CN114806621B - Process for preparing petroleum-based bitumen with high softening point - Google Patents
Process for preparing petroleum-based bitumen with high softening point Download PDFInfo
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- CN114806621B CN114806621B CN202111633817.9A CN202111633817A CN114806621B CN 114806621 B CN114806621 B CN 114806621B CN 202111633817 A CN202111633817 A CN 202111633817A CN 114806621 B CN114806621 B CN 114806621B
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- 239000003208 petroleum Substances 0.000 title claims abstract description 147
- 239000010426 asphalt Substances 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000000034 method Methods 0.000 claims abstract description 194
- 238000010438 heat treatment Methods 0.000 claims abstract description 142
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 123
- 230000003647 oxidation Effects 0.000 claims abstract description 118
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 92
- 230000001590 oxidative effect Effects 0.000 claims description 73
- 239000007789 gas Substances 0.000 claims description 46
- 239000000295 fuel oil Substances 0.000 claims description 29
- 239000000376 reactant Substances 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000197 pyrolysis Methods 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 peroxide compound Chemical class 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011301 petroleum pitch Substances 0.000 description 11
- 238000004939 coking Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 238000003763 carbonization Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 229910021382 natural graphite Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011846 petroleum-based material Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 239000006183 anode active material Substances 0.000 description 3
- 239000011847 coal-based material Substances 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002469 indenes Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
Abstract
The present disclosure relates to a method for preparing petroleum-based asphalt having a high softening point, and more particularly, to a method for preparing petroleum-based asphalt having a high softening point, the method comprising performing an oxidation heat treatment process on petroleum-based residues by using an oxidation heat treatment apparatus including an oxidation reactor, and performing a vacuum heat treatment process on oxidized and heat-treated petroleum-based residues. Here, the ratio of the height and diameter of the oxidation reactor is about 0.5 to about 2, and the content of Quinoline Insolubles (QI) in the petroleum-based asphalt having a high softening point is about 0.001 to about 0.5 wt% based on the total weight of the petroleum-based asphalt having a high softening point.
Description
Technical Field
The present disclosure herein relates to a method for preparing petroleum-based asphalt having a high softening point, and more particularly, to a method for preparing high purity petroleum-based asphalt having a high softening point, which can limit the generation of Quinoline Insolubles (QI) in an oxidative heat treatment process.
Background
Pitch having a high softening point is used as a raw material or precursor material for graphite materials or various carbon materials such as carbon fibers, activated carbon, and negative electrode materials for secondary batteries. Conventionally known methods for preparing asphalt having a high softening point prepare asphalt having a high softening point through an oxidation process and a heat treatment process by using a coal-based material or a petroleum-based material as a raw material.
When asphalt having a high softening point is used as a raw material of a negative electrode material of a secondary battery, as the content of quinoline insoluble substances, inorganic impurities such as metals, or heteroatoms such as nitrogen or sulfur in petroleum-based asphalt having a high softening point is reduced, the capacity, life characteristics, and output characteristics of the battery can be improved. Since the petroleum-based material contains almost no quinoline insolubles, the asphalt having a high softening point prepared by using the petroleum-based material as a raw material contains a smaller amount of quinoline insolubles than the asphalt having a high softening point prepared by using the coal-based material as a raw material, but a small amount of quinoline insolubles is generated in the preparation process. When asphalt having a high softening point is used as a raw material of the anode material, quinoline insolubles generated in the manufacturing process cause degradation of the performance of the secondary battery.
Because the content of quinoline insolubles in the prepared asphalt having a high softening point is high and dangerous substances such as boron compounds, hydrofluoric acid and peroxide compounds are used to prepare asphalt having a high softening point, typical techniques for preparing asphalt having a high softening point by using coal-based materials or petroleum-based materials may not economically prepare asphalt having a high softening point. In particular, when asphalt having a high softening point is prepared by using a petroleum-based material, a method of limiting the generation of quinoline insolubles in the preparation process is not proposed.
Disclosure of Invention
The present disclosure provides a method for economically preparing asphalt having a high softening point.
The present disclosure also provides a method for preparing high quality asphalt having a high softening point in which the content of Quinoline Insoluble (QI) is significantly reduced.
Embodiments of the inventive concept provide a method for preparing petroleum-based asphalt having a high softening point, the method comprising: performing an oxidation heat treatment process on the petroleum-based residue by using an oxidation heat treatment apparatus including an oxidation reactor; and performing a vacuum heat treatment process on the oxidized and heat-treated petroleum-based residue. Here, the ratio of the height and diameter of the oxidation reactor is about 0.5 to about 2, and the content of Quinoline Insolubles (QI) in the petroleum-based asphalt having a high softening point is about 0.001 to about 0.5 wt% based on the total weight of the petroleum-based asphalt having a high softening point.
Drawings
The accompanying drawings are included to provide a further understanding of the inventive concepts, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concept and, together with the description, serve to explain the principles of the inventive concept. In the drawings:
fig. 1 is a flowchart for explaining a method for preparing petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept;
fig. 2 is a schematic view for explaining an oxidation heat treatment device according to an embodiment of the inventive concept;
fig. 3 is a photograph of a negative active material prepared by using the prepared petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept; and
fig. 4 is a schematic process diagram for explaining a method for preparing petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept.
Detailed Description
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings to fully understand the constitution and effects of the present invention. This invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Furthermore, the invention is limited only by the scope of the claims.
