CN111925818A - Carbon fiber spinnable asphalt and preparation method and application thereof - Google Patents
Carbon fiber spinnable asphalt and preparation method and application thereof Download PDFInfo
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- CN111925818A CN111925818A CN202010820015.8A CN202010820015A CN111925818A CN 111925818 A CN111925818 A CN 111925818A CN 202010820015 A CN202010820015 A CN 202010820015A CN 111925818 A CN111925818 A CN 111925818A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 36
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010426 asphalt Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 58
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 238000005336 cracking Methods 0.000 claims abstract description 13
- 238000004939 coking Methods 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000011295 pitch Substances 0.000 description 10
- 239000011269 tar Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000003556 assay Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- -1 cyclic aromatic hydrocarbon Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010808 liquid waste Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
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- 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
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
The invention discloses carbon fiber spinnable asphalt and a preparation method and application thereof, belonging to the technical field of petrochemical industry and spinnable asphalt. The method takes ethylene cracking tar as a raw material, and produces the petroleum-based spinnable asphalt through the processes of primary distillation, primary polymerization, air oxidation, secondary distillation and secondary polymerization in sequence. In the preparation process of the spinnable asphalt, the carbon content and the coking value of the intermediate are increased after the first polymerization reaction and the oxidation reaction, the time of the second polymerization reaction is greatly reduced, the content of quinoline insoluble substances in the product is less than 0.5 wt.%, and the spun fiber has almost no nodules, higher strength and modulus and better quality when being used as a lithium battery negative electrode coating material.
Description
Technical Field
Embodiments of the present invention relate generally to the field of petrochemical and spinnable pitches, and more particularly, to a carbon fiber spinnable pitch and methods of making and using the same.
Background
The lithium ion battery is a new generation of green high-energy battery with excellent performance, and the main constituent materials comprise electrolyte, isolating materials, anode and cathode materials and the like. The lithium battery negative electrode material holds the safety life of the power battery, and is the most suitable negative electrode coating material due to the large specific surface area, good conductivity and strong cohesiveness of the spinnable asphalt, so that 80 percent of domestic lithium battery negative electrode coating materials are produced by using the carbon fiber spinnable asphalt.
The carbon fiber is a material with extremely excellent performance, and the general asphalt-based carbon fiber is mainly used for automobile brake pads, carbon fiber heat preservation felts, carbon paper, high-temperature and high-pressure sealing materials, electrode materials and the like. The general method for preparing carbon fibers is to prepare qualified spinning pitch, then carry out a series of treatments such as melt spinning, non-melting, carbonization, graphitization and the like, and whether carbon fibers with excellent performance can be prepared or not depends on the properties of the raw material pitch.
At present, the main domestic preparation technologies of carbon fiber spinnable asphalt are as follows:
1. imitating the American Adeland technology: a process for continuously producing high-temp asphalt with falling-film evaporator. The technology has strict requirements on raw materials, and can be prepared only by using A240 raw material of Alzerand.
2. The technology for preparing high-temperature asphalt by coal series comprises the following steps: solvent extraction process technology is used. The technical defects are as follows: a. the raw material has more impurities, so that the product has more impurities (all raw materials and coal tar); b. the method is not environment-friendly, and generates solid waste and liquid waste; c. the product contains a toxic substance, namely corpus elevator; d. long process route, high production cost and difficult industrialization.
Disclosure of Invention
According to embodiments of the present invention, a carbon fiber spinnable pitch and a preparation scheme thereof are provided.
