CN114956067A - Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method - Google Patents
Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method Download PDFInfo
- Publication number
- CN114956067A CN114956067A CN202210578904.7A CN202210578904A CN114956067A CN 114956067 A CN114956067 A CN 114956067A CN 202210578904 A CN202210578904 A CN 202210578904A CN 114956067 A CN114956067 A CN 114956067A
- Authority
- CN
- China
- Prior art keywords
- foam
- foam carbon
- mesophase pitch
- carbon
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 93
- 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 55
- 239000011148 porous material Substances 0.000 title claims abstract description 37
- 239000010439 graphite Substances 0.000 title claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007833 carbon precursor Substances 0.000 title claims abstract description 13
- 239000011302 mesophase pitch Substances 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000006011 modification reaction Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 238000005087 graphitization Methods 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 17
- 239000006185 dispersion Substances 0.000 abstract description 15
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000011295 pitch Substances 0.000 abstract 1
- 239000010426 asphalt Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000004321 preservation Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 238000005273 aeration Methods 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 238000005276 aerator Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- -1 comprises two types Chemical compound 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Images
Classifications
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a foam carbon precursor, graphite foam carbon with uniform pore diameter and a preparation method thereof, aiming at the problem of nonuniform pore diameter of the prepared foam carbon caused by the complexity of the components of mesophase pitch, the oxidation heat treatment is carried out on the mesophase pitch, and partial oxidation crosslinking reaction is carried out among the mesophase pitch molecules on the premise of keeping the thermoplasticity of the mesophase pitch, so that the thermal stability and the reaction uniformity in the foaming process are improved, and the preparation of the high-heat-conductivity foam carbon with uniform pore diameter is finally realized, and the preparation method specifically comprises the following steps: and (3) filling the mesophase pitch into a reaction kettle, introducing oxygen-containing gas, and carrying out modification reaction under stirring, wherein the temperature of the modification reaction is 280-350 ℃, the time is 0.5-48h, and the stirring speed is 30-300 r/min. And cooling after the reaction is finished to obtain the foam carbon precursor. According to the invention, no foaming auxiliary agent is added to assist the foaming of the mesophase pitch, so that the thermal conductivity and the mechanical property of the foam carbon are improved, the aperture dispersion rate is less than or equal to 20%, and the product amount of the foam carbon produced by unit raw material pitch is improved by 20-40%.
Description
Technical Field
The invention belongs to the technical field of high-performance carbon material production, and particularly relates to a foam carbon precursor, graphite foam carbon with uniform pore diameter and a preparation method thereof.
Background
The mesophase pitch-based foam carbon is a novel carbon material with a three-dimensional network structure, which is formed by pores formed in the foaming process of a precursor of the foam carbon and regularly arranged graphite ligament structures around the pores. Because the mesophase pitch-based foam carbon has the characteristics of light weight, high heat conductivity, excellent high-temperature mechanical property, wave absorption and thermal vibration resistance and the like, the mesophase pitch-based foam carbon has wide application prospect in the fields of advanced manufacturing and weaponry such as high-power heat exchanger equipment, high-power laser weapons, high-temperature electromagnetic shielding and the like.
At present, the preparation method of the mesophase pitch-based foam carbon mainly comprises two types, wherein one type is to foam the mesophase pitch as a raw material by a foaming agent, and the other type is to self-foam by high-pressure nitriding. U.S. patents 795763, 5397809 and chinese patents CN101164875B and CN101049928 report methods for preparing foam carbon by using a foaming agent, a catalyst and a surfactant to assist high-temperature foaming of mesophase pitch, but the added foaming agent, the added surfactant and the added catalyst affect the graphitization difficulty of the subsequent foam carbon to different degrees, so that the product has low graphite degree and poor mechanical properties and thermal conductivity. Compared with the prior art, the high-pressure nitriding self-foaming mainly utilizes the decomposition and self-volatilization of light components in the mesophase pitch at high temperature for foaming without introducing impurities, thereby being beneficial to improving the graphitization degree of the foam carbon and reducing the microscopic defects of the foam carbon in the heat treatment process. However, the mesophase pitch, which is a mixture with a complex composition and a wide molecular weight distribution range, causes non-uniform surface tension at high temperature due to different polymerization and decomposition conditions of different components, resulting in poor uniformity of pore size of the prepared carbon foam, and particularly, when preparing large-sized carbon foam having a foam height of more than 5cm, the non-uniformity of pore size of the raw material of the carbon foam is more pronounced due to the complexity of the components of the precursor. Therefore, in order to improve the overall performance of the mesophase pitch-based carbon foam prepared by the self-foaming method, a modification method for preparing a precursor of the carbon foam is developed to improve the uniformity of the carbon foam in the self-foaming process and prepare graphite carbon foam with uniform pore diameter, which is a key technical problem to be solved by the technical personnel in the field.