In this specification, it will also be understood that when another component is referred to as being "on" one component, it can be directly on the one component or intervening third components may also be present. In addition, in the drawings, the size of components is exaggerated for clarity of illustration. Like numbers refer to like elements throughout.
In addition, although various regions and layers are described using terms such as first, second, and third in various embodiments of the inventive concept, the regions and layers are not limited to these terms. These terms are only used to distinguish one element from another element. The embodiments described and illustrated herein include their complementary embodiments.
In the following description, technical terms are used to illustrate specific exemplary embodiments only, and not to limit the present disclosure. In the specification, unless mentioned to the contrary, singular terms may include plural. Furthermore, the meaning of "comprising," "including," or variations thereof, specify the presence of stated features, regions, integers, steps, processes, elements, and/or components, but do not preclude the presence of other features, regions, integers, steps, processes, elements, and/or components.
Fig. 1 is a flowchart for explaining a method for preparing petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept.
Fig. 2 is a schematic view for explaining an oxidation heat treatment device according to an embodiment of the inventive concept.
Fig. 4 is a schematic process diagram for explaining a method for preparing petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept.
Referring to fig. 1, 2 and 4, a method for preparing petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept may include: a process S1 of performing an oxidation heat treatment process on petroleum-based residues by using an oxidation heat treatment apparatus 1 including an oxidation reactor 100; and a process S2 of performing a vacuum heat treatment process on the oxidized and heat-treated petroleum-based residue.
The petroleum-based residue may have a higher carbonization yield than the carbonization yield of the light oil and a higher aromatic ratio than the aromatic ratio of the light oil. Thus, petroleum-based residues may be suitable as source materials for carbon materials. Petroleum-based residues may have chemical and physical properties that vary depending on the process conditions. The petroleum-based residue may include reactive materials. For example, the reactive material in the petroleum-based residue may include at least one of indene, indene derivatives, styrene, and styrene derivatives.
For example, the petroleum-based residue may include at least one of pyrolysis fuel oil (PFO, pyrolysis fuel oil), naphtha cracking bottoms (NCB, naphtha cracking bottom oil), ethylene bottoms (EBO, ethylene bottom oil), fluid catalytic cracking-decant oil (FCC-DO, fluid catalytic cracking-decont oil), residuum fluid catalytic cracking-decant oil (RFCC-DO, residue fluid catalytic cracking-decont oil), aromatic Extract (AE), and hydrogen-treated petroleum-based residue (hydro-treated petroleum-based residue).
The method for preparing petroleum-based asphalt having a high softening point may further include a process of performing a pretreatment process on the petroleum-based residue and a process of injecting the pretreated petroleum-based residue into the oxidation reactor before performing the oxidation heat treatment process. The petroleum-based residue may be used as a raw material for preparing asphalt having a high softening point through a pretreatment process. More specifically, the light oil in the petroleum-based residue may be removed by a pretreatment process. In general, the properties of asphalt having a high softening point can be easily changed according to various properties of raw materials for preparing asphalt having a high softening point. According to embodiments of the inventive concept, when light oil in petroleum-based residues is removed through a pretreatment process, properties of asphalt having a high softening point can be maintained relatively uniformly. Accordingly, a subsequent oxidation heat treatment process or a subsequent vacuum heat treatment process can be easily performed. Further, since the reactive substances contained in the light oil, such as indene, indene derivatives, styrene, and styrene derivatives, are removed by the pretreatment process, the amount of Quinoline Insoluble (QI) generated in the oxidative heat-treatment reaction can be reduced. In the present specification, quinoline Insoluble (QI) may represent solid particles insoluble in a quinoline solvent. In general, when asphalt having a high softening point is prepared from petroleum-based residues, quinoline Insolubles (QI) are generated in the preparation process. Unlike the embodiments of the inventive concept, when asphalt having a high softening point, which has a high content of Quinoline Insolubles (QI), is used as a raw material of a negative electrode material of a secondary battery, the performance of the secondary battery may be deteriorated.
The oxidation heat treatment device 1 may include an oxidation reactor 100, an oxidation gas supply part 110, an inert gas supply part 120, a gas supply part 130, a stirring part 140, an electric heater 150, first to third flow rate measurement parts 161, 162, and 163, first to third flow rate adjustment valves 171, 172, and 173, a circulation pump 180, a heating jacket 190, an upper temperature sensor 200, a middle temperature sensor 210, and a lower temperature sensor 220.
The oxidizing gas supply portion 110 may supply the oxidizing gas to the gas supply portion 130. For example, the oxidizing gas may include at least one of air, oxygen, and ozone. For example, air in the atmosphere may be directly used as the oxidizing gas.
The inert gas supply part 120 may supply inert gas to the gas supply part 130. For example, the inert gas may include at least one of nitrogen and argon.
The gas supply part 130 may be disposed between the oxidizing gas supply part 110 and the oxidation reactor 100 and between the inert gas supply part 120 and the oxidation reactor 100. An oxidizing gas or an inert gas may be charged into the oxidation reactor 100 through the gas supply part 130. In an embodiment, only the oxidizing gas may be charged into the oxidation reactor 100. In another embodiment, the oxidation reactor 100 may be charged with an oxidizing gas and an inert gas. In this case, the oxidizing gas may be diluted with an inert gas. For example, the concentration of oxygen may be adjusted by diluting the oxygen with nitrogen.