In a first aspect of the invention, a method of making a carbon fiber spinnable pitch is provided. The method takes ethylene pyrolysis tar as a raw material, and produces the carbon fiber spinnable asphalt through the processes of primary distillation, primary polymerization, air oxidation, secondary distillation and secondary polymerization in sequence. The method specifically comprises the following steps:
(1) primary distillation:
the ethylene cracking tar is subjected to heat treatment and then enters a first reduced pressure distillation tower for distillation, the temperature at the bottom of the tower is 260-300 ℃, the vacuum degree is 1300-1500 Pa, the temperature at the top of the tower is 260-280 ℃, the vacuum degree is 1300-1500 Pa, the components at the top of the tower are condensed by a condenser and enter a collection tank, and one part of the components is sent into the tower for reflux and the other part of the components is extracted;
(2) primary polymerization:
inputting the tower bottom subjected to distillation treatment in the step (1) into a first polymerization tank for polymerization, wherein the temperature of the tank is 260-320 ℃ (preferably 280-;
(3) air oxidation:
inputting the material obtained after the reaction in the step (2) into an oxidation reactor and carrying out oxidation reaction with air, wherein the reaction pressure is normal pressure, the reaction temperature is 150-180 ℃ (preferably 155-;
(4) secondary distillation:
controlling the temperature of the top of the second reduced pressure distillation tower to be 280-320 ℃ and the vacuum degree of the top of the second reduced pressure distillation tower to be 500-800 Pa in the distillation process in the second reduced pressure distillation tower; the temperature of the tower bottom is 300-350 ℃, and the vacuum degree of the tower bottom is 500-800 Pa; condensing the tower top components in a tower top condenser, feeding the condensed tower top components into a collecting tank, feeding part of the condensed tower top components into the tower for refluxing, and extracting part of the condensed tower top components;
(5) and (3) secondary polymerization:
the bottom material distilled by the second reduced pressure distillation tower enters a second polymerization kettle for polymerization reaction, the reaction temperature is 410-430 ℃, the vacuum degree is 100-200 Pa, and the reaction time is 30-40 minutes; and obtaining the carbon fiber spinnable asphalt after the secondary polymerization is finished.
Furthermore, the density (20 ℃) of the ethylene cracking tar raw material used in the invention is 0.900-1.200 g/cm3, the oxygen content is less than 0.2 wt.%, the sulfur content is less than 985ppm, the initial boiling point is not less than 150 ℃, and the flash point is not less than 55 ℃.
Further, in the step (1), the heat treatment process is as follows: firstly, filtering an ethylene cracking tar raw material by using a filter to remove impurities and purify; and then heating to 260-300 ℃ by adopting a kettle-type reboiler, and inputting into a first reduced pressure distillation tower.
Further, in the step (3), the air oxidation specifically comprises: heating an oxidation reactor to 150 ℃, inputting the material obtained after the reaction in the step (2) from the top of the oxidation reactor, feeding air into the reactor at a flow rate of 0.01-0.03m3/min through a distributor at the bottom of the reactor, and stopping feeding the air when the temperature in the reactor rises to 180 ℃; then nitrogen is introduced into the reactor at the flow rate of 0.3-0.6m3/min, the introduction of nitrogen is stopped when the temperature in the reactor is reduced to 150 ℃, and the obtained material is input into a second reduced pressure distillation tower after air is introduced again.
In a second aspect of the invention, a carbon fiber spinnable pitch is provided, which is prepared by the method of the first aspect, wherein the content of quinoline insoluble is less than 0.5 wt.%, the softening point is 245-285 ℃, and the coking value is 73-89%.
In a third aspect of the invention, there is provided a use of a carbon fiber spinnable pitch. The carbon fiber spinnable asphalt is applied to preparation of carbon fiber or lithium battery negative electrode coated carbon materials.
It should be understood that the statements herein reciting aspects are not intended to limit the critical or essential features of any embodiment of the invention, nor are they intended to limit the scope of the invention. Other features of the present invention will become apparent from the following description.
The carbon fiber spinnable asphalt with low quinoline insoluble content, proper coking value and softening point and excellent spinnability is obtained through the technological processes of twice distillation, once oxidation and twice polymerization.