Disclosure of Invention
The invention mainly aims at the problem of uneven pore diameter of the prepared foam carbon caused by the complexity of the components of the mesophase pitch, and provides a method for improving the pore diameter uniformity of the foam carbon by modifying the mesophase pitch, wherein the mesophase pitch is subjected to oxidation heat treatment, partial oxidation crosslinking reaction is generated among the molecules of the mesophase pitch under the premise of keeping the thermoplasticity of the mesophase pitch by controlling the treatment process conditions, so that the thermal stability and the reaction uniformity in the foaming process are improved, and the preparation of the high-heat-conductivity foam carbon with even pore diameter is finally realized, and the method specifically comprises the following steps:
s1, filling the mesophase pitch into a reaction kettle, introducing oxygen-containing gas, and carrying out modification reaction under stirring, wherein the temperature of the modification reaction is 280-350 ℃, the time is 0.5-48h, and the stirring speed is 30-300 r/min. And cooling after the reaction is finished to obtain the foam carbon precursor (namely the modified mesophase pitch).
Further, the mesophase pitch comprises one or more of naphthalene mesophase pitch, petroleum mesophase pitch and coal mesophase pitch, the softening point of the mesophase pitch is 240-340 ℃, the H/C molar ratio is 0.45-0.65, and the oxygen content is 0.01-2 wt%.
Further, in the step S1, the flow rate of the gas containing oxygen introduced thereinto is 0.1 to 50 L.Kg -1 ·min -1 Preferably 0.5 to 10 L.kg -1 ·min -1 Oxygen-containing gases include, but are not limited to, air or oxygen.
The prepared foam carbon precursor (namely, the modified mesophase pitch) has the oxygen content of 0.5-6 wt%, preferably the oxygen content of 1-4 wt%, and more preferably the oxygen content of 1.5-3 wt%;
the softening point of the modified mesophase pitch is 245-350 ℃, and the H/C molar ratio is 0.40-0.60;
the invention also provides a preparation method of graphite foam carbon with uniform pore diameter, which is characterized by further comprising the following subsequent steps on the basis of the preparation method of any one of claims 1 to 3:
s2, crushing, sieving and molding the foam carbon precursor, placing the foam carbon precursor into a reaction kettle, introducing inert gas for pressurization, raising the temperature to 450-600 ℃, naturally cooling after constant-temperature reaction, and discharging gas to obtain foam raw material;
and S3, carbonizing and graphitizing the foam raw material to obtain the graphite foam carbon.
Further, in the step S2, the oxygen-containing gas has an oxygen content of 3 to 100% by volume;
further, in the step S2, the pressure is increased to 0.5 to 5MPa by using an inert gas.
Further, in step S2, the temperature increase process includes: heating to 320-400 ℃ at 5-10 ℃/min, and continuing heating to 450-600 ℃ at 0.5-5 ℃/min.
Further, in the step S2, the isothermal reaction time is 0.1 to 5 hours.
The obtained foam raw material has a density of 0.2-1.1g/cm -3 The aperture dispersion is less than 20%.
Further, in step S3, the carbonization and graphitization treatment step includes: heating to 800-1500 ℃ at the speed of 0.5-2 ℃/min to obtain the carbon foam; then heating to 2400-3000 ℃ at the speed of 0.5-5 ℃/min, and cooling to obtain the graphite foam carbon.
