The spherical mesophases are the main precursors for the high tap density of carbonaceous anode batteries. However, it is challenging to control mesophase size without coalescence and no deformation since it quickly coalesces into a regular large sphere. Here, we propose a feasible extraction method to refine the spherical size of mesophase using benzene. Thermogravimetric and differential scanning calorimetry analysis of untreated pitch revealed that the maximum temperature for mesophase nucleation should not exceed 410 °C to provoke the nucleation of mesophase spheres while maintaining a high pyrolysis yield. The extraction results showed that the extraction weight tends to decrease with an increase in the solvent ratio. There is an exponential relationship between the influence of solvent ratio and the ability for extraction. The solubility of the spherical mesophase in benzene is size-dependent and can dissolve selectively spherical mesophases smaller than 5 μm. Consequently, a monodisperse spherical mesophase was obtained. The reason for forming uniform mesophase spheres can be explained by their thermodynamic state, as described by the “two-step” classical nucleation theory. Benzene effectively improves the size distribution of spherical mesophase by dissolving small sizes while retaining large ones.

It is difficult to optimize the process parameters of directly preparing carbonaceous mesophase (CMs) by solvothermal method using coal tar as raw material. To solve this problem, a Decision Tree model for CMs preparation (DTC) was established based on the relationship between the process parameters and the yields of CMs. Then, the importance of variables in the preparation process for CMs was predicted, the relationship between experimental conditions and yields was revealed, and the preparation process conditions were also optimized by the DTC. The prediction results showed that the importance of the variables was raw material type, solvothermal temperature, solvothermal time, solvent amount, and additive type in order. And the optimized reaction conditions were as follows: coal tar was pretreated by decompress distillation and centrifugation, the solvent amount was 50.0 ml, the solvothermal temperature was 230 °C, and the reaction time was 5 h. These prediction results were consistent with the actual experimental results, and the error between the predicted yields and the actual yields was about − 1.1%. Furthermore, the prediction error of DTC method was within the acceptable range when the data sample sets were reduced to 100 sets. These results proved that the established DTC for chemical process optimization can effectively lessen the experimental workload and has high application value.

Coal tar pitch is a product with high carbon content and aromatic compounds. Modified coal tar pitch is a high quality raw material for the preparation of intermediate phase pitch, needle coke, carbon microspheres, et al. In this paper, modified coal tar pitch was used as raw material, nitrogen was used as protective gas, and thermal conversion was carried out at constant temperatures (370, 390, 410, 420 °C). Polarized light microscopy, SEM, elemental analysis, FTIR spectroscopy, Raman spectroscopy and XRD diffraction combined with split-peak fitting were used to characterize the microstructures of the thermal transformation products. The results showed that the Iar and CH3/ CH2 contents of the products increased with the gradual increase of the thermal conversion temperature, and the aromatic content increased. And the higher the temperature at the same heating rate, the more the ideal graphite microcrystal content, and the defective graphite microcrystals are converted into ideal graphite microcrystals during the thermal conversion process. When the reaction temperature exceeds 390 °C, the microstructure of the thermal transformation products is anisotropic spheres, and the small spheres fuse with each other and tend to be basin-like and mosaic structure as the temperature increases.

Isotropic pitch-based carbon fiber was successfully prepared from tetrahydrofuran-soluble fraction of coal tar pitch cocarbonization with petrolatum by air-blowing. The effects of reaction temperature and time, amount of petrolatum added on the composition and spinning properties of resultant pitches were investigated. It indicated that petrolatum could effectively improve the softening point, aromaticity, hydrogen content and molecular weight of the resultant pitches by promoting cross-linking and dehydrogenation polymerization reactions at low air-blowing temperature. Moreover, more aliphatic and naphthenic structures had been introduced into resultant pitches as addition of petrolatum and also inhibited the generation of quinoline-insoluble particles. The obtained green fibers were facile to be stabilized and carbonized and the resultant carbon fibers showed fully isotropic and finer, uniform diameter with smooth surface and higher tensile strength of up to 0.92 GPa. It provided a facile chemical modification method for isotropic pitch-based carbon fiber production.

