CN114214758B - Method for preparing general-grade carbon fiber from coal liquefaction residues - Google Patents
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/145—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues
- D01F9/15—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from pitch or distillation residues from coal pitch
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Abstract
The invention discloses a method for preparing general-purpose carbon fibers by using coal liquefaction residues, and relates to the technical field of preparation of general-purpose asphalt-based carbon fibers. The method comprises the following steps: mixing and purifying coal liquefaction residues and tetrahydrofuran, mixing the obtained coal liquefaction residue extract with a chlorinating agent in an inert atmosphere, heating to melt, then chlorinating at the constant temperature of 120-260 ℃, then dechlorinating at the constant temperature of 320-370 ℃, and cooling to room temperature after the reaction is finished to obtain an asphalt precursor; adjusting the softening point of a pitch precursor to 220-260 ℃, performing melt spinning to obtain pitch fibers, and performing pre-oxidation and carbonization treatment on the pitch fibers to obtain the carbon fibers. According to the invention, the coal liquefaction residues are used as raw materials, a chlorination-dechlorination method is used for synthesizing the pitch precursor, the preparation method is simple, the operation cost is low, no strong corrosive raw materials are adopted, and the strength performance of the prepared universal carbon fiber is obviously superior to that of the conventional commercial universal carbon fiber.
Description
Technical Field
The invention relates to the technical field of preparation of universal asphalt-based carbon fibers, in particular to a method for preparing universal carbon fibers by using coal liquefaction residues.
Background
The direct coal liquefaction technology is one of clean coal technologies, and can relieve the current energy situation of lack of petroleum resources to a certain extent. The direct coal liquefaction reaction process can generate a large amount of coal liquefaction residues, which account for about 30 percent of the total coal input. The coal liquefaction residue has high carbon content and high aromatic hydrocarbon component content, but the high ash content and the high sulfur content limit the high value-added utilization of the coal liquefaction residue. The high-efficiency, reasonable and high value-added utilization of the coal liquefaction residues has important significance for the development and application of the direct coal liquefaction technology.
The preparation of carbon fiber is a mode of high value-added utilization of direct coal liquefaction residues developed in recent years, and methods such as a thermal polycondensation method, an atmospheric and vacuum distillation method, an air oxidation method and the like are generally adopted. In the document, "preparation of mesophase pitch carbon fiber [ J ] from coal direct liquefaction residue 2015(2): 176-; the pitch precursor used in the method is synthesized by thermal shrinkage polymerization, but the preparation method requires that the raw materials have good reactivity, has certain limitation on the selection of the raw materials, and the strength performance of the prepared carbon fiber (Young modulus 150GPa, tensile strength 1500MPa) is lower than that of the common mesophase pitch-based carbon fiber (Young modulus 250GPa, tensile strength 2000 MPa). The document "catalytic oil slurry preparation general-purpose pitch-based carbon fiber [ D ]. Beijing, institute of petrochemical engineering, 2015. Li pei." discloses that catalytic oil slurry is used as a raw material, the raw material is pretreated by heat treatment, and precursor pitch prepared by an extraction method is used for spinning to prepare carbon fiber. The literature, "Kim B J, Eom Y, Kato O, et al.preparation of Carbon fibers with excellent properties from iso-pitch [ J ]. Carbon,2014,77: 747-755." takes naphtha pyrolysis oil as raw material, synthesizes isotropic pitch with better spinnability by using a bromination-debromination method, and prepares isotropic pitch-based Carbon fibers with tensile strength reaching 1500MPa by spinning, but elemental bromine used in the method has high price and strong corrosivity, has certain danger and has very high requirements on the corrosion resistance of equipment.
The invention discloses a method for preparing general-purpose pitch-based carbon fibers from coal liquefaction residues, which is a Chinese patent with the application number of 202010468692.8, and reports a method for preparing general-purpose carbon fibers from coal liquefaction residues, wherein a pitch precursor with the softening point of 240-340 ℃ is obtained through settling separation, reduced pressure suction filtration and oxidative polycondensation, and then the carbon fibers are prepared through melt spinning, non-melting treatment and carbonization processes. The invention of China patent with application number CN200910019693.8 reports a preparation method of pitch carbon fiber, which comprises the processes of polycondensation, spinning, infusibility, carbonization, high-temperature graphitization, surface modification and the like, the technology uses the polycondensation method to prepare the spinning pitch, and a large amount of synthesis agent is added in the polycondensation process, so the operation cost is high, and the potential danger exists in the mixing of organic matters.