The oxidizing gas may have a flow rate of about 0.01L/min to about 1L/min based on about 1kg of the petroleum-based residue. When the flow rate of the oxidizing gas exceeds about 1L/min based on about 1kg of the petroleum-based residue, the concentration of oxygen reacting with the vaporized aromatic hydrocarbon increases, and the amount of Quinoline Insolubles (QI) formed on the inner wall of the oxidation reactor 100 increases.
The first flow measurement part 161 may be disposed between the oxidizing gas supply part 110 and the gas supply part 130, and the second flow measurement part 162 may be disposed between the inert gas supply part 120 and the gas supply part 130. The first flow rate adjustment valve 171 may be disposed between the first and second flow rate measurement portions 161 and 162 and the gas supply portion 130. The flow rate of the oxidizing gas supply portion 110 may be measured by the first flow measurement portion 161, and the flow rate of the inert gas supply portion 120 may be measured by the second flow measurement portion 162. The flow rate of the oxidizing gas or the inert gas charged into the gas supply part 130 may be adjusted by the first flow rate adjusting valve 171.
The oxidation reactor 100 may be a reactor in which an oxidative heat treatment process is performed on petroleum-based residues. The oxidation heat treatment process may be performed by using the oxidation heat treatment device 1 including the oxidation reactor 100. The oxidative heat treatment process may include a process of heating an oxidizing gas and a petroleum-based residue, which are reactants of the oxidative heat treatment process.
For example, the temperature of the reactants of the oxidative heat treatment process may be in the range of about 250 ℃ to about 400 ℃. In the present specification, the temperature of the reactant in the oxidation heat treatment process may represent the temperature of the portion filled with the reactant of the oxidation heat treatment process, for example, the temperature measured by the lower temperature sensor 220. However, when the temperature of the reactants in the oxidative heat-treatment process is lower than about 250 ℃, the yield of asphalt having a high softening point as a final product may be lowered because the molecular weight of the petroleum-based residue is not sufficiently increased. In addition, when the temperature of the reactant in the oxidative heat-treatment process is higher than about 400 ℃, a coking phenomenon occurs due to a rapid increase in the content of quinoline in the reactant insoluble in the oxidative heat-treatment process.
For example, the oxidative heat treatment process may have a process time in the range of from about 1 hour to about 20 hours. When the process time of the oxidative heat-treatment process is less than about 1 hour, the oxidation reaction may not be sufficiently generated. Further, when the process time of the oxidative heat-treatment process is more than about 20 hours, excessive polymerization reaction may be caused, and properties of asphalt having a high softening point may be changed. In particular, when the oxidation reaction is excessively performed, the oxygen content of asphalt having a high softening point may increase. Therefore, when asphalt having a high softening point is used as a raw material of a negative electrode material of a secondary battery, the performance of the secondary battery may deteriorate. In addition, when the excessive polymerization of the aromatic compound is performed upon heat-treating the petroleum-based residue under high temperature conditions or oxidation reaction conditions, the petroleum-based residue may be converted into insoluble materials.
For example, the ratio of the height L to the diameter D (L/D) of the oxidation reactor 100 may be in the range of about 0.5 to about 2. When performing an oxidative heat treatment reaction on petroleum-based residues, petroleum may be vaporized and exposed to oxidizing gases. When the oxidation heat treatment reaction is performed by mixing the petroleum-based residue with the oxidizing gas, aromatic hydrocarbons volatilized at high temperature may react with the oxidizing gas, and quinoline insoluble substances (QI) may be adsorbed onto the inner wall of the oxidation reactor 100. For example, the amount of Quinoline Insoluble (QI) adsorbed to the inner wall of the oxidation reactor 100 may be greater than the amount of Quinoline Insoluble (QI) generated from the inside of the reactants of the oxidative heat treatment process.
According to an embodiment of the inventive concept, since the ratio (L/D) of the height L and the diameter D of the oxidation reactor 100 is in the range of about 0.5 to about 2, the amount of impurities in the petroleum-based asphalt having a high softening point can be reduced and at the same time, the oxidation heat treatment reaction can be effectively performed. However, when the ratio (L/D) of the height L and the diameter D of the oxidation reactor 100 is greater than about 2, the internal area of the reactor in which quinoline insolubles are formed may be increased, and as a result, the amount of impurities in the petroleum-based asphalt having a high softening point may be increased. In addition, when the ratio (L/D) of the height L and the diameter D of the oxidation reactor 100 is less than about 0.5, as the diameter D of the oxidation reactor increases, heat transfer according to a temperature gradient in the reactor may be difficult, and thus, the efficiency of the oxidation reaction may be lowered.
An upper temperature sensor 200, a middle temperature sensor 210, and a lower temperature sensor 220 may be disposed in the oxidation reactor 100. The upper temperature sensor 200 may be disposed at an upper portion in the oxidation reactor 100. A lower temperature sensor 220 may be provided at a lower portion in the oxidation reactor 100. The middle temperature sensor 210 may be disposed between the upper temperature sensor 200 and the lower temperature sensor 220.