Drawings
The above and other features, advantages and aspects of various embodiments of the present invention will become more apparent by referring to the following detailed description when taken in conjunction with the accompanying drawings. In the drawings, like or similar reference characters designate like or similar elements, and wherein:
FIG. 1 is a flow diagram of a process for preparing carbon fiber spinnable pitch in accordance with the present invention;
FIG. 2 is a schematic structural diagram of an air oxidizer in accordance with an embodiment of the present invention; wherein, 1 is a gas distributor.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
In addition, the term "and/or" herein is only one kind of association relationship describing an associated object, and means that there may be three kinds of relationships, for example, a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
In the invention, the carbon fiber spinnable asphalt with low quinoline insoluble content, proper coking value and softening point and excellent spinnability is obtained through the technical processes of twice distillation, once oxidation and twice polymerization.
FIG. 1 shows a flow diagram of a method of making carbon fiber spinnable pitch in an embodiment of the invention.
The method takes ethylene pyrolysis tar as a raw material, and produces the carbon fiber spinnable asphalt through the processes of primary distillation, primary polymerization, air oxidation, secondary distillation and secondary polymerization in sequence.
1. The raw material is ethylene cracking tar, the appearance is brownish black liquid, the density (20 ℃) is 1.0945g/cm3g/m3, the initial boiling point is more than or equal to 150 ℃, the flash point (opening) is more than or equal to 55 ℃, the oxygen content is less than 0.2 percent, the sulfur content is 984ppm, the distillation range is as shown in the following table 1, and the composition is as shown in the following table 2.
| ％ | ℃ | ％ | ℃ | ％ | ℃ |
| IBP | 58℃ | 40％ | 326℃ | 90％ | 620℃ |
| 5％ | 138℃ | 50％ | 421℃ | 95％ | 665℃ |
| 10％ | 218℃ | 60％ | 494℃ | ||
| 20％ | 252℃ | 70％ | 566℃ | ||
| 30％ | 276℃ | 80％ | 593℃ |
Table 1 distillation range: (v/v)
TABLE 2 compositional analysis
2. Filtering and purifying an ethylene cracking tar raw material by using a filter, and heating to 260-300 ℃ by using an AKT/AKU kettle type reboiler.
3. Primary distillation:
the ethylene cracking tar is subjected to heat treatment and then enters a first reduced pressure distillation tower for distillation, the temperature at the bottom of the tower is 260-300 ℃, the vacuum degree is 1300-1500 Pa, the temperature at the top of the tower is 260-280 ℃, the vacuum degree is 1300-1500 Pa, the components at the top of the tower are condensed by a condenser and enter a collection tank, and one part of the components is sent into the tower for reflux and the other part of the components is extracted.
As an embodiment of the invention, in the first distillation process, the mixture enters a first reduced pressure distillation tower for distillation, the temperature at the bottom of the tower is 280 ℃, the vacuum degree is 1400Pa, the temperature at the top of the tower is 270 ℃, the vacuum degree is 1400Pa, the components at the top of the tower are condensed by a condenser and enter a collection tank, one part of the components are sent into the tower for reflux, the other part of the components are extracted, and the tower bottom enters a first polymerization tank for polymerization. The bottoms assay results are shown in table 3.
| Softening Point (. degree. C.) | Coking value (%) | Quinoline insolubles | Ash content |
| 38(±1) | 22-23 | 0 | 0.001 |
TABLE 3 indices of the bottoms of the primary distillation column
4. Primary polymerization:
the tower bottom after the primary distillation treatment is input into a first polymerization tank for polymerization, the temperature of the tank is 260-320 ℃ (preferably 280-300 ℃), the vacuum degree is 500-1000 Pa, and the reaction time is 50-60 minutes.
