CN111117681B - Graphene composite asphalt material and preparation method thereof - Google Patents
Graphene composite asphalt material and preparation method thereof Download PDFInfo
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- CN111117681B CN111117681B CN202010047424.9A CN202010047424A CN111117681B CN 111117681 B CN111117681 B CN 111117681B CN 202010047424 A CN202010047424 A CN 202010047424A CN 111117681 B CN111117681 B CN 111117681B
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- asphalt
- coal
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- 239000010426 asphalt Substances 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000011294 coal tar pitch Substances 0.000 claims abstract description 12
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000003245 coal Substances 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 239000011300 coal pitch Substances 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 7
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 7
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011295 pitch Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- AKROLTGTPNCGRL-UHFFFAOYSA-K tripotassium;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[K+].[K+].[K+] AKROLTGTPNCGRL-UHFFFAOYSA-K 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000004939 coking Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/023—Working-up pitch, asphalt, bitumen by chemical means reaction with inorganic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a graphene composite asphalt material and a preparation method thereof, which comprises the steps of crushing medium-temperature coal asphalt, uniformly mixing the crushed medium-temperature coal asphalt with graphene, a cross-linking agent and a catalyst, and carrying out cross-linking polymerization at 140-180 ℃ to obtain the graphene composite asphalt material. The method of the invention can obviously improve the heat-conducting property and the electric conductivity of the coal tar pitch.
Description
Technical Field
The invention relates to the technical field of deep processing of coal pitch, in particular to a preparation method of modified pitch.
Background
China is a big country of coal resources, millions of tons of medium-temperature coal tar are produced in the coal carbonization process, and the quantity of the medium-temperature coal tar is extremely considerable. The medium temperature coal tar pitch (medium temperature coal tar pitch) is the main component of medium temperature coal tar and accounts for 50-55% of the mass of the coal tar. Therefore, the full utilization of the medium-temperature coal pitch has important significance.
With the development of scientific technology and the continuous updating of experimental means, the carbon industry in China is rapidly developed, and various high-performance novel carbon materials continuously appear. At present, medium temperature pitch is mostly used as a binder of carbon material production enterprises, the requirement on the quality of a prebaked anode is higher and higher in the aluminum electrolysis production process, and the most important factor influencing the quality of the prebaked anode is the coal pitch performance serving as the binder. Therefore, it is urgent to produce high-quality coal pitch which meets the formulation of high-quality prebaked anode, but the medium temperature pitch contains less beta resin, which affects the conductivity of carbon material to some extent. The medium temperature pitch is also an important raw material in the production of the prebaked anode, and the quality of the medium temperature pitch directly affects the service performance (such as volume density, compressive strength, electrical conductivity, thermal conductivity and the like) of the prebaked anode, and the performance is related to the coal pitch binding performance, the coking carbon residue and the ash content and the sulfur content. At present, large-scale carbon material production enterprises for aluminum in China successfully adopt modified asphalt to replace medium-temperature asphalt as a binder for producing a prebaked anode, while metallurgical carbon material enterprises mainly producing graphite electrodes in China just start to update the binder asphalt, and the replacement of medium-temperature asphalt by the modified asphalt is a necessary trend along with the development and production of large-scale ultrahigh-power graphite electrodes.
Disclosure of Invention
The invention aims to provide a graphene composite asphalt material and a preparation method thereof, and aims to modify medium-temperature coal asphalt by taking graphene as a modifier and searching for proper modification conditions so as to improve the electric conductivity and the heat conductivity of the medium-temperature coal asphalt.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention discloses a preparation method of a graphene composite asphalt material, which is characterized by comprising the following steps: crushing medium-temperature coal pitch, uniformly mixing with graphene, a cross-linking agent and a catalyst, and performing cross-linking polymerization at 140-180 ℃ to obtain the graphene composite pitch material.
Further, the crosslinking agent is at least one of divinylbenzene, cinnamaldehyde, and paraformaldehyde.
Further, the catalyst is p-toluenesulfonic acid or potassium trichloride.
Further, the molar ratio of the cross-linking agent to the coal pitch is 0.25-0.75: 1. Further, divinylbenzene is preferably used as the crosslinking agent, and the molar ratio of the divinylbenzene to the coal pitch is 0.25:1, with the addition of a proper amount of cinnamaldehyde as an aid.
Further, the amount of the catalyst accounts for 1-10 wt%, preferably 5 wt% of the mass of the coal tar pitch.
Further, the graphene accounts for 1-10 wt%, preferably 5 wt% of the coal tar pitch.
Further, the pulverization is to pulverize coal asphalt into a particle size of not more than 0.1 mm.