Pitch precursors affording excellent spinnability, high-level oxidation-resistance, and good carbonization yields were prepared by bromination–dehydrobromination of various ratios of pyrolyzed fuel oil and coal tar pitch. The pitches exhibited spinnabilities that were much better than those of pitches prepared via simple distillation. A pitch prepared using a 1:2 ratio of fuel oil and coal tar pitch exhibited the best tensile strength. Pitch fibers of diameter 8.9 ± 0.1 μm were stabilized at 270 °C without soaking time after heating at a rate of 0.5 °C/min and carbonized at 1100 °C for 1 h after heating at 5 °C/min. The resulting carbon fibers exhibited a tensile strength, elongation, Young’s modulus, and average diameter of 1700 ± 170 MPa, 1.6 ± 0.1%, 106 ± 37 GPa, and 7.1 ± 0.2 μm, respectively.

Pyrolyzed fuel oil (PFO) and coal tar was blended in the feedstock to produce pitch via thermal reaction. The blended feedstock and produced pitch were characterized to investigate the effect of the blending ratio. In the feedstock analysis, coal tar exhibited a distinct distribution in its boiling point related to the number of aromatic rings and showed higher Conradson carbon residue and aromaticity values of 26.6% and 0.67%, respectively, compared with PFO. The pitch yield changed with the blending ratio, while the softening point of the produced pitch was determined by the PFO ratio in the blends. On the other hand, the carbon yield increased with increasing coal tar ratio in the blends. This phenomenon indicated that the formation of aliphatic bridges in PFO may occur during the thermal reaction, resulting in an increased softening point. In addition, it was confirmed that the molecular weight distribution of the produced pitch was associated with the predominant feedstock in the blend.

Activated carbons (ACs) have been used as EDLC (electric double-layer capacitor) electrode materials due to their high specific area, stability, and ecological advantages. In order to prepare ACs with high density and crystallinity, coal tar pitch (CTP) was activated by K2CO3 and the textural and electrochemical properties of the obtained ACs were investigated. Although the CTP ACs formed by K2CO3 activation had much smaller specific surface area and pore volume than did the CTP ACs formed by KOH activation, their volumetric specific capacitance (F/cc) levels as electrode materials for EDLC were comparable due to their higher density and micro-crystallinity. Structural characterization and EDLC-electrode performance were studied with different activation conditions of CTP/K2CO3 ratio, activation temperature, and activation period.

Spinnable pitches and carbon fibers were successfully prepared from petroleum or coal pyrolysis residues. After pyrolysis fuel oil (PFO), slurry oil, and coal tar were simply filtered to eliminate the solid impurities, the characteristics of the raw materials were evaluated by elemental analysis, 13C nuclear magnetic resonance spectrometer, matrix-assisted laser desorption/ionization time-of-flight mass spectrometer (MALDI-TOF-MS), and so on. Spinnable pitches were prepared for melt-spinning carbon fiber through a simple distillation under strong nitrogen flow, and further vacuum distillation to obtain a high softening point. Carbon fibers were produced from the above pitches by single-hole melt spinning and additional heat treatment, for oxidization and carbonization. Even though spinnable pitches and carbon fibers were processed under the same conditions, the melt-spinning and properties of the carbon fiber were different depending on the raw materials. A fine carbon fiber could not be prepared from slurry oil, and the different diameter carbon fibers were produced from the PFO and coal tar pitch. These results seem to be closely correlated with the initial characteristics of the raw materials, under this simple processing condition.

In order to use coal tar pitch (CTP) as a raw material for carbon fibers, it should have suitable properties such as a narrow range of softening point, suitable viscosity and uniform optical properties. In this study, raw CTP was modified by heat treatment with three types of polymer additives (PS, PET, and PVC) to make a spinnable pitch for carbon fibers. The yield, softening point, C/H ratio, insoluble yield, and meso-phase content of various modified CTPs with polymer additives were analyzed by changing the type of polymer additive and the heat treatment temperature. The purpose of this study was to compare the properties of CTPs modified by polymer addition with those of a commercial CTP. After the pitch spinning, the obtained green fibers were stabilized and carbonized. The properties of the respective fibers were analyzed to compare their uniformity, diameter change, and mechanical properties. Among three polymer additives, PS220 and PET261 pitches were found to be spinnable, but the carbon fibers from PET261 showed mechanical properties comparable with those of a commercial CTP produced by an air-blowing method (OCI284). The CTPs modified with polymer additive had higher β-resin fractions than the CTP with only thermal treatment indicating a beneficial effect of carbon fiber application.