Therefore, the existing preparation method of the pitch-based carbon fiber is mainly a thermal polycondensation method, and the method has poor regulation and control effects on the properties and the performances of the carbon fiber, so that the strength performance of the carbon fiber prepared by using the coal liquefaction residue as a raw material still has a large improvement space.
Disclosure of Invention
The invention aims to provide a method for preparing general-purpose carbon fibers by using coal liquefaction residues, which solves the problems in the prior art and further adopts a simple method to prepare high-performance general-purpose carbon fibers.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a method for preparing carbon fibers by using coal liquefaction residues, which comprises the following steps:
(1) mixing and purifying the coal liquefaction residue and tetrahydrofuran to obtain a tetrahydrofuran extract of the coal liquefaction residue;
(2) mixing the tetrahydrofuran extract of the coal liquefaction residue with a chlorinating agent in an inert atmosphere;
(3) melting the mixture obtained in the step (2) in an inert atmosphere, and then carrying out chlorination reaction at a constant temperature of 120-260 ℃;
(4) heating the reaction system to 320-370 ℃, carrying out dechlorination reaction at constant temperature, and cooling to room temperature after the dechlorination reaction is finished to obtain an asphalt precursor;
(5) adjusting the softening point of the pitch precursor to 220-260 ℃;
(6) carrying out melt spinning on the pitch precursor obtained in the step (5) to obtain pitch fibers;
(7) pre-oxidizing the pitch fibers;
(8) and carbonizing the pre-oxidized asphalt fiber to obtain the carbon fiber.
Further, the mass ratio of the tetrahydrofuran extract of the coal liquefaction residue to the chlorinating agent is 1: 0.1-0.4.
Further, the chlorination reaction time in the step (3) is 1-2 h.
Further, the dechlorination reaction time in the step (4) is 1-3 h.
Further, the pitch precursor is heated to 200-350 ℃ firstly, and then a rotary film is adopted for evaporation to adjust the softening point of the pitch precursor; the heating rate was 5 ℃/min.
Further, the pre-oxidation step in the step (7) is as follows: heating the asphalt fiber to the asphalt softening point at a heating rate of 0.5-2 ℃/min in the presence of oxygen, and keeping the temperature for 0-1 h;
further, the carbonization treatment step in the step (8) is as follows: in the presence of nitrogen, at a heating rate of 5-10 ℃/min, heating the pre-oxidized asphalt fiber to 800-900 ℃, and preserving heat for 5-30 min.
The invention also provides the carbon fiber prepared by the method.
The invention discloses the following technical effects:
the invention takes coal liquefaction residues as raw materials, and synthesizes asphalt precursor by using chlorination-dechlorination method, thereby improving the strength performance of carbon fiber, the preparation method of the invention is simple, the operation cost is low, no strong corrosive raw materials are adopted, simultaneously, the tensile strength of the prepared universal carbon fiber is more than 1200MPa, the Young modulus is more than 80GPa, the elongation is more than or equal to 1.5%, and the strength performance is obviously better than that of the existing universal carbon fiber.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The coal liquefaction residue used in the embodiment of the invention is a tetrahydrofuran extract of the coal liquefaction residue after purification and refining, and specifically comprises the steps of mixing the coal liquefaction residue with tetrahydrofuran, stirring for 24 hours at normal temperature, and then filtering and separating to obtain a filtrate; the filtrate was poured into a round bottom flask and rotary evaporated at 60 ℃ for 30min to obtain tetrahydrofuran extract of coal liquefaction residue.
The invention provides a method for preparing universal-grade carbon fibers by using coal liquefaction residues, which comprises the following steps:
1. pretreatment: grinding the tetrahydrofuran extract of the coal liquefaction residue, mixing the ground tetrahydrofuran extract with a chlorinating agent (benzyl chloride, chlorobenzene, polyvinyl chloride and the like) according to the mass ratio of 1: 0.1-0.4, adding the mixture into a precursor preparation reaction kettle, introducing argon at the speed of 50ml/min to achieve the inert atmosphere protection condition, and introducing and purging the mixture for 10 min.
2. Chlorination reaction: according to the difference of the softening points of the raw material asphalt, in an inert atmosphere, heating the reaction kettle to 120-180 ℃, starting a motor to start a stirring paddle after a sample is completely melted and has good fluidity, and keeping the stirring speed of 50-100 rpm. And then continuously heating to 120-260 ℃, keeping the temperature for 1-2 hours, and carrying out chlorination reaction.
