A petroleum pitch-based high-crystalline soft carbon material and a preparation method thereof

Abstract

This invention provides a petroleum asphalt-based highly crystalline soft carbon material and its preparation method, belonging to the technical fields of new energy and new materials. It utilizes in-situ phenolic resin modification to prepare high-softening-point modified petroleum asphalt, which is then carbonized to obtain a graphite-like soft carbon material. First, petroleum asphalt is melt-blended with aromatic phenolic organic compounds. Then, under the catalysis of an organic base, a condensation reaction occurs with the aromatic aldehydes to prepare in-situ phenolic resin-modified petroleum asphalt. Low-boiling-point fractions are removed by vacuum distillation, allowing for the controllable preparation of high-softening-point phenolic resin-modified petroleum asphalt. Carbonization then yields a highly crystalline, structurally controllable, layered graphite-like soft carbon material. This invention solves the technical problems of poor controllability in the carbonization process of petroleum asphalt and unsatisfactory crystallinity of carbon materials. This method provides a new pathway for the application of petroleum asphalt in high-performance green energy fields such as environmentally friendly batteries and energy storage materials.

Description

Technical Field

[0001] This invention belongs to the industrial fields of energy chemical industry, petrochemical industry, materials chemical industry and polymer chemical industry, and relates to a negative electrode material that can be used in environmentally friendly batteries and energy storage devices. It is a highly crystalline petroleum pitch-based soft carbon material and its preparation method. Background Technology

[0002] With the rapid increase in demand for electrochemical energy storage, the market's performance requirements and usage scale for green energy materials are constantly rising, and anode materials are one of the key materials. Due to limitations in industrial production technology, the anode materials currently used in lithium-ion batteries are still mainly artificial graphite, with coal tar pitch and a small portion of high-quality petroleum pitch as initial raw materials. The high pollution of the coal chemical industry has limited its overall development, leading to a gradual decrease in coal tar pitch production, which cannot meet the demand for high-performance energy materials. Petroleum pitch, an important product of the oil refining industry, has a huge output, but its aromatic content is low, its H / C ratio is high, its direct carbonization residual carbon rate is low, and its crystallinity is poor, failing to meet the performance requirements of functional carbon for anode materials. Therefore, how to regulate the preparation of high-performance petroleum pitch to meet the requirements of green energy carbon materials has become an important scientific and technological issue.

[0003] Although petroleum asphalt is considered a potential precursor for the preparation of carbon materials, it faces the following challenges: 1) Dislocations and even overlaps occur between the layers of petroleum asphalt-based carbonized materials, resulting in a disordered and unstructured distribution; 2) The high H / C ratio of petroleum asphalt easily leads to structural defects during the carbonization process, affecting the electrochemical performance of carbon materials. To address the above issues, patent CN102723492A proposes a method for preparing hard carbon by adding petroleum asphalt to an organic polymer solution containing epoxy groups, mixing it thoroughly, drying it to obtain a precursor, and then carbonizing it. Patent CN116216693A proposes a method for preparing hard carbon anode materials by ball milling pre-oxidized high softening point petroleum asphalt with ammonium phosphate salt, followed by direct carbonization. Patent CN115974065A proposes a method for preparing hard carbon anode materials by ball milling a mixture of ball-milled petroleum asphalt powder and chemical modifier 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in acetic acid, followed by carbonization. Patent CN117185285A proposes a method for preparing graphene by dissolving petroleum asphalt in an organic solvent, adding silicate cement and iron template agents, distilling to recover the organic solvent, carbonizing the asphalt mixture at high temperature, acid washing to remove cement and iron template agents, and vacuum drying. However, the above methods all suffer from poor compatibility between petroleum asphalt and modifiers and templates, require a large amount of organic solvents and special mechanical equipment for mixing, and are costly, making it difficult to meet the needs of industrial production. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a petroleum asphalt-based highly crystalline soft carbon material and its preparation method. By in-situ polymerization of aromatic phenol monomers and aromatic aldehyde monomers in liquid asphalt solution, in-situ phenolic resin-modified petroleum asphalt is obtained, achieving fine dispersion of phenolic resin in petroleum asphalt. This method can efficiently control the pyrolysis and polymerization of polycyclic aromatic hydrocarbons in asphalt and the growth of carbon materials, and can control the preparation of sheet-like layered highly crystalline graphite-like soft carbon materials.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a petroleum asphalt-based highly crystalline soft carbon material is disclosed. The method is an in-situ phenolic resin modification method for petroleum asphalt. The method involves: first, adding petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers, and an organic base into a reaction vessel for melt blending; and then, under the catalysis of the organic base, a condensation reaction occurs between the aromatic phenol monomers and aromatic aldehyde monomers to prepare in-situ phenolic resin-modified petroleum asphalt. Second, removing low-boiling-point fractions by vacuum distillation allows for the controllable preparation of high-softening-point phenolic resin-modified petroleum asphalt. Finally, carbonization treatment yields a highly crystalline, structurally controllable layered graphite-like soft carbon material. This invention, through the selection and proportioning of petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers, and catalysts, the control of polymerization reaction and vacuum distillation conditions, and the setting of the final carbonization temperature and the heating rate, enables the control of the crystallinity and structural dimensions of petroleum asphalt throughout the modification and carbonization process. Specifically, the method includes the following steps:

[0007] 1) Add petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers and organic base catalysts into the reactor, wherein the amount of aromatic aldehyde monomers is 5-10 wt% of the mass of asphalt, the amount of aromatic phenol monomers is 5-10 wt% of the mass of asphalt, and the amount of organic base is 1-10 wt% of the mass of aromatic aldehyde monomers.

[0008] 2) After slowly heating until the materials in the reactor are fully dissolved and mixed, carry out a polycondensation reaction for 2 to 8 hours in the range of 140 to 200°C to obtain in-situ phenolic resin modified petroleum asphalt.

[0009] 3) The in-situ phenolic resin modified petroleum asphalt obtained in step 2) is subjected to vacuum distillation for 1 to 6 hours at a temperature of 250 to 350°C and a pressure of 10 to 50 kPa to obtain phenolic resin modified petroleum asphalt with a softening point in the range of 170 to 270°C.

[0010] 4) Place the phenolic resin-modified asphalt obtained in step 3) into a carbonization furnace. Under inert gas protection, start from room temperature and heat up to 1000-1500℃ at a rate of 1-5℃ / min, and carry out a carbonization reaction for 2-5 hours. After cooling, obtain a layered graphite-like soft carbon material with high crystallinity and controllable structure.

[0011] Furthermore, the petroleum asphalt is one or two of oxidized petroleum asphalt, solvent-de-oiled petroleum asphalt, and blended petroleum asphalt, with a softening point of 95–125°C.

[0012] Furthermore, the aromatic phenol monomers include phenol, methylphenol, dimethylphenol, ethylphenol, propylphenol, tert-butylphenol, pentylphenol, hexylphenol, nonylphenol, cashew phenol, bisphenol A, bisphenol F, bisphenol S, phenylphenol, catechol, resorcinol, hydroquinone, naphthol, naphthol, and one or more mixtures of heavy phase residual byproducts from the distillation and purification process of phenol monomers; preferably, nonylphenol, hydroquinone, and 1,4-naphthol are used as aromatic phenol monomers.

[0013] Furthermore, the aromatic aldehyde monomers include furfural, benzaldehyde, naphthal, o-(m-, p-) phthalaldehyde, mesitylenebenzaldehyde, naphthial, etc., as well as their substituted derivatives, and one or more mixtures of the residual substrates after distillation; preferably p-phthalaldehyde, m-phthalaldehyde, and 1,4-naphthial are used as aromatic aldehyde monomers.

[0014] Furthermore, the organic base catalyst includes one or more of the following: cyclohexylamine, quinoline, indoline, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), mono(poly)alkyl-substituted imidazoles and imidazolines, and organic bases with 2 to 32 carbon atoms in the substituent; preferably, oleic acid imidazoline, cycloalkyl imidazoline, and rosin-based imidazoline are used as polymerization catalysts.

[0015] Furthermore, the inert protective atmosphere is nitrogen or argon.

[0016] A petroleum asphalt-based highly crystalline soft carbon material is prepared by the above-described method. The carbon material exhibits a uniform lamellar structure with a relatively concentrated size distribution. The lamellars are arranged in an orderly and densely packed manner, approximating parallel lengths. XRD and Raman spectral characterization results are similar to those of graphite, with a graphitization degree reaching up to 89.53% and a tap density of up to 1.056 g / cm³. 3 The true density can reach 2.16 g / cm³. 3 .