Activated carbons (ACs) were prepared by activation of coal tar pitch (CTP) in the range of 700°C-1000°C for 1-4 h using potassium hydroxide (KOH) powder as the activation agent. The optimal activation conditions were determined to be a CTP/KOH ratio of 1:4, activation temperature of 900°C, and activation time of 3 h. The obtained ACs showed increased pore size distribution in the range of 1 to 2 nm and the highest specific capacitance of 122 F/g in a two-electrode system with an organic electrolyte, as measured by a charge-discharge method in the voltage range of 0-2.7 V. In order to improve the performance of the electric double-layer capacitor electrode, various mixtures of CTP and petroleum pitch (PP) were activated at the optimal activation conditions previously determined for CTP. Although the specific capacitance of AC electrodes prepared from CTP only and the mixtures of CTP and PP was not significantly different at a current density of 1 A/g, the AC electrodes from CTP and PP mixtures showed outstanding specific capacitance at higher current rates. In particular, CTP-PP61 (6:1 mixture) had the highest specific capacitance of 132 F/g, and the specific capacitance remained above 90% at a high current density of 3 A/g. It was found that the high specific capacitance could be attributed to the increased micro-pore volume of ACs with pore sizes from 1 to 2 nm, and the high power density could be attributed to the increased meso-pore volume.

In this work, thermal treatment accompanied with different acid treatments was applied to a commercial coal tar pitch (CTP) to obtain a spinnable precursor pitch for carbon fiber. In the case of thermal treatment only, a relatively high reaction temperature of between 380˚C and 400˚C was required to obtain a softening point (SP) range of 220˚C-260˚C and many meso-phase particles were created during the application of high reaction temperature. When nitric acid or sulfuric acid treatment was conducted before the thermal treatment, the precursor pitch with a proper SP range could be obtained at reaction temperatures of 280˚C-300˚C, which were about 100˚C lower than those for the case of thermal treatment only. With the acid treatments, the yield and SP of the precursor pitch increased dramatically and the formation of meso-phase was suppressed due to the lower reaction temperatures. Since the precursor pitches with acid and thermal treatment were not spinnable due to the inhomogeneity of properties such as molecular weight distribution and viscosity, the CTP was mixed with ethanol before the consecutive nitric acid and thermal treatments. The precursor pitches with ethanol, nitric acid, and thermal treatments were easily spinnable, and their spinning and carbon fiber properties were compared to those of air blowing and thermal treated CTP.

Coal-tar pitch, a feedstock which can be heat-treated to create graphite, is composed of very complex molecules. Coal-tar pitch is a precursor of many useful carbon materials (e.g., graphite, carbon fibers, electrodes and matrices of carbon/carbon composites). Modified coal-tar pitch (MCTP) was prepared using two different heat-treatment methods and their properties were characterized and compared. One was prepared using heat treatment in nitrogen gas; the other was prepared under a pressure of 350 mmHg in air. The MCTPs were investigated to determine several properties, including softening point, C/H ratio, coke yield, formation of anisotropic mesophase and viscosity. The MCTPs were subject to considerable changes in chemical composition due to condensation and polymerization in the used-as-received coal-tar pitch after heat-treatment under different conditions. The MCTPs showed considerable increases in softening point, C/H ratio, and coke yield, compared to those of as-received coal-tar pitch. The MCTP formed by heat-treatment in nitrogen showed isotropic phases below 350˚C for 1 h of soaking time. However, MCTP heat-treated under high pressure (350 mmHg) showed isotropic phases below 300˚C, and showed anisotropic phases above 350˚C, for 1 h of soaking time. The viscosity of the MCTPs increased with increase in their softening points.

