CN107601492B - Preparation method of two-dimensional graphite-like structure material - Google Patents
Preparation method of two-dimensional graphite-like structure material Download PDFInfo
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- CN107601492B CN107601492B CN201710966657.7A CN201710966657A CN107601492B CN 107601492 B CN107601492 B CN 107601492B CN 201710966657 A CN201710966657 A CN 201710966657A CN 107601492 B CN107601492 B CN 107601492B
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- acid
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- 238000002360 preparation method Methods 0.000 title claims abstract description 36
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- 238000000034 method Methods 0.000 claims abstract description 27
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
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Images
Abstract
The invention discloses a preparation method of a two-dimensional graphite-like structure material, which comprises the steps of firstly mixing a raw material containing a polyaryl carbon structure with a proper solvent to prepare a mixture, and then carrying out a series of preparation processes such as high-speed shearing, cracking hydrogenation, shearing, centrifugal separation and the like on the mixture to obtain the two-dimensional graphite-like structure material. The preparation method has the advantages of mature process, simple and easy operation, cheap and easily-obtained raw materials, and realization of large-scale production; and the reaction byproducts can be completely recycled, so that the production cost is saved, and the environmental pollution is effectively avoided. The prepared two-dimensional graphite-like structure material is mainly formed by stacking a few-layer structure, and the graphitization degree is higher. A series of electrochemical representations show that the prepared graphite phase two-dimensional layered structure material has good electrocatalytic activity and battery energy storage characteristics.
Description
Technical Field
The invention belongs to the technical field of preparation of two-dimensional carbon materials, and relates to a preparation method of a two-dimensional graphite-like structure material.
Background
Two-dimensional materials are typically materials with a diameter of l on the monomolecular level, r → ∞, l/r → 0. The basic structure is characterized in that the vertical surface of the material has molecular scale, and the layer surface of the material presents an ordered supermolecular structure, namely l/r → 0. The two-dimensional polyaromatic carbon structure material is a material with polyaromatic carbon structure and derivative structure aromatic ring number >10 and crystal structure l/r → 0. The functional two-dimensional polyaryl carbon material is a material which carries functional compounds or metal elements (physically or chemically combined) on a two-dimensional polyaryl carbon crystal face and a material which has different crystal face sizes and different graphitization degrees and has the length-diameter ratio (l/r) <0.2, and the loaded, compounded and mixed materials show specific functionality. The material has a plurality of unique properties such as thermotropic liquid crystal property, electric conductivity and optical performance, and has application prospects in the aspects of electronic transmission materials, field effect transistors, photovoltaic cells, light emitting diodes, secondary batteries and the like, so that the material is called as the material king in the future, and becomes a research hotspot in the fields of materials science and physics.
Perfect graphene has an ideal two-dimensional structure. It is a single atom thick carbon material separated from graphite. The structure characteristic and the special electron orbit system of the high-power-density quantum well-balanced quantum well structure endow the high-power-density quantum well-balanced quantum well with a unique energy band structure, so that the high-power-density quantum well-balanced quantum. While it combines excellent electrical conductivity (capable of withstanding current densities of up to six orders of magnitude higher than copper), excellent thermal conductivity and strength, and extremely high surface area. The unique properties make the material have wide application prospect in the aspects of materials, electronic circuits and the like.
The successful separation of the graphene means that the theory is broken away from the prediction of the thermodynamic instability of the two-dimensional crystal, and the preparation of the two-dimensional graphite-like structural material is possible. At present, the preparation method of the two-dimensional graphite-like structure material comprises a chemical method and a physical method. The chemical methods include organic synthesis, oxidation-reduction, chemical vapor deposition, and the like. Physical methods include micro mechanical force stripping, ultrasonic dispersion, stamp cut transfer printing, and the like. Among them, the organic synthesis method and the Chemical Vapor Deposition (CVD) method have strict requirements on equipment and raw materials, and cannot be mass-produced; although the redox method can be used for mass preparation, a large number of defects are introduced in the reaction process, the physical and chemical properties of the redox method are seriously influenced, and the method has serious environmental pollution and is not suitable for industrial production. The physical methods have the problems of low efficiency, unstable product quality, time and labor waste and the like, are difficult to prepare on a large scale and can only be limited to small-scale experiments in laboratories.