[0017] A petroleum asphalt-based highly crystalline soft carbon material can be used as a negative electrode material for environmentally friendly batteries and energy storage devices.

[0018] Compared with existing petroleum pitch-based carbon material preparation technologies, the beneficial effects of this invention are:

[0019] (1) In this invention, petroleum asphalt is mixed with aromatic phenol monomers and aromatic aldehyde monomers. Since this polymerization reaction belongs to the category of solution polymerization, it can achieve fine dispersion of in-situ polymerized phenolic resin in petroleum asphalt.

[0020] (2) By utilizing the synergistic effect of finely dispersed phenolic resin on the thermal polymerization and thermal decomposition of polycyclic aromatic hydrocarbon molecules in asphalt, this invention can regulate the crystallinity and structural dimensions of carbon materials during the carbonization process. Attached Figure Description

[0021] Figure 1 The following is a characterization diagram of the phenolic resin-modified petroleum asphalt-based carbon material in Example 1: where, Figure 1 (a) is the XRD pattern; Figure 1 (b) is the Raman spectrum; Figure 1 (c) is an XPS plot; Figure 1 (d) is a 3000x magnified SEM image; Figure 1 (e) is a SEM image magnified 20,000 times; Figure 1 (f) is the HRTEM plot;

[0022] Figure 2 The following is a characterization diagram of the phenolic resin-modified petroleum asphalt-based carbon material in Example 2: where, Figure 2 (a) is the XRD pattern; Figure 2 (b) is the Raman spectrum; Figure 2 (c) is an XPS plot; Figure 2 (d) is a 3000x magnified SEM image; Figure 2 (e) is a SEM image magnified 20,000 times; Figure 2 (f) is the HRTEM plot;

[0023] Figure 3 The following is a characterization diagram of the phenolic resin-modified petroleum asphalt-based carbon material in Example 3: [Diagram showing the characterization process] Figure 3 (a) is the XRD pattern; Figure 3 (b) is the Raman spectrum; Figure 3 (c) is an XPS plot; Figure 3 (d) is a 3000x magnified SEM image; Figure 3 (e) is a SEM image magnified 20,000 times; Figure 3 (f) is the HRTEM plot;

[0024] Figure 4 This is a SEM image of the phenolic resin-modified petroleum asphalt-based carbon material in Example 3. Detailed Implementation

[0025] The present invention will be further described below with reference to specific implementation examples, but the present invention is not limited to these examples.

[0026] Example 1

[0027] Step 1: Add 250.8g of blended petroleum asphalt (softening point 95℃), 25.8g of hydroquinone, 12.9g of terephthalaldehyde and 0.65g of cycloalkylimidazoline to the reaction vessel.

[0028] Step 2: After slowly heating the above system until the material in the reactor is fully dissolved, stir and react at a constant temperature of 140°C for 8 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0029] Step 3: Heat to 350℃, reduce pressure to 20kPa, and distill under reduced pressure for 1 hour to obtain phenolic resin modified asphalt with a softening point of 229℃ and a coking value of 66.78%.

[0030] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1000℃ at 5℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0031] Figure 1 The characterization diagram of the phenolic resin-modified petroleum pitch-based carbon material obtained in this embodiment is as follows: Figure 1 The X-ray diffraction pattern of (a) yields a 0.336 nm interplanar spacing for 002; Figure 1 (b) The Raman spectrum can be calculated to obtain I G / I D It is 3.121; Figure 1 (c) The X-ray electron spectroscopy reveals that the elemental composition of the material is: 88.2 wt% C, 1.1 wt% N, 8.3 wt% and 1.9% S; Figure 1 (d) and Figure 1 (e) The SEM image shows that the obtained carbon material is lamellar with relatively tight interlayer packing, orderly structure, and uniform size distribution; Figure 1 (f) HRTEM showed that the material was layered, with the layers nearly parallel over long distances, and an average interlayer spacing of approximately 0.365 nm; the tap density was 0.970 g / cm³. 3 True density is 1.95 g / cm³. 3 .

[0032] Example 2

[0033] Step 1: Add 250.8g of oxidized petroleum asphalt (softening point 102℃), 25.8g of p-nonylphenol, 25.9g of p-1,4-naphthodialdehyde and 0.26g of cycloalkylimidazoline to the reaction vessel.

[0034] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 155℃ for 6 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0035] Step 3: Heat to 350℃, reduce pressure to 30kPa, and distill under reduced pressure for 2 hours to obtain phenolic resin modified asphalt with a softening point of 245℃ and a coking value of 71.58%.