Further, the time of the cross-linking polymerization is 3-5 h.
Further, the temperature increase rate of the crosslinking polymerization was 5 ℃/min.
The invention also discloses the graphene composite asphalt material obtained by the preparation method.
The invention has the beneficial effects that:
1. the method of the invention can obviously improve the heat-conducting property and the electric conductivity of the coal tar pitch.
2. According to the invention, the crosslinking agent and the catalyst are utilized to directly carry out crosslinking polymerization under normal pressure to complete the modification of the coal pitch by the graphene, and the method is simple and low in manufacturing cost.
3. The raw material proportion and the reaction temperature screened by the method can optimize the performance of the graphene composite asphalt material, particularly the heat-conducting performance.
Drawings
Fig. 1 is an SEM image of a graphene composite asphalt material obtained in example 1 of the present invention;
fig. 2 is an SEM image of the graphene composite asphalt material obtained in example 2 of the present invention;
FIG. 3 is an SEM image of a graphene composite asphalt material obtained in example 3 of the present invention;
fig. 4 is an SEM image of the graphene composite asphalt material obtained in example 4 of the present invention.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
The softening point, the quinoline insolubles, the toluene insolubles and the coking values of the samples obtained in the following examples are respectively measured according to GB/T2294-1997, GB/T8727-2008, GB/T2292-1997 and GB/T2293-2008, and the heat conductivity value is measured by a heat conductivity coefficient tester.
The softening point of the medium-temperature asphalt used in the following examples is 70-80 ℃, quinoline insoluble substances are less than or equal to 3 percent, toluene insoluble substances are 15-19 percent, and the coking value is less than or equal to 31 percent.
Example 1
Weighing 100g of medium-temperature asphalt, grinding the medium-temperature asphalt in a mortar to enable the particle size of the medium-temperature asphalt to be not more than 0.1mm, and adding the medium-temperature asphalt into a three-neck flask; then 1g (1 wt%) of graphene and 2.26g of p-toluenesulfonic acid are added into a three-neck flask, a device is fixed, 7.5mL of divinylbenzene and 2mL of cinnamaldehyde are added into the three-neck flask, then condensed water is introduced under the protection of nitrogen, and the mechanical stirring speed is controlled to be 180 r/min. And controlling the heating sleeve to heat to 180 ℃ at the speed of 5 ℃/min, and reacting for 3 hours at 180 ℃ to obtain the graphene composite asphalt material.
Example 2
Weighing 100g of medium-temperature asphalt, grinding the medium-temperature asphalt in a mortar to enable the particle size of the medium-temperature asphalt to be not more than 0.1mm, and adding the medium-temperature asphalt into a three-neck flask; then 2.5g (2.5 wt%) of graphene and 2.26g of p-toluenesulfonic acid are added into a three-neck flask, the device is fixed, 7.5mL of divinylbenzene and 2mL of cinnamaldehyde are added into the flask, then under the protection of nitrogen, condensed water is introduced, and the mechanical stirring speed is controlled to be 180 r/min. And controlling the heating sleeve to heat to 180 ℃ at the speed of 5 ℃/min, and reacting for 3 hours at 180 ℃ to obtain the graphene composite asphalt material.
Example 3
Weighing 100g of medium-temperature asphalt, grinding the medium-temperature asphalt in a mortar to enable the particle size of the medium-temperature asphalt to be not more than 0.1mm, and adding the medium-temperature asphalt into a three-neck flask; then 5g (5 wt%) of graphene and 2.26g of p-toluenesulfonic acid are added into a three-neck flask, a device is fixed, 7.5mL of divinylbenzene and 2mL of cinnamaldehyde are added into the three-neck flask, then condensed water is introduced under the protection of nitrogen, and the mechanical stirring speed is controlled to be 180 r/min. And controlling the heating sleeve to heat to 180 ℃ at the speed of 5 ℃/min, and reacting for 3 hours at 180 ℃ to obtain the graphene composite asphalt material.
Example 4
Weighing 100g of medium-temperature asphalt, grinding the medium-temperature asphalt in a mortar to enable the particle size of the medium-temperature asphalt to be not more than 0.1mm, and adding the medium-temperature asphalt into a three-neck flask; then 2.26g of p-toluenesulfonic acid is added into the three-neck flask, the device is fixed, 7.5mL of divinylbenzene and 2mL of cinnamaldehyde are added into the three-neck flask, then condensed water is introduced under the protection of nitrogen, and the mechanical stirring speed is controlled to be 180 r/min. Controlling the heating sleeve to heat to 180 ℃ at the speed of 5 ℃/min, and reacting for 3h at 180 ℃ to obtain the unmodified asphalt material for comparison.