The density of the prepared graphite foam carbon is 0.2-1.0g/cm -3 The aperture dispersion rate is less than or equal to 20 percent, and the thermal conductivity is 30-200W/(m.K)
The invention also provides graphite foam carbon with uniform pore diameter, which is prepared by the preparation method.
By adopting the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the foaming auxiliary agent is not added to assist the intermediate phase asphalt to foam, the stabilization treatment is not required, the preparation process of the foam carbon is simplified, the increase of the micro defects of the foam carbon caused by the addition of the foaming auxiliary agent is effectively avoided, and the thermal conductivity and the mechanical property of the foam carbon are improved.
(2) By controlling the processing conditions, partial oxidation crosslinking reaction is generated among the molecules of the mesophase pitch on the premise of keeping the thermoplasticity of the mesophase pitch, so that the thermal stability and the reaction uniformity in the foaming process are improved, the high-heat-conductivity graphite foam carbon with uniform pore diameter (the dispersion rate is less than or equal to 20%) is obtained, the pore diameter is controlled by the foaming process, and the average pore diameter can be controlled between 300 and 700 microns.
(3) The homogeneity of the foam carbon is improved through the modification of the mesophase asphalt, so that the utilization rate of raw materials in the preparation process of the foam carbon material is improved, and the production cost of unit materials is reduced; after the foaming uniformity is improved, the cutting amount of the upper fluffy part and the bottom compact part of the foaming raw material is reduced by 50-80%, and the amount of the foam carbon product produced by unit raw material asphalt is improved by 20-40%.
(4) The intermediate phase asphalt after modification has obviously improved thermal stability, reduced foaming pressure, reduced equipment requirement and raised operation safety.
Drawings
FIG. 1 is a thermogravimetric curve of the mesophase pitch of naphthalene series before and after modification according to the present invention;
FIG. 2 is an SEM image of a foam raw material prepared by the invention;
FIG. 3 is an SEM image of graphitized carbon foam prepared according to the present invention;
FIG. 4 is a photograph of a carbon foam product and its upper fluffed (cut away) portion before and after modification by the present invention; the figure (A) is the product before modification, and the figure (B) is the product after modification.
Description of the symbols: 1-thermal weight loss curve of modified naphthalene mesophase pitch, 2-thermal weight loss curve of modified naphthalene mesophase pitch, 3-foam carbon plate and 4-cutting material.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Other embodiments, which can be derived by those skilled in the art from the embodiments of the present invention without any creative effort, are within the protection scope of the present invention.
Example 1
A preparation method of graphite foam carbon with uniform pore diameter comprises the following steps:
s1, charging petroleum mesophase pitch with softening point of 285 deg.C, H/C molar ratio of 0.54, and oxygen content of 0.5 wt% into a high temperature asphalt tank with aeration deviceHeating the mixture in a warm reaction kettle to 310 ℃, and introducing a ventilating device with the flow of 10L-Kg -1 ·min -1 Keeping the temperature for 3 hours, keeping stirring in the heat preservation process, wherein the stirring speed is 120r/min, cooling the intermediate phase asphalt after heat preservation, and collecting the intermediate phase asphalt for later use to obtain the modified intermediate phase asphalt, wherein the softening point of the modified intermediate phase asphalt is 295 ℃, the H/C molar ratio is 0.53, and the oxygen content is 2.5 wt%;
s2, crushing, sieving and molding the modified mesophase pitch, placing the crushed, sieved and molded modified mesophase pitch into a high-temperature high-pressure reaction kettle, checking the air tightness of the reaction kettle, introducing nitrogen, pressurizing to 3MPa, heating to 360 ℃ at a speed of 5 ℃/min, continuing heating to 600 ℃ at a speed of 0.5 ℃/min, reacting for 1h at a constant temperature, naturally cooling to room temperature, and discharging air to obtain a foam raw material, wherein the density of the obtained foam raw material is 0.48g/cm -3 The aperture dispersion is 18%;
s3, heating the foam raw material to 1000 ℃ at a speed of 0.5 ℃/min to obtain foam carbon, further heating to 2400 ℃ at a speed of 0.5 ℃/min to perform graphitization treatment, and cooling to obtain graphite foam carbon with the density of 0.53g/cm -3 The pore diameter dispersion ratio was 17%, and the thermal conductivity was 140W/(m.K).