[0036] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1100℃ at 4℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0037] Figure 2 The characterization diagram of the phenolic resin-modified petroleum pitch-based carbon material obtained in this embodiment is as follows: Figure 2 The X-ray diffraction pattern of (a) yields a 0.336 nm interplanar spacing for 002; Figure 2 (b) The Raman spectrum can be calculated to obtain I G / I D It is 3.721; Figure 2 (c) The X-ray electron spectrum shows that the elemental composition of the material is: 89.3 wt% C, 1.1 wt% N, 7.6 wt% and 1.4% S; Figure 2 (d) and Figure 2 (e) The SEM image shows that the obtained carbon material is lamellar with tight interlayer packing, orderly structure, and relatively uniform size distribution. Figure 2 (f) HRTEM showed that the material was layered, with the layers nearly parallel over long distances, and an average interlayer spacing of approximately 0.3358 nm; the tap density was 0.979 g / cm³. 3 True density is 1.97 g / cm³. 3 .

[0038] Example 3

[0039] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 114℃), 12.6g of 1,4-naphthol, 12.9g of isophthalaldehyde and 1.30g of cycloalkylimidazoline to the reaction vessel.

[0040] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 170℃ for 4 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0041] Step 3: Heat to 330℃, reduce pressure to 20kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 257℃ and a coking value of 67.33%.

[0042] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 3℃ / min under an argon atmosphere, and carbonize it at high temperature for 4 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0043] Figure 3 The characterization diagram of the phenolic resin-modified petroleum pitch-based carbon material obtained in this embodiment is as follows: Figure 3 The X-ray diffraction pattern of (a) yields a 0.336 nm interplanar spacing for 002; Figure 3 (b) The Raman spectrum can be calculated to obtain I G / I D It is 3.121; Figure 3 (c) The X-ray electron spectrum shows that the elemental composition of the material is: 88.1 wt% C, 1.4 wt% N, 8.2 wt% and 1.9% S; Figure 3 (d) and Figure 3 (e) The SEM image shows that the obtained carbon material is lamellar with relatively tight interlayer packing, orderly structure, and uniform size distribution; Figure 3 (f) HRTEM showed that the material was layered, with the layers nearly parallel over long distances, and an average interlayer spacing of approximately 0.374 nm; the tap density was 0.990 g / cm³. 3 True density is 2.05 g / cm³. 3 .

[0044] Example 4

[0045] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 110℃), 25.8g of 3,5-dimethylphenol, 12.9g of o-phthalaldehyde and 0.77g of oleic acid imidazoline to the reaction vessel.

[0046] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 160℃ for 5 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0047] Step 3: Heat to 250℃, reduce pressure to 20kPa, and distill under reduced pressure for 6 hours to obtain phenolic resin modified asphalt with a softening point of 195℃ and a coking value of 58.39%.

[0048] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 2℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0049] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I DThe value is 2.769, and the tap density is 0.982 g / cm³. 3 The true density is 2.01 g / cm³. 3 .

[0050] Example 5

[0051] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 114℃), 25.8g of p-ethylphenol, 25.9g of m-phenylenedialdehyde and 1.81g of oleic acid imidazoline to the reaction vessel.

[0052] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 170℃ for 6 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0053] Step 3: Heat to 300℃, reduce pressure to 10kPa, and distill under reduced pressure for 5 hours to obtain phenolic resin modified asphalt with a softening point of 205℃ and a coking value of 59.08%.

[0054] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1500℃ at 2℃ / min under an argon atmosphere, and carbonize it at high temperature for 2 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0055] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.892, and the tap density is 1.027 g / cm³. 3 The true density is 2.12 g / cm³. 3 .

[0056] Example 6

[0057] Step 1: Add 250.8g of solvent-de-oiled petroleum asphalt (softening point 104℃), 12.8g of o-isopropylphenol, 12.9g of triphenylformaldehyde and 1.29g of oleic acid imidazoline to the reaction vessel.

[0058] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 150°C for 3 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0059] Step 3: Heat to 270℃, reduce pressure to 20kPa, and distill under reduced pressure for 6 hours to obtain phenolic resin modified asphalt with a softening point of 189℃ and a coking value of 57.38%.