In the first polymerization reaction process, because the raw material tar mainly comprises polycyclic aromatic hydrocarbons and mainly undergoes cracking and condensation reactions in the heating process, the C-C bond energy is smaller than the C-H bond energy, and the C-C bond is inevitably cracked (side chain cracking on the aromatic hydrocarbons) while the C-H bond is cracked (dehydrogenated) when being heated. And the aromatic hydrocarbon mainly undergoes condensation reaction, and the original 3-5 cyclic aromatic hydrocarbon is condensed into 7-8 cyclic aromatic hydrocarbon. After the first polymerization, an oxidation reaction is carried out, which is mainly to dehydrogenate the generated cyclized polymer or heterocyclic ring, increasing the carbon content. Thus, during the secondary polymerization reaction, the reaction time can be reduced, and the reaction temperature can be reduced, so that the secondary condensation of the fused ring aromatic hydrocarbon with larger molecular weight is reduced after the fused ring aromatic hydrocarbon is heated, the generation of quinoline insoluble substances of the product is reduced, and the product quality is improved.
In one embodiment of the present invention, the polymerization is carried out in a first polymerization tank at a tank temperature of 260 to 320 ℃ and a vacuum degree of 700 Pa. The results of the measurements of the product after the first polymerization are shown in Table 4.
| Reaction temperature | Softening Point (. degree. C.) | Coking value (%) | Quinoline insoluble (%) | Ash (%) |
| 280℃ | 40(±1) | 25-26 | 0 | 0.001 |
| 290℃ | 43(±1) | 27-28 | 0 | 0.001 |
| 300℃ | 47(±1) | 29-30 | 0 | 0.001 |
| 310℃ | 50(±1) | 32-33 | 0 | 0.001 |
TABLE 4 indices of the product of the first polymerization (vacuum environment, reaction time 50-60 minutes)
5. Air oxidation:
inputting the material obtained after the primary polymerization reaction into an oxidation reactor and carrying out oxidation reaction with air, wherein the reaction pressure is normal pressure, the reaction temperature is 150-180 ℃ (preferably 155-.
As an embodiment of the invention, the material after the polymerization reaction when the temperature of the first polymerization tank is 290 ℃ is input into an air oxidizer, the structure of the air oxidizer is shown in figure 2, the material is input from the top of the oxidation reactor, air enters the reactor through a gas distributor at the bottom of the reactor at the flow rate of 0.02m3/min, the reaction temperature in the reactor is 150-180 ℃, the pressure is normal pressure, the air introduction and the nitrogen introduction into the reactor are stopped after the reaction is kept for 90 minutes, the nitrogen flow rate is 0.5m3/min, the nitrogen introduction is stopped when the temperature in the reactor is reduced to below 150 ℃, the material obtained after the air introduction is input into a second reduced pressure distillation tower for distillation; the results of the material detection after the oxidation reaction are shown in Table 5.
| Reaction temperature | Softening Point (. degree. C.) | Coking value (%) | Quinoline insoluble (%) | Ash (%) |
| 160℃ | 124(±1) | 46-47 | 0 | 0.001 |
| 170℃ | 126(±1) | 47-48 | 0 | 0.001 |
| 180℃ | 128(±1) | 48-49 | 0 | 0.001 |
TABLE 5 Oxidation reaction products for various indices (atmospheric pressure)
6. Secondary distillation:
controlling the temperature of the top of the second reduced pressure distillation tower to be 280-320 ℃ and the vacuum degree of the top of the second reduced pressure distillation tower to be 500-800 Pa in the distillation process in the second reduced pressure distillation tower; the temperature of the tower bottom is 300-350 ℃, and the vacuum degree of the tower bottom is 500-800 Pa; the tower top components are condensed by a tower top condenser and enter a collecting tank, and a part of the components are sent into the tower to reflux, and a part of the components are extracted.