The middle temperature sensor 210 may regulate the temperature of the middle in the oxidation reactor 100. The lower temperature sensor 220 may regulate the temperature of the lower portion of the oxidation reactor 100. The upper temperature sensor 200 may regulate the temperature of the upper portion in the oxidation reactor 100. For example, the temperature of the upper portion in the oxidation reactor 100 may be maintained in the range of about 250 ℃ to about 370 ℃ or in the range of about 280 ℃ to about 360 ℃. In the present specification, the upper part in the oxidation reactor may represent a portion in which the reactants of the oxidation heat treatment process are not filled. For this purpose, the oxidation heat treatment device 1 may further include heating portions for independently heating the upper and lower portions of the oxidation reactor 100. When the temperature of the upper portion in the oxidation reactor 100 is greater than about 370 c, the rate of polymerization reaction generated by volatilized aromatic hydrocarbon and oxidizing gas increases rapidly. Therefore, the amount of Quinoline Insoluble (QI) adsorbed in the oxidation reactor 100 increases rapidly. Furthermore, the temperature of the upper portion in the oxidation reactor may be less than the temperature of the reactants of the oxidative heat treatment process.
In general, catalysts as well as oxidizing gases and peroxide-based compounds can be used under high pressure conditions to increase the softening point of bitumen with a high softening point as the final product. However, when the catalyst is used under high pressure conditions, the cost of producing asphalt having a high softening point increases because an expensive high pressure vessel is required and a separate process for removing the catalyst is required. In addition, when the peroxide-based compound is additionally mixed into the oxidizing gas, there is a risk of explosion during the preparation process due to the high reactivity of the peroxide-based compound, and the cost of the peroxide-based compound, the hazardous material management cost, and the wastewater treatment cost are increased. Thus, the economic efficiency of preparing a large amount of asphalt having a high softening point is reduced.
According to embodiments of the inventive concept, the molecular weight of the petroleum-based residue may be increased by an oxidative heat treatment process, and the yield of asphalt having a high softening point as a final product may be improved. In particular, since high pressure conditions may not be required in the oxidative heat treatment process and a catalyst may not be used, an economical and high quality petroleum-based asphalt having a high softening point may be prepared. Furthermore, according to an embodiment of the inventive concept, the peroxide-based compound may not be charged into the oxidation reactor 100 before or during the oxidation heat treatment process is performed. Since peroxide-based compounds are not used, the preparation method can be economical and explosion risks during the preparation process can be prevented.
The stirring portion 140 may be provided in the oxidation reactor 100. The reactants of the oxidative heat treatment process may be smoothly mixed by the stirring part 140.
When the heating jacket 190 is disposed on the outer wall of the oxidation reactor 100, the heating jacket 190 may cover a portion of the outer wall of the oxidation reactor 100. The heating jacket 190 may perform an insulating function, an electrical insulating function, or a warming function of the oxidation reactor 100.
The circulation pump 180 may be connected to the oxidation reactor 100. For example, the circulation pump 180 may be connected to the lower portion of the oxidation reactor 100. Reactants of the oxidative heat treatment process may be injected into the electric heater 150 through the circulation pump 180. The electric heater 150 may be connected to the circulation pump 180. That is, the circulation pump 180 may be disposed between the oxidation reactor 100 and the electric heater 150. The third flow rate measuring part 163 and the second flow rate regulating valve 172 may be disposed between the circulation pump 180 and the electric heater 150. The third flow rate measuring part 163 may be disposed adjacent to the circulation pump 180, and the second flow rate regulating valve 172 may be disposed adjacent to the electric heater 150. The third flow rate measuring part 163 may measure the flow rate of the reactant of the oxidation heat treatment process injected into the electric heater 150. The second flow rate adjustment valve 172 may adjust the flow rate of the reactants of the oxidative heat treatment process injected into the electric heater 150. The electric heater 150 may heat the reactants of the oxidative thermal treatment process. Reactants of the oxidation heat treatment process heated by the electric heater 150 may be re-injected into the oxidation reactor 100. For example, reactants of the oxidation heat treatment process heated by the electric heater 150 may be injected into the upper portion of the oxidation reactor 100. The third flow rate adjustment valve 173 may be disposed between the electric heater 150 and the upper portion of the oxidation reactor 100. The flow rate of the reactants of the oxidation heat treatment process injected into the upper portion of the oxidation reactor 100 may be adjusted by a third flow rate adjusting valve 173.
Petroleum-based asphalt may be prepared from oxidized and heat-treated petroleum-based residues by an oxidative heat treatment process. Hereinafter, in the present specification, the petroleum-based asphalt may represent petroleum-based residues oxidized and heat-treated by an oxidation heat treatment process. A vacuum heat treatment process may be performed on the petroleum-based residue. The vacuum heat treatment process may include a process of heating the petroleum-based residue under vacuum. The vacuum heat treatment process may be performed in a reduced pressure heat treatment apparatus.
In embodiments of the inventive concept, the vacuum heat treatment process may remove heavy oil of petroleum-based asphalt, increase a softening point, and increase the content of toluene insolubles, thereby increasing carbonization yield of asphalt. Unlike embodiments of the inventive concept, when an atmospheric heat treatment process or a pressing heat treatment process is performed on petroleum-based asphalt instead of a vacuum heat treatment process, it may be difficult to remove heavy oil, and the softening point of asphalt may not be increased.
For example, the vacuum heat treatment process may have a pressure in the range of about 1 torr to about 300 torr, about 1 torr to about 200 torr, or about 1 torr to about 100 torr. For example, the vacuum heat treatment process may have a heat treatment temperature in the range of about 300 ℃ to about 430 ℃. When the heat treatment temperature of the vacuum heat treatment process is less than about 300 ℃, it may be difficult to remove heavy oil, and as the generation of toluene insolubles is reduced, it may be difficult to prepare high quality asphalt having a high softening point. Further, since heavy oil in asphalt is not sufficiently removed, there is a limit to increasing the softening point of petroleum-based asphalt. When the heat treatment temperature of the vacuum heat treatment process is greater than about 430 c, a coking phenomenon of petroleum-based asphalt occurs to provide coke, or the content of Quinoline Insoluble (QI) increases rapidly.