[0060] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1300℃ at 2℃ / min under an argon atmosphere, and carbonize it at high temperature for 4 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0061] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.337 nm, and the Raman spectrum shows an I... G / I D The value is 2.739, and the tap density is 0.992 g / cm³. 3 The true density is 2.04 g / cm³. 3 .

[0062] Example 7

[0063] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 99℃), 25.8g of phenol, 12.9g of furfural and 0.13g of oleic acid imidazoline to the reaction vessel.

[0064] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 150°C for 7 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0065] Step 3: Heat to 300℃, reduce pressure to 40kPa, and distill under reduced pressure for 5 hours to obtain phenolic resin modified asphalt with a softening point of 201℃ and a coking value of 58.69%.

[0066] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1500℃ at 1℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0067] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.769, and the tap density is 1.056 g / cm³. 3 The true density is 2.16 g / cm³. 3 .

[0068] Example 8

[0069] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 104℃), 25.8g of p-methylphenol, 25.9g of benzaldehyde and 0.52g of oleic acid imidazoline to the reaction vessel.

[0070] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 155℃ for 8 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0071] Step 3: Heat to 300℃, reduce pressure to 20kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 191℃ and a coking value of 56.69%.

[0072] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 2.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0073] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.338 nm, and the Raman spectrum shows an I... G / I D The value is 2.131, and the tap density is 0.967 g / cm³. 3 The true density is 1.96 g / cm³. 3 .

[0074] Example 9

[0075] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 117℃), 12.8g of 4-tert-butylphenol, 12.9g of α-naphthaldehyde and 0.90g of rosin-based imidazoline to the reaction vessel.

[0076] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 175°C for 2 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0077] Step 3: Heat to 320℃, reduce pressure to 40kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 224℃ and a coking value of 59.88%.

[0078] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1300℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 4 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0079] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.337 nm, and the Raman spectrum shows an I... G / I D The value is 2.705, and the tap density is 0.989 g / cm³. 3 The true density is 2.07 g / cm³. 3 .

[0080] Example 10

[0081] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 102℃), 25.8g of 4-n-pentylphenol, 12.9g of terephthalaldehyde and 0.60g of DBU to the reaction vessel.

[0082] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 165℃ for 4 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0083] Step 3: Heat to 310℃, reduce pressure to 20kPa, and distill under reduced pressure for 5 hours to obtain phenolic resin modified asphalt with a softening point of 231℃ and a coking value of 61.12%.

[0084] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0085] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.926, and the tap density is 0.982 g / cm³. 3 The true density is 2.06 g / cm³. 3 .

[0086] Example 11

[0087] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 119℃), 25.8g of 4-n-hexylphenol, 24.9g of terephthalaldehyde and 1.99g of indoline to the reaction vessel.

[0088] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 180°C for 3 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0089] Step 3: Heat to 330℃, reduce pressure to 30kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 218℃ and a coking value of 60.37%.

[0090] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0091] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I DThe value is 2.351, and the tap density is 0.977 g / cm³. 3 The true density is 2.00 g / cm³. 3 .

[0092] Example 12

[0093] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 104℃), 12.8g of resorcinol, 12.9g of terephthalaldehyde and 1.16g of indoline to the reaction vessel.

[0094] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 160℃ for 6 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0095] Step 3: Heat to 330℃, reduce pressure to 10kPa, and distill under reduced pressure for 6 hours to obtain phenolic resin modified asphalt with a softening point of 265℃ and a coking value of 65.31%.

[0096] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1400℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0097] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 3.076, and the tap density is 1.032 g / cm³. 3 The true density is 2.13 g / cm³. 3 .

[0098] Example 13

[0099] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 104℃), 25.8g of 2-phenylphenol, 12.9g of terephthalaldehyde and 0.79g of MTBD to the reaction vessel.

[0100] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 170℃ for 4 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0101] Step 3: Heat to 340℃, reduce pressure to 10kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 249℃ and a coking value of 63.26%.

[0102] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1400℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0103] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.337 nm, and the Raman spectrum shows an I... G / I D The value is 2.873, and the tap density is 1.055 g / cm³. 3 The true density is 2.15 g / cm³. 3 .

[0104] Example 14

[0105] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 112℃), 25.8g of catechol, 12.9g of terephthalaldehyde and 0.25g of indoline to the reaction vessel.

[0106] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 165℃ for 5 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0107] Step 3: Heat to 350℃, reduce pressure to 50kPa, and distill under reduced pressure for 4 hours to obtain phenolic resin modified asphalt with a softening point of 244℃ and a coking value of 63.29%.