As an embodiment of the invention, the material after oxidation reaction at 160 ℃ is input into a second reduced pressure distillation tower for distillation, the tower top temperature is 290 ℃, the vacuum degree is 600Pa, the tower bottom temperature is 320 ℃, and the vacuum degree is 600 Pa. The tower top components are condensed by a tower top condenser and enter a collecting tank, one part of the components is sent into the tower to reflux, and the other part of the components is extracted. The bottoms assay results are shown in table 6.
| Softening Point (. degree. C.) | Coking value (%) | Quinoline insoluble (%) | Ash (%) |
| 143(±1) | 54-55 | 0 | 0.001 |
TABLE 6 indexes of bottoms of secondary distillation column
7. And (3) secondary polymerization:
the bottom material distilled by the second reduced pressure distillation tower enters a second polymerization kettle for polymerization reaction, the reaction temperature is 410-430 ℃, the vacuum degree is 100-200 Pa, and the reaction time is 30-40 minutes; and obtaining the carbon fiber spinnable asphalt after the secondary polymerization is finished.
As an embodiment of the invention, the bottom material after the second distillation enters a second polymerization kettle for polymerization reaction, the reaction temperature is 400-450 ℃, and the vacuum degree is 100-200 Pa. And after the reaction is finished, the obtained carbon fiber spinnable asphalt product is molded and packaged. The results of the measurements on the product after the second polymerization are shown in Table 7.
| Reaction temperature | Softening Point (. degree. C.) | Coking value (%) | Quinoline insoluble (%) | Ash (%) |
| 400℃ | 245(±2) | 63-64 | 0.03 | 0.001-0.002 |
| 410℃ | 255(±2) | 73-74 | 0.1 | 0.001-0.002 |
| 420℃ | 265(±2) | 80-82 | 0.12 | 0.001-0.002 |
| 430℃ | 275(±2) | 85-89 | 0.17 | 0.001-0.002 |
| 440℃ | 285(±3) | 92-93 | 1-5 | 0.001-0.002 |
TABLE 7 indices of the product of the second polymerization (reaction time 30-40 minutes in vacuum)
As can be seen from the data in Table 7, when the secondary polymerization temperature is 430 ℃ at 410-.
Because the carbon component and the coking value of the intermediate are increased after the first polymerization reaction and the oxidation reaction, the time of the second polymerization reaction is greatly reduced, the reaction temperature is reduced, and the content of quinoline insoluble substances in the product is less than 0.5 wt%, which is far better than that of the quinoline insoluble substances in other existing methods by 1-5%; the spinnable asphalt has a softening point of 245-.
The invention uses ethylene cracking tar as raw material to prepare spinnable asphalt, the raw material used in the process is sufficient, the price is low, the carbon-hydrogen ratio is high, the purity is high, the viscosity is moderate, and the method is very suitable for producing spinnable asphalt. In addition, the process of the invention does not use any catalyst or other additives, does not have violent chemical reaction, is safe and economic, does not have a complex link for processing the catalyst and other additives, and ensures that the product has higher purity and better quality. The process does not produce solid waste and liquid waste substances in the production process, is more environment-friendly and is very suitable for building large-scale industrial production devices.
The carbon fiber spinnable asphalt prepared by the invention has lower content of benzopyrene compounds (with toxicity) (table 8).
| Type of technology | Content of benzopyrene |
| Preparation of spinnable asphalt by coal- |
1％-2％ |
| The invention prepares spinnable asphalt | ＜0.1％ |
TABLE 8
The carbon fiber spinnable asphalt prepared by the method has the advantages of large specific surface area, good conductivity and strong cohesiveness, and is better in quality when used as a lithium battery negative electrode coating material (performance data are shown in a table 9).
TABLE 9
Claims (7)
1. The preparation method of the carbon fiber spinnable asphalt is characterized in that ethylene pyrolysis tar is used as a raw material, and the carbon fiber spinnable asphalt is produced through the processes of primary distillation, primary polymerization, air oxidation, secondary distillation and secondary polymerization in sequence.