Example 2
A preparation method of graphite foam carbon with uniform pore diameter comprises the following steps:
s1, filling petroleum mesophase pitch with a softening point of 294 ℃, an H/C molar ratio of 0.54 and an oxygen content of 0.5 wt% into a high-temperature reaction kettle with an aeration device, raising the temperature to 330 ℃, and introducing 10L & Kg of flow through the aeration device -1 ·min -1 Keeping the temperature for 2 hours, keeping stirring in the heat preservation process, wherein the stirring speed is 200r/min, cooling the intermediate phase asphalt after heat preservation, and collecting the intermediate phase asphalt for later use, namely the modified intermediate phase asphalt, wherein the softening point of the modified intermediate phase asphalt is 310 ℃, the H/C molar ratio is 0.52, and the oxygen content is 3.0 wt%;
s2, crushing, sieving and molding the modified mesophase pitch, putting the crushed, sieved and molded modified mesophase pitch into a high-temperature high-pressure reaction, checking the air tightness of a reaction kettle, introducing nitrogen, pressurizing to 5MPa, heating to 360 ℃ at 8 ℃/min, continuing heating to 600 ℃ at 1 ℃/min, keeping the temperature for 1h, naturally cooling to room temperature, and discharging air to obtain a foam raw material, wherein the density of the obtained foam raw material is0.52g/cm -3 The aperture dispersion is 16%;
s3, heating the foam raw material to 1000 ℃ at a speed of 1 ℃/min to obtain foam carbon, further heating to 3000 ℃ at a speed of 1 ℃/min to perform graphitization treatment, and cooling to obtain graphite foam carbon with a density of 0.60g/cm -3 The pore diameter dispersion was 15%, and the thermal conductivity was 160W/(m.K).
Example 3
A preparation method of graphite foam carbon with uniform pore diameter comprises the following steps:
s1, putting coal-series mesophase pitch with the softening point of 304 ℃, the H/C molar ratio of 0.46 and the oxygen content of 0.8 wt% into a high-temperature reaction kettle with an aeration device, heating to 350 ℃, introducing mixed gas of air and oxygen into the aeration device, wherein the volume content of the oxygen in the mixed gas is 50%, and the flow rate of the mixed gas is 20 L.Kg -1 ·min -1 Keeping the temperature for 10 hours, keeping stirring in the heat preservation process, wherein the stirring speed is 80r/min, cooling the intermediate phase asphalt after heat preservation, and collecting the intermediate phase asphalt for later use, namely the modified intermediate phase asphalt, wherein the softening point of the modified intermediate phase asphalt is 315 ℃, the H/C molar ratio is 0.45, and the oxygen content is 1.5 wt%;
s2, crushing, sieving and molding the modified mesophase pitch, putting the crushed, sieved and molded modified mesophase pitch into a high-temperature high-pressure reaction, checking the air tightness of a reaction kettle, introducing nitrogen, pressurizing to 5MPa, heating to 390 ℃ at a speed of 5 ℃/min, continuing heating to 500 ℃ at a speed of 4 ℃/min, keeping the temperature for 5 hours, naturally cooling to room temperature, and discharging air to obtain a foam raw material, wherein the density of the obtained foam raw material is 0.60g/cm -3 The aperture dispersion is 20%;
s3, heating the foam raw material to 1200 ℃ at a speed of 1.2 ℃/min to obtain foam carbon, further heating to 2900 ℃ at a speed of 5 ℃/min to perform graphitization treatment, and cooling to obtain graphite foam carbon with the density of 0.62g/cm -3 The pore diameter dispersion ratio was 18%, and the thermal conductivity was 120W/(m.K).