3. And (3) dechlorination reaction: and (3) raising the temperature of the reaction kettle to 320-370 ℃, keeping the temperature for 1-3 hours, and performing dechlorination reaction. The purging flow of the inert gas argon is increased to 200 ml/min. While maintaining the stirring speed of 50-100 rpm. Stopping heating after the dechlorination reaction is finished, removing the heating furnace, naturally cooling, and stopping stirring when the temperature is cooled to 180 ℃. And after the sample is completely cooled to the room temperature, taking out the sample to obtain the pitch precursor.
4. Rotary thin film evaporation: crushing a sample into blocks, putting the blocks into a reaction test tube, vacuumizing the reaction test tube by using a rotary evaporator, simultaneously heating the test tube to 200-350 ℃, wherein the heating rate is 5 ℃/min, and adjusting the softening point of an asphalt precursor to 220-260 ℃ by using a rotary thin film evaporation method.
5. Melt spinning: and (2) putting the milled powder of the pitch precursor into a melt spinning machine, heating to 270-310 ℃ under the protection of nitrogen, keeping the temperature for 20-30 min, and carrying out melt spinning under the conditions that the pressure is 0.1-0.3 MPa and the rotating speed of a take-up cylinder is 500-1000 m/min to obtain the pitch fiber.
6. Pre-oxidation: placing the asphalt fiber in a tube furnace for pre-oxidation, and introducing O at the flow rate of 50-100 ml/min 2 Heating to the softening point of the asphalt at a heating rate of 0.5-2 ℃/min, and keeping the temperature for 0-1 h.
7. Carbonizing: placing the pre-oxidized fiber in a tube furnace for carbonization, and introducing N at the flow rate of 100-200 ml/min 2 Heating to 800-900 ℃ at a heating rate of 5-10 ℃/minAnd preserving the heat for 5-30 min to obtain the universal carbon fiber.
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) Pretreatment: grinding the tetrahydrofuran extract of the coal liquefaction residue, mixing the ground tetrahydrofuran extract with benzyl chloride according to the mass ratio of 1:0.1, adding the mixture into a precursor preparation reaction kettle, introducing argon at the speed of 50ml/min to achieve the inert atmosphere protection condition, and introducing and purging the argon for 10 min.
(2) Chlorination reaction: in an inert atmosphere, the reaction kettle is heated to 180 ℃, after a sample is completely melted and has good fluidity, a motor is started to start a stirring paddle, and the stirring speed of 50rpm is kept. Then, the temperature is continuously increased to 260 ℃, and the constant temperature is kept for 1h, so that the chlorination reaction is carried out.
(3) And (3) dechlorination reaction: the temperature of the reaction kettle is raised to 370 ℃, and the constant temperature is kept for 1.5h for dechlorination reaction. The purging flow of the inert gas argon is increased to 200 ml/min. During which a stirring speed of 50rpm was maintained. Stopping heating after the dechlorination reaction is finished, removing the heating furnace, naturally cooling, and stopping stirring when the temperature is cooled to 180 ℃. After cooling to room temperature completely, the sample was taken out.
(4) Rotary thin film evaporation: crushing the sample into blocks, putting the blocks into a reaction test tube, vacuumizing by using a rotary evaporator, heating the test tube at a heating rate of 5 ℃/min for 3 times at temperatures of 270 ℃,300 ℃ and 330 ℃, and adjusting the softening point of an asphalt precursor to 230 ℃ by using a rotary thin film evaporation method.
(5) Melt spinning: and (3) putting the milled powder of the pitch precursor into a melt spinning machine, heating to 280 ℃ under the protection of nitrogen, keeping the temperature for 30min, and carrying out melt spinning under the conditions that the pressure is 0.3MPa and the rotating speed of a filament collecting cylinder is 1000m/min to obtain the pitch fiber.
(6) Pre-oxidation: the asphalt fiber is put into a tube furnace for pre-oxidation, and O is introduced at the flow rate of 50ml/min 2 Heating to the softening point of the asphalt at the heating rate of 0.5 ℃/min, and keeping the temperature for 0.5 h.
(7) Carbonizing: placing the pre-oxidized fiber in a tube furnace for carbonization, and introducing N at the flow rate of 200ml/min 2 Heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 30min to obtain the universal-grade carbon fiber.