2. Method according to claim 1, characterized in that it comprises the following steps:
(1) primary distillation:
the ethylene cracking tar is subjected to heat treatment and then enters a first reduced pressure distillation tower for distillation, the temperature at the bottom of the tower is 260-300 ℃, the vacuum degree is 1300-1500 Pa, the temperature at the top of the tower is 260-280 ℃, the vacuum degree is 1300-1500 Pa, the components at the top of the tower are condensed by a condenser and enter a collection tank, and one part of the components is sent into the tower for reflux and the other part of the components is extracted;
(2) primary polymerization:
inputting the tower bottom subjected to distillation treatment in the step (1) into a first polymerization tank for polymerization, wherein the tank temperature is 260-320 ℃, the vacuum degree is 500-1000 Pa, and the reaction time is 50-60 minutes;
(3) air oxidation:
inputting the material obtained after the reaction in the step (2) into an oxidation reactor and carrying out oxidation reaction with air, wherein the reaction pressure is normal pressure, the reaction temperature is 150-180 ℃, and the material obtained after the reaction enters a second reduced pressure distillation tower for distillation;
(4) secondary distillation:
controlling the temperature of the top of the second reduced pressure distillation tower to be 280-320 ℃ and the vacuum degree of the top of the second reduced pressure distillation tower to be 500-800 Pa in the distillation process in the second reduced pressure distillation tower; the temperature of the tower bottom is 300-350 ℃, and the vacuum degree of the tower bottom is 500-800 Pa; condensing the tower top components in a tower top condenser, feeding the condensed tower top components into a collecting tank, feeding part of the condensed tower top components into the tower for refluxing, and extracting part of the condensed tower top components;
(5) and (3) secondary polymerization:
the bottom material distilled by the second reduced pressure distillation tower enters a second polymerization kettle for polymerization reaction, the reaction temperature is 410-430 ℃, the vacuum degree is 100-200 Pa, and the reaction time is 30-40 minutes; and obtaining the carbon fiber spinnable asphalt after the secondary polymerization is finished.
3. The method of claim 2, wherein: the density (20 ℃) of the ethylene cracking tar raw material is 0.900-1.200 g/cm3, the oxygen content is less than 0.2 wt.%, the sulfur content is less than 985ppm, the initial boiling point is not less than 150 ℃, and the flash point is not less than 55 ℃.
4. The method of claim 2, wherein: in the step (1), the heat treatment process is as follows: firstly, filtering an ethylene cracking tar raw material by using a filter to remove impurities and purify; and then heating to 260-300 ℃ by adopting a kettle-type reboiler, and inputting into a first reduced pressure distillation tower.
5. The method of claim 2, wherein: in the step (3), the air oxidation specifically comprises the following steps: heating an oxidation reactor to 150 ℃, inputting the material obtained after the reaction in the step (2) from the top of the oxidation reactor, feeding air into the reactor at a flow rate of 0.01-0.03m3/min through a distributor at the bottom of the reactor, and stopping feeding the air when the temperature in the reactor rises to 180 ℃; then nitrogen is introduced into the reactor at the flow rate of 0.3-0.6m3/min, the introduction of nitrogen is stopped when the temperature in the reactor is reduced to 150 ℃, and the obtained material is input into a second reduced pressure distillation tower after air is introduced again.
6. A carbon fiber spinnable pitch made by the process of any of claims 1-5, wherein: the content of quinoline insoluble substances in the carbon fiber spinnable asphalt is less than 0.5 wt%, the softening point is 245-285 ℃, and the coking value is 73-89%.
7. Use of a carbon fiber spinnable pitch according to claim 6, characterized in that: the carbon fiber spinnable asphalt is applied to preparation of carbon fiber or lithium battery negative electrode coated carbon materials.
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| CN114736705A (en) * | 2022-04-18 | 2022-07-12 | 中国石油化工股份有限公司 | Method and device for preparing coated asphalt by adopting ethylene tar and coated asphalt |
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