For example, the vacuum heat treatment process may have a process time in the range of from about 1 hour to about 20 hours or from about 2 hours to about 10 hours. When the process time of the vacuum heat treatment process is less than about 1 hour, heavy oil may not be sufficiently removed, and thus it may be difficult to prepare asphalt having a high softening point. In addition, toluene insolubles may not be sufficiently produced due to lack of thermal polymerization reaction time, and low quality asphalt having a high softening point and a low carbonization yield may be produced. When the process time of the vacuum heat treatment process is more than about 20 hours, toluene insolubles may be excessively generated as the polymerization reaction is excessively performed, and as the process time increases, the cost of operating the process and the cost of preparing the product may increase.
The vacuum heat treatment process may also include a process of mixing inert gas or steam (steam). Heavy oil in petroleum-based asphalt can be effectively removed in a vacuum heat treatment apparatus through a vacuum heat treatment process. For example, the inert gas may include at least one of nitrogen and argon.
For example, the flow rate of the inert gas or steam may be in the range of about 0.01L/min to about 2.0L/min based on about 1kg of petroleum-based bitumen. Unlike embodiments of the inventive concept, when an oxidizing gas is charged while a vacuum heat treatment process is performed, quinoline insolubles are rapidly formed through an oxidation reaction at a high temperature. Therefore, according to an embodiment of the inventive concept, an inert gas or steam may be filled in the vacuum heat treatment process. In particular, heavy oil can be further effectively removed when heated and filled with inert gas or steam.
The method for preparing a petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept may further perform an atmospheric pressure heat treatment process on the petroleum-based asphalt after the vacuum heat treatment process. The toluene insoluble matter content of petroleum-based asphalt having a high softening point can be increased by an atmospheric pressure heat treatment process. For example, the atmospheric pressure heat treatment process may have a heat treatment temperature in the range of about 300 ℃ to about 430 ℃. When the heat treatment temperature of the atmospheric heat treatment process is less than about 300 c, heavy oil toluene insolubles may not be generated. When the heat treatment temperature of the atmospheric heat treatment process is greater than about 430 ℃, coking of petroleum-based asphalt may occur to provide coke, or the content of quinoline insoluble may rapidly increase.
For example, the atmospheric pressure heat treatment process may have a process time in the range of about 30 minutes to about 20 hours. When the process time of the atmospheric pressure heat treatment process is less than about 30 minutes, toluene insolubles may not be sufficiently produced. When the process time of the atmospheric pressure heat treatment process is more than about 20 hours, the cost of operating the process and the cost of preparing the product may increase with the increase of the process time.
The petroleum-based asphalt having a high softening point, prepared by the method for preparing the petroleum-based asphalt having a high softening point according to an embodiment of the inventive concept, may have a softening point in a range of about 150 ℃ to about 300 ℃. For example, the content of Quinoline Insolubles (QI) of the petroleum-based asphalt having a high softening point may be equal to or less than about 0.5 wt%, or in the range of about 0.001 wt% to about 0.5 wt%, based on the total weight of the petroleum-based asphalt having a high softening point. That is, according to embodiments of the inventive concept, petroleum-based asphalt having a high softening point may have a high softening point while reducing the content of quinoline insolubles therein.
According to an embodiment of the inventive concept, the petroleum-based pitch having a high softening point may be prepared by using the petroleum-based residue as a raw material through an oxidation heat treatment process and a vacuum heat treatment process, and the petroleum-based pitch having a high softening point may be used as a raw material of a carbon material or a graphite material and a precursor material of the carbon material or the graphite material. For example, the carbon material or the graphite material may include carbon fiber, activated carbon, a negative electrode material of a secondary battery.
In general, when petroleum-based asphalt having a high softening point is used as a raw material of a negative electrode material of a secondary battery, the performance of the secondary battery may be deteriorated due to quinoline insolubles. That is, as the content of quinoline insolubles, inorganic impurities such as metals, or heteroatoms such as nitrogen or sulfur in the petroleum-based asphalt having a high softening point is reduced, the capacity, life characteristics, and output characteristics of the battery may be improved.
Since the petroleum-based asphalt having a high softening point, which is prepared by the method for preparing the petroleum-based asphalt having a high softening point according to the embodiment of the inventive concept, has a high softening point and at the same time has a reduced content of quinoline insolubles, the performance of the secondary battery may be improved by using the petroleum-based asphalt having a high softening point as a raw material of the negative electrode material of the secondary battery.
In an embodiment, petroleum-based pitch having a high softening point may be used as a binder material or a coating material of a negative electrode material (e.g., a natural graphite negative electrode material or an artificial graphite negative electrode material). In another embodiment, the carbonization process may be performed on petroleum-based pitch having a high softening point to be used as the carbon negative electrode material.
In addition, the petroleum-based pitch having a high softening point prepared by the method according to the embodiments of the inventive concept may be used as a precursor material through a carbonization process and a graphitization process. When the petroleum-based pitch having a high softening point according to embodiments of the inventive concept is used as a precursor material of carbon fibers, the prepared carbon fibers may have improved properties such as tensile strength and tensile modulus by a high softening point and carbonization yield and a low content of quinoline insolubles of the petroleum-based pitch having a high softening point.
