carbon. The invention combines a soft template and a spray drying process to synthesize the spherical porous carbon with uniform macroporous structure. The soft template is directly removed in the carbonization process, micron-sized spherical particles can be directly obtained by spray drying, the spheroidization and crushing processes are omitted, and the original pore diameter structure of the porous carbon is reserved.
Description
Technical Field
The invention belongs to the technical field of porous carbon preparation, and relates to a preparation method of porous carbon and the porous carbon prepared by the preparation method.
Background
Due to the unique properties, the porous carbon material has wide application in the aspects of application such as lithium ion electrode materials, catalysis, drug loading, adsorption and the like. According to IUPAC regulations, porous carbon materials can be classified into the following three types based on their pore size: micropores are less than 2nm, mesopores are less than 50nm and macropores are more than 50 nm.
The preparation method of the porous carbon with the macroporous structure mainly comprises a template method, and the conventional steps for synthesizing the porous carbon by using the template method comprise: (1) preparation of a carbon precursor/template composite, (2) carbonization and removal of the template. The templates may be classified into hard templates and soft templates according to the kinds of the templates. The hard template method is to introduce some inorganic metal precursor into the hard template pore passage, roast to produce oxide crystal in the nanometer pore passage and eliminate the hard template to prepare the corresponding mesoporous material. Ideally, the obtained material can keep the pore channel morphology of the original template. Commonly used hard templates comprise inorganic colloids or preformed porous inorganic structures, such as monodisperse silica spheres or zeolites. The soft templates are mainly polymer colloids, of which PMMA and PS colloids are the most commonly used. The use of a hard template requires an additional template removal process after the carbonization process, and is liable to generate toxic and harmful corrosive substances during the template removal process.
The conventional processes for synthesizing the macroporous porous carbon comprise a polymerization method and a Chemical Vapor Deposition (CVD) method. The polymerization method is to mix the template and the carbon precursor, polymerize the carbon precursor on the surface of the template under the action of the catalyst to generate polymerization reaction, and obtain the porous carbon with the macroporous structure by carbonizing and removing the template. The chemical vapor deposition method is to remove the template by taking a hard template as a substrate through vapor deposition to obtain the porous carbon with the macroporous structure.
CN108745326A discloses a preparation process of a three-dimensional ordered porous carbon material and a preparation process of an intermediate thereof, wherein SiO is used for the preparation process2The microsphere suspension is used as an intermediate for preparing the three-dimensional ordered porous carbon material with the aperture specification of 5nm or more and the aperture of 50nm or less, and the PMMA emulsion is used as an intermediate for preparing the three-dimensional ordered porous carbon material with the aperture specification of 50nm or more and the aperture of 50 mu m or less, so that a uniform and compact pore canal structure is formed.
The carbon material synthesized by a polymerization method and a Chemical Vapor Deposition (CVD) method needs to be subjected to a crushing process to obtain micron-sized particles, so that not only is the crushing process flow required to be increased, but also the crushing process can seriously damage the special macroporous structure of the material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of porous carbon and the prepared porous carbon. The soft template is directly removed in the carbonization process, micron-sized spherical particles can be directly obtained by spray drying, the spheroidization and crushing processes are omitted, and the original pore diameter structure of the porous carbon is reserved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of macroporous porous carbon, which comprises the following steps:
and mixing the template emulsion with a carbon source, and then spray-drying to obtain a porous carbon precursor, and carbonizing the porous carbon precursor to obtain the porous carbon.
The invention combines a soft template and a spray drying process to synthesize the spherical porous carbon with uniform macroporous structure. The soft template is directly removed in the carbonization process, micron-sized spherical particles can be directly obtained by spray drying, the spheroidization and crushing processes are omitted, and the original pore diameter structure of the porous carbon is reserved.
The main invention point of the invention is that the soft template method and the spray drying are organically integrated, and the spheroidization and pulverization steps in the traditional soft template method process are replaced by the spray drying, while the pulverization steps in the traditional soft template method can seriously damage the pore structure of the porous carbon, and the micron-sized particles can be directly obtained by adopting the spray drying high-temperature granulation without influencing the pore structure of the porous carbon. Therefore, it can be understood that the core invention of the present invention lies in using spray drying in the soft template method, and the inherent process steps and process conditions of the soft template method are not within the protection scope and disclosure scope of the present invention, and those skilled in the art can make adaptive adjustment or simple replacement on the soft template method, i.e. the type, ratio and preparation process of the template agent in the template emulsion defined in the present application, and can also achieve the technical effects expressed by the present invention. In other words, any template emulsion that is currently used in the present invention falls within the scope of the present invention.