Example 4
A preparation method of graphite foam carbon with uniform pore diameter comprises the following steps:
s1, leaching the naphthalene mesophase with the softening point of 275 ℃, the H/C molar ratio of 0.60 and the oxygen content of 0.01 wt%Charging folium Isatidis into high temperature reaction kettle with aerator, heating to 300 deg.C, introducing mixed gas of nitrogen and oxygen into the aerator, wherein the volume content of oxygen in the mixed gas is 10%, and the flow rate is 70 L.Kg -1 ·min -1 Keeping the temperature for 5 hours, keeping stirring in the heat preservation process, wherein the stirring speed is 120r/min, cooling the intermediate phase asphalt after heat preservation, and collecting the intermediate phase asphalt for later use to obtain the modified intermediate phase asphalt, wherein the softening point of the modified intermediate phase asphalt is 301 ℃, the H/C molar ratio is 0.58, and the oxygen content is 1.5 wt%;
s2, crushing, sieving and molding the modified mesophase pitch, putting the crushed, sieved and molded modified mesophase pitch into a high-temperature high-pressure reaction, checking the air tightness of a reaction kettle, pressurizing the nitrogen to 3MPa, heating the nitrogen to 360 ℃ at a speed of 10 ℃/min, continuing heating the nitrogen to 600 ℃ at a speed of 3 ℃/min, keeping the temperature for 2 hours, naturally cooling the nitrogen to room temperature, and discharging the air to obtain a foam raw material, wherein the density of the obtained foam raw material is 0.51g/cm -3 The aperture dispersion is 16%;
s3, heating the foam raw material to 800 ℃ at a speed of 2 ℃/min to obtain foam carbon, further heating to 2600 ℃ at a speed of 4 ℃/min to perform graphitization treatment, and cooling to obtain graphite foam carbon with the density of 0.52g/cm -3 The pore diameter dispersion was 15%, and the thermal conductivity was 50W/(m.K).
Example 5
A preparation method of graphite foam carbon with uniform pore diameter comprises the following steps:
s1, putting naphthalene mesophase pitch with the softening point of 285 ℃, the H/C molar ratio of 0.54 and the oxygen content of 0.01 wt% into a high-temperature reaction kettle with an aeration device, heating to 320 ℃, introducing a mixed gas of nitrogen and oxygen into the aeration device, wherein the volume content of the oxygen in the mixed gas is 30%, and the flow rate of the mixed gas is 10 L.Kg -1 ·min -1 Keeping the temperature for 5 hours, keeping stirring in the heat preservation process, wherein the stirring speed is 120r/min, cooling the intermediate phase asphalt after heat preservation, and collecting the intermediate phase asphalt for later use, namely the modified intermediate phase asphalt, wherein the softening point of the modified intermediate phase asphalt is 308 ℃, the H/C molar ratio is 0.53, and the oxygen content is 2.4 wt%;
s2, crushing the modified mesophase pitch, sieving, filling into a mold, putting into a high-temperature high-pressure reaction, checking the air tightness of the reaction kettle, adding nitrogen gasPressing to 5MPa, heating to 320 deg.C at 6 deg.C/min, heating to 460 deg.C at 2 deg.C/min, holding for 4 hr, naturally cooling to room temperature, and discharging gas to obtain foam raw material with density of 0.6g/cm -3 The aperture dispersion is 18%;
s3, heating the foam raw material to 1400 ℃ at a speed of 1.8 ℃/min to obtain foam carbon, further heating to 2800 ℃ at a speed of 3 ℃/min to perform graphitization treatment, and cooling to obtain graphite foam carbon with the density of 0.65g/cm -3 The pore diameter dispersion ratio was 18%, and the thermal conductivity was 110W/(m.K).
FIG. 1 is the thermal weight loss curve of naphthalene mesophase pitch before and after modification, and it can be seen that the mesophase pitch after modification treatment according to the present invention has significantly improved thermal stability.
Fig. 2 and fig. 3 respectively show that the pore sizes of the foam raw material and the graphitized foam carbon prepared by the invention are relatively uniform, and the pore size dispersion rate is small.
Fig. 4 shows that, after the uniformity of the pore diameter of the graphite foam carbon plate prepared by the method of the present invention is improved, the thickness of the cutting material of the product when cutting the plate is obviously reduced, that is, when cutting the plate with the same thickness (40mm), the amount of the precursor used after the improvement is reduced, the number of the products made of unit raw material is improved, and the cost is reduced.