In addition, the petroleum-based pitch having a high softening point prepared by the method according to the embodiments of the inventive concept may be used as a precursor material of activated carbon through a carbonization process and an activation process. Since the petroleum-based asphalt having a high softening point according to the embodiments of the inventive concept has a high softening point, a high carbonization yield, high mechanical properties, and a low impurity content, the prepared activated carbon may have improved specific surface area and mechanical strength.
Examples
Example 1
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 1.6. The oxidative heat treatment process was performed by charging air at a flow rate of about 0.5L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 370 c and the upper portion in the oxidation reactor has a temperature of about 350 c. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 251 deg.c, the content of quinoline insolubles was about 0.08 wt% based on the total weight of the petroleum-based asphalt having a high softening point, and the coking value was about 65 wt%.
Example 2
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 1.6. The oxidative heat treatment process was performed by charging air at a flow rate of about 0.2L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 370 c and the upper portion in the oxidation reactor has a temperature of about 350 c. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 254 ℃, the content of quinoline insolubles was about 0.02 wt% and the coking value was about 64 wt% based on the total weight of the petroleum-based asphalt having a high softening point.
Example 3
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 1.6. The oxidative heat treatment process was performed by charging air at a flow rate of about 0.5L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 370 c and the upper portion of the oxidation reactor has a temperature of about 360 c. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 254 ℃, the content of quinoline insolubles was about 0.24 wt% and the coking value was about 68 wt% based on the total weight of the petroleum-based asphalt having a high softening point.
Comparative example 1
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 2.5. The oxidative heat treatment process was performed by charging air at a flow rate of about 0.5L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 370 c and the upper portion in the oxidation reactor has a temperature of about 350 c. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 245 ℃, the content of quinoline insolubles was about 0.76 wt% and the coking value was about 66 wt% based on the total weight of the petroleum-based asphalt having a high softening point.
Comparative example 2
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 1.6. The oxidative heat treatment process was performed by charging air at a flow rate of about 0.5L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 380 ℃ and the upper portion in the oxidation reactor has a temperature of about 380 ℃. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 244 deg.c, the content of quinoline insolubles was about 1.06 wt% based on the total weight of the petroleum-based asphalt having a high softening point, and the coking value was about 64 wt%.
Comparative example 3
Pyrolysis Fuel Oil (PFO) is used as petroleum-based residue and air is used as oxidizing gas. Pyrolysis Fuel Oil (PFO) is injected into an oxidation reactor in which the ratio (L/D) of height (L) to diameter (D) is about 1.6. The oxidative heat treatment process was performed by charging air at a flow rate of about 1.5L/min based on about 1kg of Pyrolysis Fuel Oil (PFO). The reactants of the oxidative heat treatment process have a temperature of about 370 c and the upper portion of the oxidation reactor has a temperature of about 360 c. The oxidation heat treatment process was performed for about 4 hours.
Thereafter, petroleum-based asphalt having a high softening point is prepared by depressurizing to a pressure of about 80 torr at a temperature of about 400 ℃ and performing a vacuum heat treatment process for about 10 hours. The softening point of the prepared petroleum-based asphalt having a high softening point was about 248 deg.c, the content of quinoline insolubles was about 0.93 wt% based on the total weight of the petroleum-based asphalt having a high softening point, and the coking value was about 58 wt%.
The ratio (L/D) of the height (L) and diameter (D) of the oxidation reactor, the temperature of the upper part in the oxidation reactor, the flow rate of the oxidizing gas, and the properties of the petroleum-based asphalt having a high softening point in the oxidation heat treatment processes of examples 1 to 3 and comparative examples 1 to 3 are described in table 1 below.
[ Table 1 ]
Referring to table 1 above, it can be understood that the petroleum-based asphalt having a high softening point of examples 1 to 3 has a high softening point of about 200 ℃, a quinoline insoluble content of about 0.5% by weight or less, and a high coking value of about 60% or more.
Although comparative example 1 uses the same petroleum-based residue as in example 1, as the ratio (L/D) of the oxidation reactor increases, the adsorption amount of quinoline insoluble matters in the oxidation reactor increases, and as a result, the impurity content in the petroleum-based asphalt having a high softening point may be high.
Although comparative example 2 uses the same petroleum-based residue and the same size oxidation reactor as in example 1, since the upper portion of the oxidation reactor has a high temperature to increase the reaction rate between the aromatic hydrocarbon material and the oxidizing gas, the amount of quinoline insoluble matters generated may increase, and as a result, the impurity content in the petroleum-based asphalt having a high softening point may be high.
Although comparative example 3 uses the same petroleum-based residue and the same size oxidation reactor as in example 3, since the flow rate of the oxidizing gas charged into the oxidation reactor is increased, the content of quinoline insoluble matters generated by the polymerization reaction is increased with the increase in the amount of oxygen reacted when the aromatic hydrocarbon substances volatilize, and as a result, the impurity content in the petroleum-based asphalt having a high softening point is high.
Experimental example
Experimental example 1: preparation of secondary batteries Using Petroleum-based asphalt having high softening Point prepared according to example 1
A secondary battery was prepared by using the petroleum-based asphalt having a high softening point prepared according to example 1 as a coating material of a negative electrode material of the secondary battery.