The strength properties of the universal grade carbon fiber prepared in example 1 were as follows:
tensile strength: 1230 MPa; young's modulus: 82 GPa; elongation percentage: 1.5 percent.
Example 2
(1) Pretreatment: grinding the tetrahydrofuran extract of the coal liquefaction residue, mixing the ground tetrahydrofuran extract with benzyl chloride according to the mass ratio of 1:0.2, adding the mixture into a precursor preparation reaction kettle, introducing argon at the speed of 50ml/min to achieve the inert atmosphere protection condition, and introducing and purging the argon for 10 min.
(2) Chlorination reaction: in an inert atmosphere, the reaction kettle is heated to 180 ℃, after a sample is completely melted and has good fluidity, a motor is started to start a stirring paddle, and the stirring speed of 50rpm is kept. Then, the temperature is continuously increased to 260 ℃, and the constant temperature is kept for 1h, so that the chlorination reaction is carried out.
(3) And (3) dechlorination reaction: the temperature of the reaction kettle is raised to 370 ℃, and the constant temperature is kept for 1.5h for dechlorination reaction. The purging flow of the inert gas argon is increased to 200 ml/min. During which a stirring speed of 50rpm was maintained. Stopping heating after the dechlorination reaction is finished, removing the heating furnace, naturally cooling, and stopping stirring when the temperature is cooled to 180 ℃. After cooling to room temperature completely, the sample was taken out.
(4) Rotary thin film evaporation: crushing the sample into blocks, putting the blocks into a reaction test tube, vacuumizing by using a rotary evaporator, heating the test tube at a heating rate of 5 ℃/min for 3 times at temperatures of 270 ℃,300 ℃ and 330 ℃, and adjusting the softening point of an asphalt precursor to 230 ℃ by using a rotary thin film evaporation method.
(5) Melt spinning: and (3) putting the milled powder of the pitch precursor into a melt spinning machine, heating to 280 ℃ under the protection of nitrogen, keeping the temperature for 30min, and carrying out melt spinning under the conditions that the pressure is 0.3MPa and the rotating speed of a filament collecting cylinder is 1000m/min to obtain the pitch fiber.
(6) Pre-oxidation: the asphalt fiber is put into a tube furnace for pre-oxidation, and O is introduced at the flow rate of 50ml/min 2 Heating to the softening point of the asphalt at the heating rate of 0.5 ℃/min, and keeping the temperature for 0.5 h.
(7) Carbonizing: placing the pre-oxidized fiber in a tube furnace for carbonization, and introducing N at the flow rate of 200ml/min 2 Heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 30min to obtain the universal-grade carbon fiber.
The strength properties of the universal grade carbon fiber prepared in example 2 were as follows:
tensile strength: 1340 MPa; young's modulus: 86 GPa; elongation percentage: 1.6 percent.
Example 3
(1) Pretreatment: grinding the tetrahydrofuran extract of the coal liquefaction residue, mixing the ground tetrahydrofuran extract with benzyl chloride according to the mass ratio of 1:0.3, adding the mixture into a precursor preparation reaction kettle, introducing argon at the speed of 50ml/min to achieve the inert atmosphere protection condition, and introducing and purging the argon for 10 min.
(2) Chlorination reaction: in an inert atmosphere, the reaction kettle is heated to 180 ℃, after a sample is completely melted and has good fluidity, a motor is started to start a stirring paddle, and the stirring speed of 50rpm is kept. Then, the temperature is continuously increased to 260 ℃, and the constant temperature is kept for 1h, so that the chlorination reaction is carried out.
(3) And (3) dechlorination reaction: the temperature of the reaction kettle is raised to 370 ℃, and the constant temperature is kept for 1.5h for dechlorination reaction. The purging flow of the inert gas argon is increased to 200 ml/min. During which a stirring speed of 50rpm was maintained. Stopping heating after the dechlorination reaction is finished, removing the heating furnace, naturally cooling, and stopping stirring when the temperature is cooled to 180 ℃. After cooling to room temperature completely, the sample was taken out.
(4) Rotary thin film evaporation: crushing the sample into blocks, putting the blocks into a reaction test tube, vacuumizing by using a rotary evaporator, heating the test tube at a heating rate of 5 ℃/min for 3 times at temperatures of 270 ℃,300 ℃ and 330 ℃, and adjusting the softening point of an asphalt precursor to 230 ℃ by using a rotary thin film evaporation method.