Recently, there are a number of proprietary processes for the production of two-dimensional carbon materials based on coal-based feedstocks, such as: CN103803538A, CN103833028A, CN103288076A, CN103922329A and the like. However, the patented technology continues to use a physical and physicochemical method for graphene preparation, and is only a simple replacement of raw materials. The method has the advantages that the relationship between the maturity of coal-based raw materials and the size of the crystal face of the aromatic ring graphite structure is not classified, the chemical separation of the alkyl structure and the aromatic ring structure in the coal molecule cannot be realized, and the graphitization degree of the integrity of the graphite structure is improved. The carbon material prepared by the patented technology has some excellent properties, but the required production cost is high, excessive environmental polluting substances are introduced into the adopted production process, and the purity of the obtained product is not high enough. Therefore, a low-cost production raw material of the two-dimensional graphite-like structural material is developed, a more reasonable production process is designed based on the raw material, the production cost and the production difficulty can be effectively reduced, the product purity is improved, and the mass production of the two-dimensional graphite-like structural material is possible.
Disclosure of Invention
The invention aims to provide a preparation method of a two-dimensional graphite-like structure material, which can greatly reduce the comprehensive production cost and realize the minimum emission of the environment.
In one aspect of the invention, a preparation method of a two-dimensional graphite-like structure material is provided, which is characterized by comprising the following steps:
a. reacting raw material slurry oil containing a polyaryl carbon structure under a first engineering condition to prepare raw material engineering fluid;
b. introducing H into the raw engineering fluid2Carrying out cracking hydrogenation reaction to obtain hydrogenation engineering fluid containing a polyaromatic carbon structural component as a dispersed phase;
c. reacting the obtained hydrogenation engineering fluid under a second engineering condition to obtain a degassed hydrogenation engineering fluid;
d. naturally settling the degassed and hydrogenated engineering fluid for 12-24 h, and performing centrifugal separation on the obtained upper-layer sol oil slurry at the rotating speed of 5000-20000 rmp to prepare size-graded sol type two-dimensional graphite structure material oil slurry;
e. and reacting the obtained size-graded sol-gel type two-dimensional graphite-like structural material slurry under a third engineering condition to prepare the size-graded two-dimensional graphite-like structural material.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the raw material oil slurry containing the polyaromatic carbon structure in the step a comprises the following components in percentage by weight: 9.52 to 9.71 percent of raw material containing polyaryl carbon structure, 85.71 to 87.38 percent of solvent and 2.91 to 4.76 percent of soluble metal compound.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the raw material containing the polyaromatic carbon structure is coal containing the polyaromatic carbon structure, graphite containing the polyaromatic carbon structure or a mixture thereof.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the coal containing the polyaromatic carbon structure is selected from the following: anthracite with aromatic ring number more than 10 and maturity R degree more than or equal to 1.5; coal with heteroatom-rich aromatic ring number greater than 10 and maturity degree of R DEG equal to or greater than 1.2; gas coal with maturity R DEG >1.2, anthracite with maturity R DEG >2.5 and anthracite with maturity R DEG >10.0, or mixtures thereof.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the graphite containing the polyaromatic carbon structure is one or a mixture of aromatic layer graphite, micro-column graphite, soft and wrinkled graphite and straight graphite with the graphitization degree G being more than or equal to 20%.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the solvent comprises the following components: 28 to 45 weight percent of heavy aromatic oil, 28 to 45 weight percent of polycyclic aromatic oil, 2 to 5 weight percent of heterocyclic compound, 31.58 to 32.26 weight percent of coal with the maturity of not more than 0.75 degree, 2 to 5 weight percent of solubilizer, 0.05 to 10.0 weight percent of complexing agent or 0.01 to 5.0 weight percent of complexing auxiliary agent.