As a preferred technical scheme of the present invention, the preparation method specifically comprises:
mixing and stirring a polymer monomer, deionized water and an initiator, and reacting to prepare a template emulsion;
(II) mixing the template emulsion with a carbon source, diluting to obtain a mixed precursor solution, and spray drying to obtain a porous carbon precursor;
and (III) carbonizing the porous carbon precursor to obtain the porous carbon.
As a preferable technical scheme, in the step (I), the template emulsion is prepared by adopting the following method:
the adding sequence of the polymer monomer, the water and the initiator is as follows: adding a polymer monomer into deionized water, uniformly stirring, heating, introducing nitrogen, adding an initiator after the temperature is stable, and reacting to obtain the template emulsion.
In a preferred embodiment of the present invention, the polymer monomer is MMA.
The molar ratio of water to MMA is preferably (13.7 to 39: 1), and may be, for example, 13.7:1, 20:1, 22:1, 24:1, 26:1, 28:1, 30:1, 32:1, 34:1, 36:1, 38:1 or 39:1, but is not limited to the enumerated values, and other unrecited values within this range are also applicable, and more preferably (18.7 to 34): 1.
Preferably, the nitrogen gas is introduced for 20 to 30min, for example, 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min or 30min, but not limited to the values listed, and other values not listed in the range of the values are also applicable, and further preferably 30 min.
Preferably, the stirring rate is 300-400 r/min, such as 300r/min, 310r/min, 320r/min, 330r/min, 340r/min, 350r/min, 360r/min, 370r/min, 380r/min, 390r/min or 400r/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable, and more preferably 350 r/min.
The temperature rise is preferably 60 to 80 ℃ and may be, for example, 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃ or 80 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and more preferably 65 to 75 ℃.
Preferably, the initiator is potassium persulfate.
Preferably, the initiator is added in an amount of 0.05 to 0.4g/L, for example, 0.05g/L, 0.1g/L, 0.15g/L, 0.2g/L, 0.25g/L, 0.3g/L, 0.35g/L or 0.4g/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the reaction time is 1.5 to 3 hours, for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2.0 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3.0 hours, but not limited to the values listed, and other values not listed in the range of the values are also applicable, and further 2 hours are more preferable.
In a preferred embodiment of the present invention, in step (ii), the carbon source is phenolic resin.
Preferably, the temperature of the spray drying is 150 to 250 ℃, for example, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but not limited to the values listed, and other values not listed within the range of the values are also applicable, and more preferably 180 to 220 ℃. Preferably, the feeding amount of the spray drying is 1 to 20kg/h, for example, 1kg/h, 2kg/h, 3kg/h, 4kg/h, 5kg/h, 6kg/h, 7kg/h, 8kg/h, 9kg/h, 10kg/h, 11kg/h, 12kg/h, 13kg/h, 14kg/h, 15kg/h, 16kg/h, 17kg/h, 18kg/h, 19kg/h or 20kg/h, but is not limited to the enumerated values, and other non-enumerated values in the numerical range are also applicable, and further preferably 5 to 15 kg/h.
In the invention, the feeding amount of spray drying is particularly limited to 1-20 kg/h, and when the feeding amount is less than 1kg/h, the particle size of the prepared porous carbon is too small, and when the feeding amount is more than 20kg/h, the particle size of the prepared porous carbon is too large.
Preferably, the total concentration of the template emulsion and the carbon source in the mixed precursor solution is 1 to 25 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, or 25 wt%, but not limited to the recited values, and other values not recited in the range of values are also applicable, preferably 5 to 20 wt%.
In a preferred embodiment of the present invention, in step (II), the mixed precursor solution is fed through a atomizing disk.
Preferably, the rotational speed of the atomizing disk is 10000 to 30000r/min, such as 10000r/min, 12000r/min, 14000r/min, 16000r/min, 18000r/min, 20000r/min, 22000r/min, 24000r/min, 26000r/min, 28000r/min or 30000r/min, but not limited to the listed values, and other values not listed in the range of the values are also applicable, preferably 15000 to 25000 r/min.