[0108] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1300℃ at 2.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0109] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.979, and the tap density is 1.009 g / cm³. 3 The true density is 2.09 g / cm³. 3 .

[0110] Example 15

[0111] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 112℃), 25.8g of cashew phenol, 12.9g of terephthalaldehyde and 1.03g of TBD to the reaction vessel.

[0112] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 190℃ for 5 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0113] Step 3: Heat to 350℃, reduce pressure to 40kPa, and distill under reduced pressure for 3 hours to obtain phenolic resin modified asphalt with a softening point of 243℃ and a coking value of 64.19%.

[0114] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1500℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 2.5h to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0115] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.337 nm, and the Raman spectrum shows an I... G / I D The value is 2.786, and the tap density is 1.023 g / cm³. 3 The true density is 2.13 g / cm³. 3 .

[0116] Example 16

[0117] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 125℃), 25.8g of heavy phase residual byproducts from the nonylphenol distillation purification process, 12.9g of 1,4-naphthial dialdehyde, and 1.30g of indoline to the reaction vessel.

[0118] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 200℃ for 2 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0119] Step 3: Heat to 330℃, reduce pressure to 20kPa, and distill under reduced pressure for 6 hours to obtain phenolic resin modified asphalt with a softening point of 255℃ and a coking value of 63.77%.

[0120] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1300℃ at 2.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 5 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0121] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.912, and the tap density is 0.996 g / cm³. 3 The true density is 2.06 g / cm³. 3 .

[0122] Example 17

[0123] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 112℃), 25.8g of bisphenol S, 12.9g of terephthalaldehyde and 1.18g of quinoline to the reaction vessel.

[0124] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 180°C for 4 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0125] Step 3: Heat to 320℃, reduce pressure to 30kPa, and distill under reduced pressure for 4 hours to obtain phenolic resin modified asphalt with a softening point of 225℃ and a coking value of 58.01%.

[0126] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0127] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.276, and the tap density is 0.968 g / cm³. 3 The true density is 2.03 g / cm³. 3 .

[0128] Example 18

[0129] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 112℃), 25.8g of α-naphthol, 12.9g of terephthalaldehyde and 0.65g of cyclohexylamine to the reaction vessel.

[0130] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 170℃ for 6 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0131] Step 3: Heat to 300℃, reduce pressure to 20kPa, and distill under reduced pressure for 6 hours to obtain phenolic resin modified asphalt with a softening point of 238℃ and a coking value of 60.88%.

[0132] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1500℃ at 2.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0133] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.337 nm, and the Raman spectrum shows an I... G / I D The value is 2.763, and the tap density is 1.039 g / cm³. 3 The true density is 2.14 g / cm³. 3 .

[0134] Example 19

[0135] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 112℃), 25.8g of bisphenol A, 12.9g of terephthalaldehyde and 0.83g of quinoline to the reaction vessel.

[0136] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 180°C for 4 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0137] Step 3: Heat to 300℃, reduce pressure to 10kPa, and distill under reduced pressure for 4 hours to obtain phenolic resin modified asphalt with a softening point of 248℃ and a coking value of 62.31%.

[0138] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1200℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0139] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.336 nm, and the Raman spectrum shows an I... G / I D The value is 2.841, and the tap density is 1.003 g / cm³. 3 The true density is 2.08 g / cm³. 3 .

[0140] Example 20

[0141] Step 1: Add 250.8g of solvent-degreased petroleum asphalt (softening point 122℃), 25.8g of bisphenol F, 12.9g of terephthalaldehyde and 0.95g of cyclohexylamine to the reaction vessel.

[0142] Step 2: After slowly heating until the material in the reactor is fully dissolved, stir and react at a constant temperature of 180°C for 3 hours to complete the in-situ polymerization of phenolic resin in petroleum asphalt.

[0143] Step 3: Heat to 340℃, reduce pressure to 10kPa, and distill under reduced pressure for 1 hour to obtain phenolic resin modified asphalt with a softening point of 225℃ and a coking value of 58.01%.

[0144] Step 4: Place the modified petroleum asphalt obtained above into a carbonization furnace, heat it to 1250℃ at 1.5℃ / min under an argon atmosphere, and carbonize it at high temperature for 3 hours to obtain phenolic resin modified petroleum asphalt-based carbon material.