The invention also provides a preparation method of the two-dimensional graphite structure material, wherein the solubilizer is selected from o-cresol, m-cresol, p-cresol, catechol, resorcinol, naphthoyl and derivatives thereof or mixtures thereof.
The invention also provides a preparation method of the two-dimensional graphite structure material, wherein the complexing agent comprises at least one of 1, 10-phenanthroline, Ethylene Diamine Tetraacetic Acid (EDTA), dimercaprol, dimercaptopropane sodium sulfonate, mercaptoethylamine, mercaptoacetic acid, thiourea, 8-hydroxyquinoline, cyanide, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid (EGTA), ethylene diamine tetraacetic acid, triethylene tetramine, lignosulfonic acid, humic acid and sulfonated humic acid.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the complexing auxiliary agent is at least one of sodium alkoxide, sodium methylsiliconate, urea, NaOH and KOH.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the raw material oil slurry containing the polyaromatic carbon structure in the step a is prepared by mixing the raw material containing the polyaromatic carbon structure, the solvent and the soluble metal compound, and stirring at the temperature of 20-250 ℃ and under normal pressure for 2-6 hours.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the first engineering condition in the step a is as follows: the temperature is 220-330 ℃, the pressure is 1-5 MPa, and the shear rate is 1000-20000 s-1The shearing time is 1-6 h, the aging temperature is 120-220 ℃, and the aging time is 12-48 h.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the hydrogen and the raw material engineering fluid are mixed according to the volume ratio (100-10000 Nm & lt/EN & gt) in the step b3/m3): 1, at a pressure of 10-30 MPa, a temperature of 400-550 ℃ and H2The space velocity is 0.1-10 h-1The following reaction is carried out.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein in the step c, the second engineering conditions comprise the temperature of 110-350 ℃, the pressure of 2-18 MPa and the shear rate of 2000-3 × 50000s-1。
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the lower-layer sol-oil slurry can be further obtained after the degassing and hydrogenation engineering fluid is naturally settled for 12-24 hours in the step d.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein hydrogenated liquid and carbon-containing inorganic residues can be prepared from the sol-oil slurry at the lower layer after solid-liquid separation.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein distillate oil gas which is obtained by fractionating hydrogenated liquid and is less than or equal to 350 ℃ can be used as light hydrocarbon liquid fuel, and the obtained distillate oil which is more than 350 ℃ can be used as circulating solvent.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the third engineering condition in the step e is as follows: the spraying speed is 8-14 m/s, the temperature is 300-400 ℃, and the pressure is 0.001-0.008 MPa.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein in the step e, the two-dimensional graphite-like structure material can be further roasted in a graphite furnace under the protection of argon or hydrogen to prepare the graphitized two-dimensional material.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the roasting conditions of the graphite furnace are as follows: the introducing speed of hydrogen or argon is 1-5 m/s and the temperature is 2500-3000 ℃.
The invention also provides a preparation method of the two-dimensional graphite-like structure material, wherein the circulating solvent can be added into the step a for repeated use.
The invention has the advantages that:
(1) the raw materials used in the invention are cheap and easy to obtain, and the industrial production of the two-dimensional graphite-like structural material is realized by reasonably preparing the raw material slurry oil containing the polyaromatic carbon structure. In addition, substances such as light hydrocarbon fuel and the like are generated, and the comprehensive utilization of the organic carbon raw material is realized to the maximum extent.
(2) The extra products such as the circulating solvent, the carbon-containing inorganic matters and the like generated by the invention can be recycled, so that the minimum emission of the environment is realized while the comprehensive production cost is greatly reduced.
(3) By adopting the comprehensive engineering system, the large-scale production of two-dimensional graphite-like structural materials, high-graphitization-degree two-dimensional materials, graphene materials and the like can be realized at the same time.
(4) The preparation method provided by the invention realizes chemical separation of the alkyl structure and the aromatic ring structure in the coal molecule, and improves the graphitization degree of graphite. The obtained material has small median of particle size distribution, high content of few-layer graphite and good catalytic performance.
(5) The industrial device system designed by the invention has high safety reliability and running stability, and the whole process is finished in a dehydration or anhydrous environment, so that resources are saved.