(5) Melt spinning: and (3) putting the milled powder of the pitch precursor into a melt spinning machine, heating to 280 ℃ under the protection of nitrogen, keeping the temperature for 30min, and carrying out melt spinning under the conditions that the pressure is 0.3MPa and the rotating speed of a filament collecting cylinder is 1000m/min to obtain the pitch fiber.
(6) Pre-oxidation: placing pitch fibers in the tubePre-oxidizing in a furnace, introducing O at a flow rate of 50ml/min 2 Heating to the softening point of the asphalt at the heating rate of 0.5 ℃/min, and keeping the temperature for 0.5 h.
(7) Carbonizing: placing the pre-oxidized fiber in a tube furnace for carbonization, and introducing N at the flow rate of 200ml/min 2 Heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 30min to obtain the universal-grade carbon fiber.
The strength properties of the universal grade carbon fiber prepared in example 3 were as follows:
tensile strength: 1396 MPa; young's modulus: 93 GPa; elongation percentage: 1.5 percent.
Example 4
(1) Pretreatment: grinding the tetrahydrofuran extract of the coal liquefaction residue, mixing the ground tetrahydrofuran extract with benzyl chloride according to the mass ratio of 1:0.4, adding the mixture into a precursor preparation reaction kettle, introducing argon at the speed of 50ml/min to achieve the inert atmosphere protection condition, and introducing and purging the argon for 10 min.
(2) Chlorination reaction: in an inert atmosphere, the reaction kettle is heated to 180 ℃, after a sample is completely melted and has good fluidity, a motor is started to start a stirring paddle, and the stirring speed of 50rpm is kept. Then, the temperature is continuously increased to 260 ℃, and the constant temperature is kept for 1h, so that the chlorination reaction is carried out.
(3) And (3) dechlorination reaction: the temperature of the reaction kettle is raised to 370 ℃, and the constant temperature is kept for 1.5h for dechlorination reaction. The purging flow of the inert gas argon is increased to 200 ml/min. During which a stirring speed of 50rpm was maintained. Stopping heating after the dechlorination reaction is finished, removing the heating furnace, naturally cooling, and stopping stirring when the temperature is cooled to 180 ℃. After complete cooling to room temperature, the sample was removed.
(4) Rotary thin film evaporation: crushing the sample into blocks, putting the blocks into a reaction test tube, vacuumizing by using a rotary evaporator, heating the test tube at a heating rate of 5 ℃/min for 3 times at temperatures of 270 ℃,300 ℃ and 330 ℃, and adjusting the softening point of an asphalt precursor to 230 ℃ by using a rotary thin film evaporation method.
(5) Melt spinning: and (3) putting the milled powder of the pitch precursor into a melt spinning machine, heating to 280 ℃ under the protection of nitrogen, keeping the temperature for 30min, and carrying out melt spinning under the conditions that the pressure is 0.3MPa and the rotating speed of a filament collecting cylinder is 1000m/min to obtain the pitch fiber.
(6) Pre-oxidation: the asphalt fiber is put into a tube furnace for pre-oxidation, and O is introduced at the flow rate of 50ml/min 2 Heating to the softening point of the asphalt at the heating rate of 0.5 ℃/min, and keeping the temperature for 0.5 h.
(7) Carbonizing: placing the pre-oxidized fiber in a tube furnace for carbonization, and introducing N at the flow rate of 200ml/min 2 Heating to 800 ℃ at the heating rate of 5 ℃/min, and preserving the heat for 30min to obtain the universal-grade carbon fiber.
The strength properties of the universal grade carbon fiber prepared in example 4 were as follows:
tensile strength: 1263 MPa; young's modulus: 82 GPa; elongation percentage: 1.5 percent.
The strength performance of the current general-grade carbon fiber by market vendors is as follows: tensile strength: 500-1000 MPa; young's modulus: 30-50 GPa; elongation percentage: not less than 1.5 percent. The strength performance of the universal-grade carbon fiber prepared by the process is as follows: tensile strength >1200 MPa; young's modulus >80 GPa; the elongation is more than or equal to 1.5 percent.