In the invention, the rotating speed of the atomizing disk is particularly limited to 10000-30000 r/min, when the rotating speed is lower than 10000r/min, the particle size of the prepared porous carbon is too large, and when the rotating speed is higher than 30000r/min, the particle size of the prepared porous carbon is too small.
In a preferred embodiment of the present invention, in the step (III), the carbonization temperature is 600 to 1100 ℃, and may be, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, or 1100 ℃, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values are also applicable.
Preferably, the temperature increase rate of the carbonization process is 1-10 ℃/min, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min, 6 ℃/min, 7 ℃/min, 8 ℃/min, 9 ℃/min or 10 ℃/min, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the carbonization time is 1 to 5 hours, for example, 1.0 hour, 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours or 5.0 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is (13.7-39): 1, mixing and stirring at 300-400 r/min, heating to 60-80 ℃, introducing nitrogen for 20-30 min, adding 0.05-0.4 g/L of initiator potassium persulfate after the temperature is stable, and reacting for 1.5-3 h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion and phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 1-25 wt%, feeding the mixed precursor solution through an atomizing disc with the rotation speed of 10000-30000 r/min at the flow rate of 1-20 kg/h, and performing spray drying to obtain a porous carbon precursor;
(3) and heating the porous carbon precursor to 600-1100 ℃ at the heating rate of 1-10 ℃/min, and carbonizing for 1-5 h to obtain the porous carbon.
In a second aspect, the present invention provides a porous carbon prepared by the preparation method of the first aspect.
In a preferred embodiment of the present invention, the porous carbon has a pore size of more than 50nm, for example, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm or 200nm, but the pore size is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, preferably 100 to 200 nm.
Preferably, the pore size of the macroporous porous carbon is 1 to 40 μm, and may be, for example, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm or 40 μm, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the number of particles with the particle size of 12-18 μm in the porous carbon accounts for 50%.
Compared with the prior art, the invention has the beneficial effects that:
the invention combines a soft template and a spray drying process to synthesize the spherical porous carbon with uniform macroporous structure. The soft template is directly removed in the carbonization process, micron-sized spherical particles can be directly obtained by spray drying, the spheroidization and crushing processes are omitted, and the original pore diameter structure of the porous carbon is reserved.
Drawings
FIG. 1 is an electron micrograph of porous carbon prepared in example 3 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a preparation method of porous carbon, which comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 13.7:1, mixing and stirring at 300r/min, heating to 60 ℃, introducing nitrogen for 20min, adding 0.05g/L of initiator potassium persulfate after the temperature is stable, and reacting for 3h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 1 wt%, feeding the mixed precursor solution through an atomizing disc at the rotating speed of 10000r/min at the flow rate of 1kg/h, and carrying out spray drying at the temperature of 150 ℃ to obtain a porous carbon precursor;
(3) and (3) heating the porous carbon precursor to 600 ℃ at the heating rate of 1 ℃/min, and carbonizing for 5h to obtain the porous carbon.
Example 2
The embodiment provides a preparation method of porous carbon, which comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 18.7:1, mixing and stirring at 300r/min, heating to 65 ℃, introducing nitrogen for 23min, adding 0.1g/L of initiator potassium persulfate after the temperature is stable, and reacting for 2.5h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 5 wt%, feeding the mixed precursor solution through an atomizing disc with the rotation speed of 15000r/min at the flow rate of 5kg/h, and carrying out spray drying at 180 ℃ to obtain a porous carbon precursor;
(3) and (3) heating the porous carbon precursor to 700 ℃ at the heating rate of 3 ℃/min, and carbonizing for 4h to obtain the porous carbon.
Example 3
The embodiment provides a preparation method of porous carbon, which comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 25:1, mixing and stirring at 350r/min, heating to 70 ℃, introducing nitrogen for 25min, adding 0.2g/L of initiator potassium persulfate after the temperature is stable, and reacting for 2h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 10 wt%, feeding the mixed precursor solution through an atomizing disc with the rotating speed of 20000r/min at the flow rate of 10kg/h, and spray-drying at the temperature of 200 ℃ to obtain a porous carbon precursor;
(3) and heating the porous carbon precursor to 800 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3h to obtain the porous carbon.
An electron micrograph of the porous carbon prepared in this example is shown in fig. 1.