The foregoing description is only an overview of the technical solutions of the present invention, and the embodiments of the present invention are described below in order to make the technical means of the present invention more clearly understood and to make the above and other objects, features, and advantages of the present invention more clearly understandable.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is TEM and HRTEM images of two-dimensional graphite-like structure material obtained in example 13 of the present invention;
fig. 3 is a raman spectrum of a two-dimensional graphite-like structural material obtained in example 13 of the present invention;
fig. 4 is a charge-discharge curve and cycle performance chart of the two-dimensional graphite-like structural material obtained in example 13 of the present invention.
Detailed Description
The present invention is further illustrated below with reference to examples, which are intended to illustrate the invention and not to limit the scope of the invention. Furthermore, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings herein, and such equivalents may fall within the scope of the invention as defined in the appended claims.
Definition of
Unless otherwise indicated, the term "first engineering conditions" herein refers to raw engineering fluid preparation conditions, including temperature pressure, shear rate, shear time, aging temperature, and aging time. "second engineering conditions" refers to degassing hydrogenation and phase separation conditions, including temperature, pressure, and shear rate. "third engineering conditions" refers to reduced pressure flash conditions, including spray rate, temperature, and pressure.
Unless otherwise indicated, the term "heavy aromatic oil" as used herein refers to an aromatic oil having a C.gtoreq.10, herein referred to as a base solvent oil, including but not limited to one or more of coker gas oil, catalytically cracked clarified oil or slurry oil, high phenol gas oil, lube oil furfural refined extract oil, coal tar coker gas oil, hydrogenated heavy oil, and hydrogenated light heavy oil.
The term "polycyclic aromatic hydrocarbon oil" as used herein refers to a compound oil having two or more benzene rings, and is also used to refer to a partially or fully hydrogenated product thereof or a derivative thereof, including but not limited to one or more of naphthalene, anthracene, phenanthrene, acetonaphthalene, 1-methylnaphthalene, 2-methylnaphthalene, 1,2,3, 4-tetrahydronaphthalene, gamma-methylpyridine, isoquinoline, dihydronaphthalene, decalin, 9, 10-dihydroanthracene, and 9, 10-dihydrophenanthrene.
As used herein, the term "heterocyclic compound" is used to refer to an organic compound containing a heteroatom in the phenyl ring, including, but not limited to, one or a mixture of compounds such as: furan, thiophene, pyrrole, imidazole, pyridine, pyrazine, pyrimidine, indole, quinoline, pteridine, acridine and N-methylpyrrolidone.
As used herein, the term "metal compound" refers to a mixture of one or more of inorganic salts, organic salts, complexes, and chelates of metals that can be dissolved or dispersed in a solvent in an ionic state, a molecular state, a complexed state, or a multi-molecular polymerized state, including but not limited to one or more of inorganic salts, organic salts, complexes, and chelates consisting of the following metal elements: iron, nickel, molybdenum, copper, zinc, tin, aluminum, tungsten, manganese, titanium, vanadium, chromium, cobalt, gold, cadmium, mercury, cerium, lithium, magnesium, vanadium, tungsten, lanthanum.
Preparation of two-dimensional graphite-like structural material
Examples 1 to 6
Raw material slurry composition
Solvent(s): the high-purity petroleum coke is prepared by mixing the coking wax oil, catalytic cracking slurry oil, high-phenol wax oil, distillate oil with the temperature of more than or equal to 350 ℃ in the deslagging hydrogenation engineering fluid, Yumen vacuum residue oil, rice bran oil, catechol, 1, 10-phenanthroline, dimercaptopropanol complexing agent, lignin, humic acid and sodium methylsiliconate auxiliary agent.
Pulverized lignite of Yuanbaoshan inner Mongolia(more than or equal to 120 meshes, maturity R DEG is 0.42, ash content is 6.2 wt%, coal powder water content is 2.5 wt%, organic phase content (daf) is 91.3 wt%, hydrocarbon phase content is 78.9 wt%).