Claims (10)
1. The preparation method of the foam carbon precursor is characterized by comprising the following steps of:
s1, filling the mesophase pitch into a reaction kettle, introducing oxygen-containing gas, and carrying out modification reaction under stirring, wherein the temperature of the modification reaction is 280-350 ℃, the time is 0.5-48h, and the stirring speed is 30-300 r/min. And cooling after the reaction is finished to obtain the foam carbon precursor.
2. The method of claim 1, wherein in step S1, the mesophase pitch comprises one or more of naphthalene mesophase pitch, petroleum mesophase pitch, and coal mesophase pitch.
3. The method of claim 1, wherein in step S1, the flow rate of the oxygen-containing gas is 0.1-50L-Kg -1 ·min -1 。
4. A method for preparing graphite foam carbon with uniform pore diameter is characterized by comprising the following subsequent steps on the basis of the preparation method of any one of claims 1 to 3:
s2, crushing, sieving and molding the foam carbon precursor, placing the foam carbon precursor into a reaction kettle, introducing inert gas for pressurization, raising the temperature to 450-600 ℃, naturally cooling after constant-temperature reaction, and discharging gas to obtain foam raw material;
and S3, carbonizing and graphitizing the foam raw material to obtain the graphite foam carbon.
5. The method as claimed in claim 4, wherein the oxygen-containing gas has an oxygen content of 3-100% by volume in step S2.
6. The method of claim 4, wherein in step S2, the graphite carbon foam with uniform pore size is pressurized to 0.5-5MPa by using inert gas.
7. The method for preparing graphite foam carbon with uniform pore size according to claim 4, wherein in the step S2, the temperature rising process is as follows: heating to 320-400 ℃ at 5-10 ℃/min, and continuing heating to 450-600 ℃ at 0.5-5 ℃/min.
8. The method of claim 4, wherein in step S2, the isothermal reaction time is 0.1-5 h.
9. The method for preparing graphite foam carbon with uniform pore size according to claim 4, wherein in step S3, the carbonization and graphitization treatment steps are as follows: heating to 800-1500 ℃ at the speed of 0.5-2 ℃/min to obtain the carbon foam; then heating to 2400-3000 ℃ at the speed of 0.5-5 ℃/min, and cooling to obtain the graphite foam carbon.
10. Graphite carbon foam having a uniform pore size, which is produced by the production method according to any one of claims 4 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210578904.7A CN114956067A (en) | 2022-05-25 | 2022-05-25 | Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210578904.7A CN114956067A (en) | 2022-05-25 | 2022-05-25 | Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114956067A true CN114956067A (en) | 2022-08-30 |
Family
ID=82956217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210578904.7A Pending CN114956067A (en) | 2022-05-25 | 2022-05-25 | Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114956067A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345666A (en) * | 1992-06-15 | 1993-12-27 | Kobe Steel Ltd | Production of formed carbon material |
| JPH06144812A (en) * | 1992-06-19 | 1994-05-24 | Mitsubishi Gas Chem Co Inc | Self-fusible carbonaceous powder and high-density carbon material |
| CN101066757A (en) * | 2007-05-11 | 2007-11-07 | 东华大学 | Process of preparing asphalt carbon foam material |
| CN104445136A (en) * | 2013-09-23 | 2015-03-25 | 上海宝钢化工有限公司 | Foam carbon for energy-saving building thermal insulation material and preparation method thereof |
| CN104591131A (en) * | 2015-01-27 | 2015-05-06 | 航天材料及工艺研究所 | Preparation method of high-thermal-conductivity graphene-enhanced foamy carbon |
| CN104946289A (en) * | 2014-03-28 | 2015-09-30 | 上海宝钢化工有限公司 | High-softening-point asphalt, and preparation method and application thereof |
-
2022
- 2022-05-25 CN CN202210578904.7A patent/CN114956067A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345666A (en) * | 1992-06-15 | 1993-12-27 | Kobe Steel Ltd | Production of formed carbon material |