Coal tar is the primary feedstock of premium graphitizable carbon precursor. Coal tars are residues formed as byproducts of thermal treatments of coal. Coal tar pitches were prepared through two different heat treatment schedules and their properties were characterized. One was prepared with argon and oxidation treatment with oxygen; the other was prepared with oxygen treatment at low temperature and then argon treatment at high temperature; both used coal tar to prepare coal tar pitches. To modulate the properties, different heat treatment temperatures (300~400˚C) were used for the coal tar pitches. The prepared coal tar pitches were investigated to determine several properties, such as softening point, C/H ratio, coke yield, and aromaticity index. The coal tar pitches were subject to considerable changes in chemical composition that arose due to polymerization after heat treatment. Coal tar pitch showed considerable increases in softening point, C/H ratio, coke yields, and aromaticity index compared to those characteristics for coal tar. The contents of gamma resin, which consists of low molecular weight compounds in the pitches and is insoluble in toluene, showed that the degree of polymerization in the pitches was proportional to C/H ratio. Using an oxidizing atmosphere like air to prepare the pitches from coal tar was an effective way to increase the aromaticity index at relatively low temperature.

MCMB (Mesocarbon microbeads) is a kind of anode material for lithium-ion secondary battery. MCMB charge/discharge cycle stability is one of the important criterion at lithium-ion battery operation. In this study, the cycling stability of a lithium-ion secondary battery has been examined. MCMB was made by the direct solvent extraction method. After the MCMB was carbonized and graphitized, the measurement of charge/discharge capacity and efficiency were carried out. In the result, discharge capacity of MCMB in the initial cycle was above 290.0 mAh/g. After the second cycle, efficiency of charge/discharge MCMB was about 98%. These results were similar to the commercial MCMB product.

MCMB (mesocarbon microbeads) has been synthesized from coal tar pitch, petroleum pitch and polymer compound generally. But yield of MCMB was low about 20~40 wt% and was not above 50 wt%. Neither MCMB was replaced with natural graphite because of economic performance, refining MCMB, and control of the particle size distribution. This study was performed to elevate yield of MCMB and to develop technique of particle size distribution. As the result, yield of MCMB that was synthesized from coal tar pitch increased more than 60 wt% about raw material and particle size of MCMB was restrained according to control of QI (quinoline insoluble) ingredient in raw pitch, heat treatment temperature and time.

Quinoline insoluble formed by the heat treatment was hot-pressed near its softening point. The green body was stabilized in the temperature range of 300~400℃ and subsequently carbonized below 1300℃ in an argon atmosphere. The behaviors of QI formation was examined with varying the heat treatment temperature and the lapse of time of the sample carbonized at various temperatures. And the mechanical property, corrosion resistance, and friction behavior were also measured optimum content of mesophase pitch ensured a dense structure and high LC(002) value, which resulted in high mechanical properties, good corrosion resistance, and low-stable friction behavior.

A series of activated carbons were prepared from coconut shells and coal-tar pitch binder by physical activation with steam in this study. The effect of variable processes such as activation temperature, activation time and ratio of mixing was investigated for optimizing those preparation parameters. The activation processes were carried out continuously. The nitrogen adsorption isotherms at 77 K on pellet-shaped activated carbons show the same trend of Type I by IUPAC classification. The average pore sizes were about 19-21a. The specific surface areas (SBET) of pellet typed ACs increased with increasing the activation temperature and time. Specific surface area of AC treated for 90 min at temperature 900℃ was 1082 m2/g. The methylene blue numbers continuously increased with increasing the activation temperature and time. On the other hand, iodine numbers highly increased till activation time of 60 min, but the rate of increase of iodine numbers decreased after that time. This indicates that new micropores were created and the existing micropores turned into mesopores and macropores because of increased reactivity of carbon surface and H2O.

Raman spectroscopy has been used to investigate the structure of coal tar pitch heat-treated up to 3000℃ by using 514.5 run Ar ion laser line. Four critical temperature ranges were found on pyrolyzing coal tar pitch, which correspond to four distinct processes from disordered carbons to the well-ordered graphite structure. The range of heat treat temperature (HTT) below 1000℃ corresponds to gas evolution during the pyrolysis of coal tar pitch. Above the HTT are correlated to rearrangements of enlarged molecules, growth of the molecules along the direction of plane, finally stacking in the normal direction of the plane, in the respective HTT ranges of 1000-2000, above 2000 and 2500-3000℃.