Low-rank anthracite coal powder of Hebei peak(more than or equal to 200 meshes, maturity R DEG is 2.9, ash content is 4.7 wt%, coal powder water content is 1.3 wt%, organic phase content (daf) is 94.0 wt%, hydrocarbon phase content is 91.9 wt%, and sericin content is less than or equal to 0.7 wt% (daf)).
Soluble metal compound solvent: water soluble Fe2+A compound, and an auxiliary metal ion M ═ Al3+、Ti4+La is a rare earth water-soluble compound. The specific reaction conditions and the relevant reaction parameters are shown in Table 1.
TABLE 1 relevant reaction conditions and parameters for examples 1-6
Examples 7 to 12
Raw material slurry composition
Solvent(s): the high-purity petroleum coke is prepared by mixing the coking wax oil, catalytic cracking slurry oil, high-phenol wax oil, distillate oil with the temperature of more than or equal to 350 ℃ in the deslagging hydrogenation engineering fluid, Yumen vacuum residue oil, rice bran oil, catechol, 1, 10-phenanthroline, dimercaptopropanol complexing agent, lignin, humic acid and sodium methylsiliconate auxiliary agent.
Pulverized lignite of Yuanbaoshan inner Mongolia(more than or equal to 120 meshes, maturity R DEG is 0.42, ash content is 6.2 wt%, coal powder water content is 2.5 wt%, organic phase content (daf) is 91.3 wt%, hydrocarbon phase content is 78.9 wt%).
Ningxia Ru osmunda ditch fine-selection high-order anthracite coal powder(more than or equal to 200 meshes, the maturity R DEG is 6.5, the ash content is 2.2 wt%, the water content of coal powder is 0.8 wt%, the organic phase content (daf) is 97.0 wt%, the hydrocarbon phase content is 96.7 wt%, the structure content of polyaryl carbon graphite is 65.8 wt% (daf%), and the content of sericin is less than or equal to 0.2 wt% (daf)).
Soluble metal compound solvent: water soluble Ni2+、Mo2+、W6+And an auxiliary metal ion La-based rare earth water-soluble compound. Specific reaction conditions and related reaction parameters are shown in tables 2 and 3.
TABLE 2 relevant reaction conditions and parameters in examples 7-12
TABLE 3 relevant reaction conditions and parameters for the work-up units of examples 7 to 12
Examples 13 to 15
Raw material slurry composition
Solvent(s): the high-purity petroleum coke is prepared by mixing the coking wax oil, catalytic cracking slurry oil, high-phenol wax oil, distillate oil with the temperature of more than or equal to 350 ℃ in the deslagging hydrogenation engineering fluid, Yumen vacuum residue oil, rice bran oil, catechol, 1, 10-phenanthroline, dimercaptopropanol complexing agent, lignin, humic acid and sodium methylsiliconate auxiliary agent.
Pulverized lignite of Yuanbaoshan inner Mongolia(200 meshes or more, maturity R ° -2.9, ash content-4.7 wt%, coal powder water content-1.3 wt%, organic phase content (daf) -94.0 wt%, hydrocarbon phase content-91.9 wt%).
Fine-selection flake conductive graphite powder for Heilongjiang sheep nosesThe graphite has the following characteristics that the graphite is larger than or equal to 325 meshes, the graphitization degree G is 92%, the organic phase content is 98.98 wt%, the carbon content (daf) is 98.02 wt%, the ash content is 0.72 wt%, the water content is 0.3 wt%, the electric conductivity is 1.22S/m, and the polyaryl carbon graphite structure content is 95.1 wt%.
Soluble metal compound solvent: water soluble Fe2+A compound, and an auxiliary metal ion M ═ Mo4+、Ni2+、Ce4+Preparing 5 wt% aqueous solution according to a certain proportion. The specific parameters and conditions are shown in tables 4-7.