Example 4
The embodiment provides a preparation method of porous carbon, which comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 34:1, mixing and stirring at 370r/min, heating to 75 ℃, introducing nitrogen for 28min, adding 0.3g/L of initiator potassium persulfate after the temperature is stable, and reacting for 1.8h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 20 wt%, feeding the mixed precursor solution through an atomizing disc with the rotating speed of 25000r/min at the flow rate of 15kg/h, and carrying out spray drying at 220 ℃ to obtain a porous carbon precursor;
(3) and (3) heating the porous carbon precursor to 1000 ℃ at the heating rate of 7 ℃/min, and carbonizing for 2h to obtain the porous carbon.
Example 5
The embodiment provides a preparation method of porous carbon, which comprises the following steps:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 39:1, mixing and stirring at 400r/min, heating to 80 ℃, introducing nitrogen for 30min, adding 0.4g/L of initiator potassium persulfate after the temperature is stable, and reacting for 1.5h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 25 wt%, feeding the mixed precursor solution through an atomizing disc with the rotating speed of 30000r/min at the flow rate of 20kg/h, and carrying out spray drying at 250 ℃ to obtain a porous carbon precursor;
(3) and heating the porous carbon precursor to 1100 ℃ at the heating rate of 10 ℃/min, and carbonizing for 1h to obtain the porous carbon.
Example 6
This example provides a method for producing porous carbon, and differs from example 3 in that the feeding amount of the mixed precursor solution in step (2) is 0.5kg/h, and the remaining process steps and condition parameters are exactly the same as those in example 3.
Example 7
This example provides a method for producing porous carbon, which differs from example 3 in that the mixed precursor solution is fed in an amount of 25kg/h in step (2), and the remaining process steps and condition parameters are exactly the same as those in example 3.
Example 8
This example provides a process for the preparation of porous carbon which differs from example 3 in that in step (2) the rotational speed of the atomizing disk is 9000r/min and the remaining process steps and condition parameters are exactly the same as in example 3.
Example 9
This example provides a process for the preparation of porous carbon, which differs from example 3 in that in step (2) the rotation speed of the atomizer disk is 32000r/min, and the remaining process steps and condition parameters are exactly the same as in example 3.
Comparative example 1
The present comparative example provides a method of preparing a porous carbon, the method comprising:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is 25:1, mixing and stirring at 350r/min, heating to 70 ℃, introducing nitrogen for 25min, adding 0.2g/L of initiator potassium persulfate after the temperature is stable, and reacting for 2h to obtain the PMMA emulsion;
(2) mixing the PMMA emulsion with phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 10 wt%, and stirring and drying at the temperature of 80 ℃ to obtain a porous carbon precursor;
(3) and heating the porous carbon precursor to 800 ℃ at the heating rate of 5 ℃/min, carbonizing for 3h to obtain the porous carbon, and then crushing and spheroidizing to obtain the spherical porous carbon.
The pore diameters and average particle diameters of the porous carbons prepared by the preparation methods provided in examples 1 to 9 and comparative example 1 are shown in table 1.
TABLE 1
| Examples | Pore size (nm) | Average particle diameter (μm) |
| Example 1 | 245 | 23.3 |
| Example 2 | 220 | 25.6 |
| Example 3 | 180 | 27.4 |
| Example 4 | 165 | 30.1 |
| Example 5 | 145 | 33.4 |
| Example 6 | 180 | 16.3 |
| Example 7 | 180 | 42.5 |
| Example 8 | 180 | 32.5 |
| Example 9 | 180 | 15.5 |
| Comparative example 1 | 238 | 11.95 |
From comparison of the average particle size data of comparative example 3, example 6 and example 7, it can be seen that the average particle size of the porous carbon prepared in example 6 is smaller than that of example 3, while the average particle size of the porous carbon prepared in example 7 is larger than that of example 3, and thus it can be seen that when the feeding amount is less than 1kg/h, the average particle size of the porous carbon prepared is too small, and when the feeding amount is more than 20kg/h, the particle size of the porous carbon prepared is too large.
From comparison of the average particle size data of example 3, example 8 and example 9, it can be seen that the average particle size of the porous carbon prepared in example 8 is larger than that of example 3, while the average particle size of the porous carbon prepared in example 9 is smaller than that of example 3, and thus it can be seen that when the feeding amount is less than 10000r/min, the particle size of the porous carbon prepared is too large, and when the feeding amount is more than 30000r/min, the particle size of the porous carbon prepared is too small.