SEM images of samples obtained in examples 1, 2, 3 and 4 are shown in FIGS. 1 to 4, respectively, and it can be seen that graphene is attached to the products obtained in examples 1, 2 and 3.
The performance indexes of the samples obtained in examples 1, 2, 3 and 4 are shown in Table 1,
TABLE 1
As can be seen from Table 1, the performance of the samples obtained in examples 1 to 4 is improved compared with that of the raw materials, which is related to the improvement of the degree of crosslinking of the polymer in each example, and the improvement of examples 1 to 3 is more significant, which is related to the addition of graphene.
The beta value (toluene insoluble-quinoline insoluble) of the sample is related to the conductivity of the sample, and the larger the beta value, the better the conductivity. In comparison, it is found that the samples obtained in examples 1 to 2 have higher β values and higher conductivity than the sample obtained in example 4.
Meanwhile, the comparison shows that the thermal conductivity value of the coal tar pitch without the graphene in example 4 is lower than that of the coal tar pitch with the graphene in examples 1 to 3, mainly because the graphene can promote the thermal conductivity, and the thermal conductivity value of example 2 is the highest, which corresponds to fig. 1 to 4, and the graphene is attached most in fig. 2, so the thermal conductivity value is correspondingly the highest, which also indicates that the graphene can be better attached to the coal tar pitch when the content of the added graphene accounts for 2.5% of the mass of the coal tar pitch.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Any person skilled in the art may, using the teachings disclosed above, change or modify the equivalent embodiments with equivalent changes. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a graphene composite asphalt material is characterized by comprising the following steps: crushing medium-temperature coal pitch, uniformly mixing the crushed medium-temperature coal pitch with graphene, a cross-linking agent and a catalyst, and then carrying out cross-linking polymerization at 140-180 ℃ to obtain a graphene composite pitch material;
the cross-linking agent is a mixture of divinylbenzene and cinnamaldehyde;
the molar ratio of the cross-linking agent to the coal pitch is 0.25-0.75: 1; the amount of the graphene accounts for 1-10 wt% of the mass of the coal tar pitch.
2. The method of claim 1, wherein: the catalyst is p-toluenesulfonic acid or potassium trichloride.
3. The production method according to claim 1 or 2, characterized in that: the amount of the catalyst accounts for 1-10 wt% of the mass of the coal tar pitch.
4. The method of claim 1, wherein: the pulverization is to pulverize the coal asphalt to a particle size of not more than 0.1 mm.
5. The method of claim 1, wherein: the time of the cross-linking polymerization is 3-5 h.
6. The method of claim 1, wherein: the heating rate of the crosslinking polymerization is 5 ℃/min.
7. A graphene composite asphalt material obtained by the preparation method of any one of claims 1 to 6.
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| CN202010047424.9A CN111117681B (en) | 2020-01-16 | 2020-01-16 | Graphene composite asphalt material and preparation method thereof |
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| CN202010047424.9A CN111117681B (en) | 2020-01-16 | 2020-01-16 | Graphene composite asphalt material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570026A (en) * | 2003-07-24 | 2005-01-26 | 鞍山科技大学 | Modified asphalt and its production method |
| US20100143798A1 (en) * | 2008-12-04 | 2010-06-10 | Aruna Zhamu | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
| CN105885906A (en) * | 2016-04-12 | 2016-08-24 | 方大炭素新材料科技股份有限公司 | Preparation method of oxidized graphene modified medium-temperature coal tar pitch |
| CN108707450A (en) * | 2018-03-30 | 2018-10-26 | 国家能源投资集团有限责任公司 | Binder pitch and preparation method |
| CN109768277A (en) * | 2019-01-11 | 2019-05-17 | 北京科技大学 | A kind of graphene oxide modified coal pitch binder and preparation method thereof |
-
2020
- 2020-01-16 CN CN202010047424.9A patent/CN111117681B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1570026A (en) * | 2003-07-24 | 2005-01-26 | 鞍山科技大学 | Modified asphalt and its production method |
| US20100143798A1 (en) * | 2008-12-04 | 2010-06-10 | Aruna Zhamu | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
| CN105885906A (en) * | 2016-04-12 | 2016-08-24 | 方大炭素新材料科技股份有限公司 | Preparation method of oxidized graphene modified medium-temperature coal tar pitch |
| CN108707450A (en) * | 2018-03-30 | 2018-10-26 | 国家能源投资集团有限责任公司 | Binder pitch and preparation method |
| CN109768277A (en) * | 2019-01-11 | 2019-05-17 | 北京科技大学 | A kind of graphene oxide modified coal pitch binder and preparation method thereof |
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