TABLE 4 relevant reaction conditions and parameters for examples 13-15
TABLE 5 relevant reaction conditions and parameters in the work-up unit of example 13
TABLE 6 relevant reaction conditions and parameters in the work-up unit of example 14
TABLE 7 relevant reaction conditions and parameters in the work-up unit of example 15
FIG. 2 is TEM and HRTEM images of two-dimensional graphite-like structure material obtained in example 13 of the present invention. From fig. 2, it can be seen that the obtained two-dimensional graphite-like structure material has a two-dimensional lamellar structure and a porous structure.
Fig. 3 is a raman spectrum of the two-dimensional graphite-like structural material obtained in example 13 of the present invention. From fig. 3, it can be seen that the prepared two-dimensional graphite-like structure material has a D peak, a G peak and a 2D peak which are possessed by the graphene material.
Performance determination of two-dimensional graphite-like structure material
Examples 16 to 25 two-dimensional graphite-like structural Material as negative electrode Material for lithium ion batteries
The materials selected in the performance test are the two-dimensional graphite-like structural materials prepared from the sol (1) in examples 1, 3, 5 and 7, the sol (1) in 9, the sol (1) in 11 and the sol (13) in 11. In the material performance test, a lithium sheet is used as a counter electrode, the material product obtained in the above example is used as a sample, wherein the material sample, a conductive agent (super P) and a binder (PVDF) in a mass ratio of 8:1:1 are used as a working electrode, 1M LiPF6(EC/DMC of 1:1V/V) is selected as an electrolyte, a button cell (half cell) is assembled for testing, the voltage interval is 2-4V, the current density is 0.5A, 2A and 5A, and the material sample electrode has a good charge and discharge platform in the charge and discharge process after 200 and 2000 times of cyclic charge and discharge. The sample of the example 24 has good cycling stability, the capacity is kept at 448mAh/g after 2000 cycles, the sample of the example 25 has excellent stability after 2000 cycles of 5A charge and discharge, the capacity is unchanged at 385mAh/g, and the initial coulombic efficiency is as high as more than 92%. The test results are shown in Table 8.
TABLE 8 test results of two-dimensional graphite-like structural material as negative electrode material of lithium ion battery
Examples 26-35 two-dimensional graphite-like structural materials as catalytic electrode materials for methanol fuel cells
The materials selected in the performance test are the two-dimensional graphite-like structural materials prepared from the sol (1) in the examples 2, 4, 6 and 8, the sol (1) in the example 10, the sol (1) in the example 12 and the sol (14) in the example 14. The process of catalyzing oxygen reduction is a direct four-electron process at O2In a saturated 0.1M NaOH solution, the sweep rate is 100 mV. s-1Electrochemical tests under the conditions show that the catalyst has strong methanol resistance, good catalytic activity and high stability. The two-dimensional graphite-like structure material of the example 34 has better peak potential compared with the catalytic electrode material Pt/C of the methanol fuel cell, and the catalytic electrical property of the material of the example 35 is obviously better than that of the Pt/C. The test results are shown in Table 9.
TABLE 9 test results of two-dimensional graphite-like structural materials as catalytic electrode materials for methanol fuel cells
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention disclosed herein should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (13)
1. A preparation method of a two-dimensional graphite-like structure material is characterized by comprising the following steps:
a. reacting raw material oil slurry containing a polyaromatic carbon structure under a first engineering condition to prepare raw material engineering fluid, wherein the raw material oil slurry containing the polyaromatic carbon structure is prepared by stirring 9.52-9.71% of raw material containing the polyaromatic carbon structure, 85.71-87.38% of solvent and 2.91-4.76% of soluble metal compound for 2-6 hours at the temperature of 20-250 ℃ under normal pressure, and the first engineering condition is as follows: the temperature is 220-330 ℃, the pressure is 1-5 MPa, the shear rate is 1000-20000 s < -1 >, the shear time is 1-6 h, the aging temperature is 120-220 ℃, and the aging time is 12-48 h;
b. introducing H into the raw engineering fluid2，H2The volume ratio of the raw material engineering fluid to the raw material engineering fluid is (100-10000 Nm)3/m3) 1, under the pressure of 10-30 MPa and the temperature of 400-550 ℃ and H2The space velocity is 0.1-10 h-1Carrying out the reaction to obtain hydrogenation engineering fluid containing a polyaromatic carbon structural component as a dispersed phase;
c. reacting the obtained hydrogenation engineering fluid under a second engineering condition to obtain degassed hydrogenation engineering fluid, wherein the second engineering condition is that the temperature is 110-350 ℃, the pressure is 2-18 MPa, and the shear rate is 2000-3 × 50000s-1；
d. Naturally settling the degassed and hydrogenated engineering fluid for 12-24 h, and performing centrifugal separation on the obtained upper-layer sol oil slurry at the rotating speed of 5000-20000 rmp to prepare size-graded sol type two-dimensional graphite structure material oil slurry;
e. the obtained size-graded sol-gel type two-dimensional graphite-like structural material slurry is reacted under a third engineering condition to prepare a size-graded two-dimensional graphite-like structural material, wherein the third engineering condition is as follows: the spraying speed is 8-14 m/s, the temperature is 300-400 ℃, and the pressure is 0.001-0.008 MPa.