[0145] The phenolic resin-modified petroleum asphalt-based carbon material obtained in this embodiment exhibits a uniform lamellar structure. The 002 interplanar spacing in the X-ray diffraction spectrum is 0.338 nm, and the Raman spectrum shows an I... G / I D The value is 2.276, and the tap density is 0.956 g / cm³. 3 The true density is 1.94 g / cm³. 3 .

[0146] The above-described embodiments are merely illustrative of the implementation methods of the present invention, but should not be construed as limiting the scope of the present invention to these embodiments. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the protection scope of the present invention.

Claims

1. A method for preparing a petroleum asphalt-based highly crystalline soft carbon material, characterized in that, The method first involves melt-blending petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers, and an organic base. Under the catalysis of the organic base, the aromatic phenol monomers and aromatic aldehyde monomers undergo a condensation reaction to obtain in-situ phenolic resin-modified petroleum asphalt. Second, the low-boiling-point fraction is removed by vacuum distillation to controllably prepare high-softening-point phenolic resin-modified petroleum asphalt. Finally, after carbonization, a highly crystalline, structurally controllable layered graphite-like soft carbon material is prepared. By selecting and regulating the types and proportions of petroleum asphalt, aromatic phenol monomers, aromatic aldehyde monomers, and catalysts, controlling the conditions of polymerization reaction and vacuum distillation, and setting the final carbonization temperature and controlling the heating rate, it is possible to regulate the crystallinity and structural dimensions of petroleum asphalt throughout the modification and carbonization process.

2. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 1, characterized in that, Specifically, the steps include the following: 1) Add petroleum asphalt, aromatic phenol monomer, aromatic aldehyde monomer and organic base catalyst to the reactor, wherein the amount of aromatic aldehyde monomer is 5-10 wt% of the mass of asphalt, the amount of aromatic phenol monomer is 5-10 wt% of the mass of asphalt, and the amount of organic base is 1-10 wt% of the mass of aromatic aldehyde monomer. 2) After slowly heating until the materials in the reactor are fully dissolved and mixed, carry out a polycondensation reaction for 2 to 8 hours in the range of 140 to 200°C to obtain in-situ phenolic resin modified petroleum asphalt. 3) The in-situ phenolic resin modified petroleum asphalt obtained in step 2) is subjected to vacuum distillation for 1 to 6 hours at a temperature of 250 to 350℃ and a pressure of 10 to 50 kPa to obtain phenolic resin modified petroleum asphalt with a softening point in the range of 170 to 270℃. 4) The phenolic resin-modified asphalt obtained in step 3) is subjected to carbonization reaction at 1000-1500℃ for 2-5 hours under inert gas protection. After cooling, a layered graphite-like soft carbon material with high crystallinity and controllable structure is obtained.

3. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 2, characterized in that, The petroleum asphalt is one or two of oxidized petroleum asphalt, solvent-de-oiled petroleum asphalt, and blended petroleum asphalt.

4. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 2, characterized in that, The aromatic phenol monomers include one or more of the following: phenol, methylphenol, dimethylphenol, ethylphenol, propylphenol, tert-butylphenol, pentylphenol, hexylphenol, nonylphenol, cashew phenol, bisphenol A, bisphenol F, bisphenol S, phenylphenol, catechol, resorcinol, hydroquinone, naphthol, or naphthol.

5. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 2, characterized in that, The aromatic aldehyde monomers include one or more of furfural, benzaldehyde, naphthal, o-phthalaldehyde, iso-phthalaldehyde, terephthalaldehyde, mestribenzaldehyde, naphthalenedialdehyde and their derivatives.

6. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 2, characterized in that, The organic base catalyst comprises one or more of the following: cyclohexylamine, quinoline, indoline, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), monoalkyl-substituted imidazoles, monoalkyl-substituted imidazolines, polyalkyl-substituted imidazoles, or polyalkyl-substituted imidazolines.

7. The method for preparing a petroleum asphalt-based highly crystalline soft carbon material according to claim 2, characterized in that, The inert protective atmosphere is nitrogen or argon.

8. A petroleum asphalt-based highly crystalline soft carbon material, characterized in that, The highly crystalline soft carbon material is obtained by any one of the preparation methods described in claims 1-7.

9. The application of the petroleum asphalt-based highly crystalline soft carbon material according to claim 8, characterized in that, It can be used as a negative electrode material in environmentally friendly batteries and energy storage devices.

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