Specifically, about 5g of petroleum-based pitch having a high softening point prepared according to example 1 was mixed with about 95g of spherical natural graphite having an average diameter of about 15 μm. Thereafter, the surface of the natural graphite was coated with petroleum-based pitch having a high softening point by using a mechanical stirring device. After the coating was completed, the anode active material was prepared by performing heat treatment at a temperature of about 1,100 ℃ for about 1 hour.
The shape of the negative electrode active material prepared by using the petroleum-based asphalt having a high softening point prepared according to example 1 is shown in fig. 3. It can be checked that natural graphite is uniformly coated with petroleum-based pitch having a high softening point.
A composition for a negative electrode slurry was prepared by a negative electrode active material prepared by using the petroleum-based asphalt having a high softening point prepared according to example 1. Specifically, a composition for an anode slurry was prepared by mixing an anode active material, carbon black, carboxymethyl cellulose, and styrene butadiene into water in a weight ratio of the anode active material to the carbon black to the carboxymethyl cellulose to the styrene butadiene of about 91:5:2:2. A negative electrode of a secondary battery was prepared by coating a copper current collector with a composition for a negative electrode slurry and performing drying and pressing for about 1 hour.
Thereafter, by sequentially stacking a negative electrode, a separator, an electrolyte, and a lithium electrode for a secondary batteryTo prepare a button cell type secondary battery. Here, the electrolyte is one in which ethylene carbonate and dimethyl carbonate are mixed in a weight ratio of about 1:1 and 1.0M LiPF is added 6 Is a solvent of (a) and (b).
Experimental example 2: preparation of secondary batteries using petroleum-based asphalt having high softening point prepared according to comparative example 2
A secondary battery was prepared by using the petroleum-based asphalt having a high softening point prepared according to comparative example 2 as a coating material of a negative electrode material of the secondary battery.
The petroleum-based asphalt having a high softening point prepared according to comparative example 2 was used instead of using the petroleum-based asphalt having a high softening point prepared according to example 1, and except for this, a secondary battery was prepared by substantially the same method as that of experimental example 1.
Experimental example 3: measurement of charge and discharge capacity and initial efficiency of secondary battery
The properties of secondary batteries prepared by using the petroleum-based asphalt having a high softening point prepared according to example 1 and comparative example 2 as a coating material of a negative electrode material of the secondary batteries were measured.
Specifically, the charge and discharge capacity and initial efficiency of each prepared secondary battery were measured according to the following conditions. Specifically, the charging is performed at a constant current of about 0.2C up to about 0.01V, and at a constant voltage of about 0.01C up to about 0.01C. Thereafter, discharge was performed at a constant current of about 0.2C up to about 1.5V. The above procedure was repeated by the 1 st cycle, the 50 th cycle and the 100 th cycle, and the initial efficiency and discharge capacity of each cycle were measured. The results are shown in table 2 below.
[ Table 2 ]
Referring to table 2 above, when the petroleum-based asphalt having a high softening point prepared according to comparative example 2 was used as a coating material for natural graphite, the discharge capacity was small, and the initial efficiency was also lower than that in the case where the petroleum-based asphalt having a high softening point prepared according to example 1 was used as a coating material for natural graphite. This result can be obtained because the petroleum-based asphalt having a high softening point prepared according to comparative example 2 has a higher content of quinoline insolubles than the petroleum-based asphalt having a high softening point prepared according to example 1.
The method for preparing petroleum-based asphalt having a high softening point according to the embodiments of the inventive concept can significantly reduce quinoline insolubles formed in the preparation process, and thus prepare high quality petroleum-based asphalt having a high softening point with a small amount of impurities.
Because a catalyst and high pressure conditions are unnecessary, the method for preparing petroleum-based asphalt having a high softening point according to the embodiments of the inventive concept may not require a separate process of removing the catalyst, and may not use an expensive high pressure vessel. In addition, since the peroxide-based compound is not used, the method may not have a risk of explosion during the preparation process and may not cause environmental pollution. Thus, high quality petroleum-based asphalt having a high softening point can be economically produced.
Since the petroleum-based asphalt having a high softening point prepared by the method for preparing the petroleum-based asphalt having a high softening point according to the embodiment of the inventive concept reduces the content of quinoline insolubles, the capacity, life, and charge and discharge efficiency of the secondary battery to which the petroleum-based asphalt having a high softening point is applied can be improved.
Although the exemplary embodiments of the present invention have been described, it is understood that the present invention should not be limited to these exemplary embodiments, but various changes and modifications can be made by one of ordinary skill in the art within the spirit and scope of the present invention as hereinafter claimed.
Claims (13)
1. A process for preparing a petroleum-based asphalt having a high softening point, the process comprising the steps of:
performing an oxidation heat treatment process on the petroleum-based residue by using an oxidation heat treatment apparatus, the oxidation heat treatment apparatus including an oxidation reactor; and
a vacuum heat treatment process is performed on the oxidized and heat treated petroleum-based residue,
wherein the ratio of the height to the diameter of the oxidation reactor is from 0.5 to 2,
the content of quinoline insoluble in the petroleum-based asphalt having a high softening point is 0.001 to 0.5% by weight based on the total weight of the petroleum-based asphalt having a high softening point,
the method further comprises charging an oxidizing gas to the oxidation reactor prior to performing the oxidative thermal treatment process,
wherein the flow rate of the oxidizing gas is 0.01L/min to 1L/min based on 1kg of the petroleum-based residue, and the temperature of the upper part in the oxidation reactor is maintained in the range of 250 ℃ to 370 ℃, and
wherein the petroleum-based asphalt having a high softening point has a softening point of 150 ℃ to 300 ℃.