It can be seen from the average particle size data of example 1 and comparative example 1 that the average particle size of the porous carbon prepared in comparative example 1 is much smaller than that of example 3, because the porous carbon has a pore structure seriously damaged by the conventional crushing and spheroidizing operation adopted in comparative example 1, and the micron-sized particles can be directly obtained by spray drying and high-temperature granulation adopted in example 3 without affecting the pore structure of the porous carbon. The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of porous carbon is characterized by comprising the following steps:
and mixing the template emulsion with a carbon source, and then spray-drying to obtain a porous carbon precursor, and carbonizing the porous carbon precursor to obtain the porous carbon.
2. The preparation method according to claim 1, wherein the preparation method specifically comprises:
mixing and stirring a polymer monomer, deionized water and an initiator, and reacting to prepare a template emulsion;
(II) mixing the template emulsion with a carbon source, diluting to obtain a mixed precursor solution, and spray drying to obtain a porous carbon precursor;
and (III) carbonizing the porous carbon precursor to obtain the porous carbon.
3. The method according to claim 2, wherein in step (i), the template emulsion is prepared by the following method:
adding a polymer monomer into deionized water, uniformly stirring, heating, introducing nitrogen, adding an initiator after the temperature is stable, and reacting to obtain the template emulsion.
4. The method according to claim 3, wherein the polymer monomer is MMA;
preferably, the molar ratio of the deionized water to the MMA is (13.7-39): 1, and more preferably (18.7-34): 1;
preferably, nitrogen is introduced for 20-30 min, and further preferably for 30 min;
preferably, the stirring speed is 300-400 r/min, and further preferably 350 r/min;
preferably, the temperature is increased to 60-80 ℃, and further preferably 65-75 ℃;
preferably, the initiator is potassium persulfate;
preferably, the addition amount of the initiator is 0.05-0.4 g/L;
preferably, the reaction time is 1.5-3 h, and more preferably 2 h.
5. The process according to any one of claims 2 to 4, wherein in the step (II), the carbon source is a phenolic resin;
preferably, the temperature of the spray drying is 150-250 ℃, and further preferably 180-220 ℃;
preferably, the feeding amount of the spray drying is 1-20 kg/h, and further preferably 5-15 kg/h;
preferably, the total concentration of the template emulsion and the carbon source in the mixed precursor solution is 1-25 wt%, preferably 5-20 wt%.
6. The process according to any one of claims 2 to 5, wherein in step (II), the mixed precursor solution is fed through a atomizing disk;
preferably, the rotating speed of the atomizing disk is 10000-30000 r/min, preferably 15000-25000 r/min.
7. The method according to any one of claims 2 to 6, wherein in the step (III), the carbonization temperature is 600 to 1100 ℃;
preferably, the temperature rise rate in the carbonization process is 1-10 ℃/min;
preferably, the carbonization time is 1-5 h.
8. The method according to any one of claims 1 to 7, wherein the method comprises the steps of:
(1) adding a polymer monomer MMA into deionized water, wherein the molar ratio of the deionized water to the MMA is (13.7-39): 1, mixing and stirring at 300-400 r/min, heating to 60-80 ℃, introducing nitrogen for 20-30 min, adding 0.05-0.4 g/L of initiator potassium persulfate after the temperature is stable, and reacting for 1.5-3 h to obtain the PMMA emulsion;
(2) mixing PMMA emulsion and phenolic resin to obtain a mixed precursor solution, wherein the concentration of the PMMA emulsion in the mixed precursor solution is 1-25 wt%, feeding the mixed precursor solution through an atomizing disc with the rotation speed of 10000-30000 r/min at the flow rate of 1-20 kg/h, and performing spray drying to obtain a porous carbon precursor;
(3) and heating the porous carbon precursor to 600-1100 ℃ at the heating rate of 1-10 ℃/min, and carbonizing for 1-5 h to obtain the porous carbon.
9. A macroporous porous carbon prepared by the preparation method of any one of claims 1 to 8.
10. The macroporous porous carbon according to claim 9, wherein the pore size of the porous carbon is greater than 50nm, preferably 100-200 nm;
preferably, the pore diameter of the macroporous porous carbon is 1-40 μm;
preferably, the number of particles with the particle size of 12-18 μm in the porous carbon accounts for 50%.
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