2. The method according to claim 1, wherein the raw material containing a polyaromatic carbon structure is coal containing a polyaromatic carbon structure, graphite containing a polyaromatic carbon structure, or a mixture thereof.
3. The method of claim 2, wherein the coal containing a polyaromatic carbon structure is selected from: anthracite with aromatic ring number more than 10 and maturity R degree more than or equal to 1.5; the number of aromatic rings rich in hetero atoms is more than 10, and the maturity R degree is more than or equal to 1.2.
4. The method according to claim 2, wherein the graphite containing the polyaryl carbon structure is one or a mixture of aromatic layer graphite, micro-column graphite, rugose graphite and straight graphite with the graphitization degree G being more than or equal to 20%.
5. The method of claim 1, wherein the solvent comprises the following components: 28 to 45 weight percent of heavy aromatic oil, 28 to 45 weight percent of polycyclic aromatic oil, 2 to 5 weight percent of heterocyclic compound, 31.58 to 32.26 weight percent of coal with the maturity of R0.75, 2 to 5 weight percent of solubilizer, 0.05 to 10.0 weight percent of complexing agent and 0.01 to 5.0 weight percent of complexing auxiliary agent.
6. The process according to claim 5, wherein the solubilizing agent is selected from o-cresol, m-cresol, p-cresol, catechol, resorcinol, naphthoyl and derivatives thereof or mixtures thereof.
7. The method of claim 5, wherein the complexing agent is at least one of the group consisting of 1, 10-phenanthroline, ethylenediaminetetraacetic acid (EDTA), dimercaprol, sodium dimercaptopropane sulfonate, mercaptoethylamine, thioglycolic acid, thiourea, 8-hydroxyquinoline, cyanide, citric acid, tartaric acid, oxalic acid, sulfosalicylic acid, triethanolamine, ethyleneglycol bis (2-aminoethyl ether) tetraacetic acid (EGTA), ethylenediaminetetraacetic acid, triethylenetetramine, lignosulfonic acid, humic acid, and sulfonated humic acid.
8. The method of claim 5, wherein the complexing agent is at least one of sodium alkoxide, sodium methyl silanol, urea, NaOH, KOH.
9. The method according to claim 1, wherein a lower layer of sol-oil slurry is further obtained after the degassed and hydrogenated engineering fluid is naturally settled for 12-24 hours in the step d.
10. The method of claim 9, wherein the lower layer sol-gel slurry is subjected to solid-liquid separation to produce a hydrogenated liquid and a carbon-containing inorganic residue.
11. The method of claim 10, wherein the hydrogenated liquid is fractionated to obtain 350 ℃ or less distillate oil gas as light hydrocarbon liquid fuel, and the obtained 350 ℃ or more distillate oil as circulating solvent.
12. The method according to claim 1, wherein the two-dimensional graphite-like structural material in the step e is further calcined in a graphite furnace under the protection of argon or hydrogen to prepare a graphitized two-dimensional material.
13. The method of claim 12, wherein the graphite furnace firing conditions are: the introducing speed of hydrogen or argon is 1-m/s and the temperature is 2500-3000 ℃.
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