2. The method according to claim 1, wherein the oxidation heat treatment device further comprises an upper temperature sensor provided at an upper portion in the oxidation reactor and a heating portion configured to independently heat the upper portion and the lower portion of the oxidation reactor,
wherein the upper temperature sensor regulates the temperature of the upper portion in the oxidation reactor.
3. The method of claim 1, wherein the oxidative thermal treatment apparatus further comprises a gas supply configured to supply an oxidizing gas or an inert gas to the oxidation reactor.
4. The method of claim 3, wherein the oxidizing gas comprises at least one of air, oxygen, and ozone, and
the inert gas includes at least one of nitrogen and argon.
5. The method of claim 1, wherein the petroleum-based residue comprises at least one of pyrolysis fuel oil, naphtha cracking bottoms, ethylene bottoms, fluid catalytic cracking-decant oil, resid fluid catalytic cracking-decant oil, aromatic extract, and hydrogen-treated petroleum-based residue.
6. The method of claim 1, the method further comprising: before the oxidation heat treatment process is performed,
performing a pretreatment process on the petroleum-based residue; and
the petroleum-based residue after the pretreatment process is injected into an oxidation reactor,
wherein the light oil in the petroleum-based residue is removed by a pretreatment process.
7. The method according to claim 1, wherein the temperature of the reactants of the oxidative heat treatment process is 250 ℃ to 400 ℃, and
the process time of the oxidation heat treatment process is 1 to 20 hours.
8. The method of claim 1, wherein the vacuum heat treatment process has a pressure of 1 torr to 300 torr,
the heat treatment temperature of the vacuum heat treatment process is 300 ℃ to 430 ℃, and
the process time of the vacuum heat treatment process is 1 to 20 hours.
9. The method of claim 1, wherein the vacuum heat treatment process further comprises mixing an inert gas or steam,
wherein the inert gas includes at least one of nitrogen and argon.
10. The method of claim 1, further comprising performing an atmospheric pressure heat treatment process on the petroleum-based residue after performing the vacuum heat treatment process,
wherein the toluene insoluble matter content in the petroleum-based asphalt having a high softening point is increased by an atmospheric pressure heat treatment process.
11. The method according to claim 10, wherein the heat treatment temperature of the atmospheric heat treatment process is 300 ℃ to 430 ℃, and
the process time of the atmospheric pressure heat treatment process is 3 minutes to 20 hours.
12. The method of claim 1, wherein the peroxide compound is not charged to the oxidation reactor.
13. The method of claim 1, wherein the temperature of the upper portion of the oxidation reactor is less than the temperature of the reactants of the oxidative thermal treatment process.
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| KR1020210006931A KR20220105211A (en) | 2021-01-18 | 2021-01-18 | The manufacturing method for petroleum-based high softening point pitch |
| KR10-2021-0006931 | 2021-01-18 |
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| EP (1) | EP4029923A1 (en) |
| JP (1) | JP7253031B2 (en) |
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| KR20240022341A (en) * | 2022-08-11 | 2024-02-20 | 오씨아이 주식회사 | The manufacturing method for petroleum-based high softening point pitch |
| WO2024034928A1 (en) * | 2022-08-11 | 2024-02-15 | 오씨아이 주식회사 | Method for producing petroleum-based high softening point pitch |
| WO2024071623A1 (en) * | 2022-09-28 | 2024-04-04 | 오씨아이 주식회사 | Method for producing petroleum-based high-softening-point pitch |
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| US5429739A (en) * | 1992-08-25 | 1995-07-04 | Ashland Inc. | Pitch precursor production by distillation |
| JPH08134468A (en) * | 1994-11-07 | 1996-05-28 | Showa Shell Sekiyu Kk | Production of isotropic pitch for carbon fiber |
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| CN102453491A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of softening-point-controlled oxidation asphalt product |
| KR101916392B1 (en) * | 2016-12-27 | 2018-11-09 | 한국화학연구원 | A method of preparing impregnating pitch from petroleum material and impregnating pitch prepared using the same |
| KR102030002B1 (en) * | 2017-11-21 | 2019-10-08 | 한국화학연구원 | Apparatus and method to collect samples from pitch synthesis reactors |
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| US4671864A (en) * | 1982-12-03 | 1987-06-09 | Ashland Oil, Inc. | Process for the manufacture of carbon fibers and feedstock therefor |
| GB2156378A (en) * | 1984-03-26 | 1985-10-09 | Idemitsu Kosan Co | Pitch materials |
| CN105602597A (en) * | 2014-10-17 | 2016-05-25 | Oci有限公司 | High-purity pitch as carbonaceous raw material, and manufacturing method thereof |
| WO2018088765A1 (en) * | 2016-11-08 | 2018-05-17 | 한국화학연구원 | Method for preparing isotropic pitch having high softening point, and carbon fiber comprising same |
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| Publication number | Publication date |
|---|---|
| JP2022111062A (en) | 2022-07-29 |
| KR20220105211A (en) | 2022-07-27 |
| EP4029923A1 (en) | 2022-07-20 |
| CN114806621A (en) | 2022-07-29 |
| JP7253031B2 (en) | 2023-04-05 |
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