The preparation method is simple, the operation cost is low, no strong corrosive raw material is adopted, and the strength performance of the prepared carbon fiber is obviously superior to that of the existing general-grade carbon fiber.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (6)
1. A method for preparing carbon fibers by using coal liquefaction residues is characterized by comprising the following steps:
(1) mixing and purifying the coal liquefaction residue and tetrahydrofuran to obtain a tetrahydrofuran extract of the coal liquefaction residue;
(2) mixing the tetrahydrofuran extract of the coal liquefaction residue with a chlorinating agent in an inert atmosphere;
(3) melting the mixture obtained in the step (2) in an inert atmosphere, and then carrying out chlorination reaction at a constant temperature of 120-260 ℃;
(4) heating the reaction system to 320-370 ℃, carrying out dechlorination reaction at constant temperature, and cooling to room temperature after the dechlorination reaction is finished to obtain an asphalt precursor;
(5) adjusting the softening point of the pitch precursor to 220-260 ℃;
(6) carrying out melt spinning on the pitch precursor obtained in the step (5) to obtain pitch fibers;
(7) pre-oxidizing the pitch fibers;
(8) carbonizing the pre-oxidized asphalt fiber to obtain the carbon fiber; the mass ratio of the tetrahydrofuran extract of the coal liquefaction residue to the chlorinating agent is 1: 0.1-0.4;
the chlorination reaction time in the step (3) is 1-2 h;
the dechlorination reaction time in the step (4) is 1-3 h; the chlorinating agent is benzyl chloride.
2. The method according to claim 1, wherein the pitch precursor is heated to 200-350 ℃ in step (5), and then the softening point of the pitch precursor is adjusted by a rotary thin film evaporation method.
3. The method according to claim 2, wherein the temperature rise rate is 5 ℃/min.
4. The method according to claim 1, wherein the pre-oxidation step of step (7) is: and under the condition of oxygen, heating the asphalt fiber to the asphalt softening point at a heating rate of 0.5-2 ℃/min, and preserving heat for 0-1 h.
5. The method according to claim 1, wherein the carbonization treatment in step (8) comprises the following steps: in the presence of nitrogen, at a heating rate of 5-10 ℃/min, heating the pre-oxidized asphalt fiber to 800-900 ℃, and preserving heat for 5-30 min.
6. Carbon fibres obtainable by a process according to any one of claims 1 to 5.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477595A (en) * | 2010-11-22 | 2012-05-30 | 大连创达技术交易市场有限公司 | Pitch-based carbon fiber and preparation method thereof |
| CN103755926A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Condensed polynuclear polycyclic aromatic hydrocarbon resin and preparation method thereof |
| CN104004536A (en) * | 2013-02-22 | 2014-08-27 | 神华集团有限责任公司 | Mesophase pitch and preparation method thereof |
| CN107630267A (en) * | 2016-07-19 | 2018-01-26 | 神华集团有限责任公司 | A kind of coal liquefaction residue system can spin pitch and preparation method thereof and carbon fiber |
| CN107988713A (en) * | 2017-12-18 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing carbon nano-fiber non-woven fabrics using coal hydroliquefaction residue base pitch alkenes material |
| CN110699107A (en) * | 2019-10-14 | 2020-01-17 | 郑州中科新兴产业技术研究院 | Method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111996619A (en) * | 2020-09-29 | 2020-11-27 | 中国矿业大学(北京) | Preparation method of general-purpose asphalt-based carbon fiber |
-
2022
- 2022-01-13 CN CN202210035208.1A patent/CN114214758B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477595A (en) * | 2010-11-22 | 2012-05-30 | 大连创达技术交易市场有限公司 | Pitch-based carbon fiber and preparation method thereof |
| CN104004536A (en) * | 2013-02-22 | 2014-08-27 | 神华集团有限责任公司 | Mesophase pitch and preparation method thereof |
| CN103755926A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Condensed polynuclear polycyclic aromatic hydrocarbon resin and preparation method thereof |
| CN107630267A (en) * | 2016-07-19 | 2018-01-26 | 神华集团有限责任公司 | A kind of coal liquefaction residue system can spin pitch and preparation method thereof and carbon fiber |
| CN107988713A (en) * | 2017-12-18 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of method for preparing carbon nano-fiber non-woven fabrics using coal hydroliquefaction residue base pitch alkenes material |
| CN110699107A (en) * | 2019-10-14 | 2020-01-17 | 郑州中科新兴产业技术研究院 | Method for preparing spinnable mesophase pitch by coal pitch hydrogen catalysis-hydrogen supply treatment |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111996619A (en) * | 2020-09-29 | 2020-11-27 | 中国矿业大学(北京) | Preparation method of general-purpose asphalt-based carbon fiber |
Non-Patent Citations (1)
| Title |
|---|
| 《煤系通用型碳纤维的制备与研究》;刘金昌等;《煤炭科学技术》;20210228;第49卷(第2期);254-261 * |
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