| JPH06144812A (en) * | 1992-06-19 | 1994-05-24 | Mitsubishi Gas Chem Co Inc | Self-fusible carbonaceous powder and high-density carbon material |
| CN101066757A (en) * | 2007-05-11 | 2007-11-07 | 东华大学 | Process of preparing asphalt carbon foam material |
| CN104445136A (en) * | 2013-09-23 | 2015-03-25 | 上海宝钢化工有限公司 | Foam carbon for energy-saving building thermal insulation material and preparation method thereof |
| CN104946289A (en) * | 2014-03-28 | 2015-09-30 | 上海宝钢化工有限公司 | High-softening-point asphalt, and preparation method and application thereof |
| CN104591131A (en) * | 2015-01-27 | 2015-05-06 | 航天材料及工艺研究所 | Preparation method of high-thermal-conductivity graphene-enhanced foamy carbon |
Non-Patent Citations (1)
| Title |
|---|
| 张红波 等: "预氧化时间对中间相沥青及其泡沫炭的影响", 湖南大学学报（自然科学版）, vol. 37, no. 10, pages 67 - 71 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5868974A (en) | Process for preparing pitch foams | |
| WO2019218540A1 (en) | Method for preparing polyacrylonitrile-based three-dimensional macroporous carbon block | |
| US20020136680A1 (en) | Carbon foam, graphite foam and production processes of these | |
| US11167991B2 (en) | Method for preparing carbon nanotube/polymer composite | |
| CN107304490B (en) | Preparation method of graphene/polyimide composite carbon fiber | |
| CN100374367C (en) | Technical method and schedule for preparation of foam carbon material used asphalt as raw material | |
| CN101049928B (en) | Method for manufacturing high heat conducting foam material of graphite with even apertures | |
| CN102502595A (en) | Preparation method of isotropic graphite | |
| CN105197912A (en) | Method for preparing foam carbon composite material | |
| CN101066757A (en) | Process of preparing asphalt carbon foam material | |
| CN108164268B (en) | Preparation method of graphene composite silicon-carbon-nitrogen precursor ceramic | |
| CN114956067A (en) | Foam carbon precursor, graphite foam carbon with uniform pore diameter and preparation method | |
| CN110527129B (en) | Polyether-ether-ketone porous foam material and preparation method thereof | |
| CN112608474A (en) | Polyimide film and graphite film | |
| CN116536034A (en) | Preparation method of polyimide graphitized film | |
| CN1733603A (en) | Asphalt carbon foamed material preparation method | |
| CN114989429A (en) | Polyimide film, graphite sheet, corresponding preparation method and resin composition | |
| JPH06183835A (en) | Production of preform body for staple fiber-reinforced c/c composite and preform body production by the same method | |
| CN113353926A (en) | Polyimide film for preparing graphite film, high-thermal-conductivity graphite film prepared from polyimide film and preparation method of high-thermal-conductivity graphite film | |
| CN113087501A (en) | High-strength quartz ceramic roller and preparation process thereof | |
| CN116354741A (en) | Method for preparing low-density hierarchical pore isostatic pressing graphite material by template method | |
| CN110615433B (en) | Preparation method of high-thermal-conductivity mesophase pitch-based foamy carbon | |
| CN114410328B (en) | High carbon coke with wrinkled carbon layer and preparation method thereof | |
| CN114989851B (en) | Foam carbon precursor, graphite foam carbon and preparation method of graphite foam carbon | |
| CN109133027B (en) | Method for preparing mesoporous carbon material by catalyzing phenolic polymerization with magnesium carbonate trihydrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240109 Address after: 437300 Chibi High Quality Development Research Institute, Building 33, High tech Zone Beautiful Health Industrial Park, Zhonghuopu Town, Chibi City, Xianning City, Hubei Province Applicant after: Hubei Haoke Carbon Material Technology Co.,Ltd. Address before: No. 947, Peace Avenue, Wuhan, Hubei Province, Hubei Applicant before: WUHAN University OF SCIENCE AND TECHNOLOGY |
|
| TA01 | Transfer of patent application right |