Search Results (17)

This study investigates the effect of controlled acid demineralization of coal shale from Shubarkol Komir JSC using HCl solutions with concentrations of 9–37% by mass on its structural characteristics, the kinetics of thermal decomposition, and the ability to concentrate rare and dispersed trace elements in the solid residue from the hydrodemetallization of the heavy fraction of coal tar. Analysis of IR spectroscopy, TG/DTG and isoconversional kinetics showed that acid treatment leads to the removal of carbonate and partially iron-containing phases while maintaining the aluminosilicate framework, increasing the structural uniformity of the matrix and moving to a more ordered thermal decomposition mechanism. The activation energy in the range of α = 0.1–0.7 is 83–87 kJ/mol for all modified samples, increasing to 96.20 kJ/mol at α = 0.9 for CS100. It has been established that the ability of coal shale to concentrate rare and dispersed trace elements in the solid residue of hydrodemetallization changes non-monotonically: the total content of trace elements reaches a maximum of 1452.19 g/t with moderate acid treatment (CS50) and sharply decreases to 137.85 g/t with deep demineralization (CS100). It has been shown that the degree of acid treatment acts as a controlled parameter that allows for purposefully regulating the ability of coal shale to concentrate rare and dispersed trace elements in the process of hydrodemetallization of heavy hydrocarbon raw materials. Full article

Mesophase pitch (MP) is a high-performance precursor for carbon materials. However, its conventional preparation process is limited by stringent conditions and high costs. In this study, heavy coal tar (HCT) was used as a low-cost carbon source, and polyethylene (PE) was introduced as a modifier to induce MP formation under relatively mild conditions, thereby promoting the thermal polycondensation of HCT. Characterization results show that the addition of different types of PE facilitates the condensation of aromatic molecules and significantly enhances the conversion efficiency of HCT to MP. Among the tested PE types, HDPE exhibits the best performance, with an optimal addition of 6 wt.% at 400 °C, yielding the highest number of uniform mesophase carbon microspheres and the most ordered structure. Based on comprehensive characterization data, an average molecular structure model of the product was constructed, addressing a research gap regarding the role of PE in the thermal polycondensation of HCT. This work provides a new pathway for the energy-efficient preparation and property regulation of MP. Full article

The extra-heavy oil in the Tahe Oilfield of China has extremely high viscosity, as it is rich in the heavy components asphaltene and resin, creating significant difficulties in its exploitation and transportation. Therefore, it is important to effectively reduce the viscosity and improve the fluidity of this extra-heavy oil. The traditional viscosity reduction method suffers from a high blending ratio and a shortage of light crude oil resources for extra-heavy oil blending. In this study, coal tar and washing oil—widely available low-cost by-products of the coal chemical industry—are used for extra-heavy oil blending and viscosity reduction. Washing oil—containing light components distilled from coal tar—was highly effective in reducing the viscosity of extra-heavy oil. When the dilution ratio of washing oil is 0.25, the viscosity of extra-heavy oil is reduced to 1214 mPa·s, and the viscosity reduction rate is 99.8%, indicating that washing oil is an efficient viscosity-reducing agent in extra-heavy oil blending. GC-MS showed that the washing oil contained abundant aromatic hydrocarbons and aromatic heterocyclic rings. A multi-component viscosity reduction system using washing oil coupled with toluene, xylene, and surfactant achieved an even better viscosity reduction effect. In conclusion, we designed a low-cost, high-efficiency, multi-component, and multi-functional synergistic system for extra-heavy oil viscosity reduction in the Tahe Oilfield. In the proposed working mechanism, aromatic hydrocarbons and aromatic heterocyclic rings in washing oil can intercalate into the layered structure of dense asphaltene aggregates, thereby dispersing and dissociating them. Full article

Coal pyrolysis and gasification are among the key technologies for the clean and efficient utilization of coal. This work examined the individual and synergistic effects of Na and CO₂ on gas/tar generation during rapid coal pyrolysis using a fixed-bed reactor integrated with gas chromatography–mass spectrometry (GC-MS) and a flue gas analyzer. Key findings reveal that Na, CO₂, and Na/CO₂ synergism increased total gas volume by 671 vol.%, 772 vol.%, and 667 vol.%, respectively, while reducing tar yields by 4.14%, 3.12%, and 7.15%. Light oil yields reached 27.18%, 27.93%, and 40.35% under corresponding conditions. Crucially, Na significantly enhanced CO and CH₄ release (dose-dependent), with low-concentration Na (1–3%) promoting light-component condensation versus high-concentration Na (5%) facilitating heavy-component cracking. Na/CO₂ synergism intensified heavy-component fragmentation (efficacy increasing with Na loading), while low-concentration Na (1–3%) substantially boosted CO yield, highlighting its potential for selective syngas modulation. This work plays a pivotal role in advancing the low-emission, high-efficiency utilization of coal energy, aligning with global carbon reduction strategies. Full article

This study presents an integrated approach to processing the heavy fraction of coal tar (HFCT) using oil shale (OS) from Shubarkol Komir JSC to simultaneously increase the yield of valuable hydrocarbon fractions and extract rare and dispersed trace elements. The lack of data on the effect of shale on the process and the kinetics of multi-component “tar + shale” systems limits the development of effective technologies. TG/DTG analysis was combined with the Friedman, Ozawa–Flynn–Wall, and Šesták–Berggren methods for the first time to evaluate the role of oil shale (OS). It was shown that the addition of 13% OS provides a sustained reduction in activation energy (~85–86 kJ/mol) and optimal conditions for hydrometallization. At 420 °C, an initial H₂ pressure of 4 MPa, and a reaction time of 60 min, the yield of light fractions reaches 62.6%, and the solid residue concentrates Ti, Mo, Ge, and other rare and dispersed elements reach up to 66,000 g/t in total. The possibility of extracting Ge using the Purolite C100 sorbent has also been confirmed. The novelty of the study lies in demonstrating the donor–catalytic effect of shale and the practical prospects of solid residue as a secondary mineral raw materials. Full article

The chemical composition and molecular structure of the pitch-like products obtained by liquid-phase reaction of bituminous coal with heavy hydrocarbon fractions of coal and petroleum origin as solvents at a moderate temperature were comprehensively characterized in terms of a new aromatic feedstock for needle coke and other valuable high-tech carbon materials. The molecular parameters of the products were characterized by using FTIR, ¹H NMR, ¹³C NMR and XPS. Liquid-phase chromatography was used to analyze benzo(a)pyrene (BaP) as a carcinogenicity marker. The chemical composition and the characteristics of the molecular structure of the products were shown to depend greatly on the solvent used. The product obtained using coal tar as a solvent was highly aromatic, its polyaromatic nuclei consisted predominantly of protonated and pericondensed cycles sparsely substituted by CH₃ and occasionally CH₂ groups. The product obtained using petroleum-derived heavy gas oil as solvent was much less aromatic and prone to autogenous surface oxidation. Its aromatic nuclei contained mainly protonated and highly alkylated catacondensed chains. The intermediate structural parameters were characteristic of the product obtained using binary solvent. A remarkable feature of the pitch-like products obtained was a reduced BaP concentration (up to 40 times compared to typical coal-tar pitch). In terms of the molecular structure, the pitch-like products obtained by low-temperature dissolution of coal can serve as a new polyaromatic feedstock with a reduced carcinogenicity for the production of valuable high-tech carbon materials, needle coke, in particular. Full article

This study focuses on the preparation of mesophase pitch via the thermal polycondensation of heavy components from low-temperature coal tar. By altering the coal tar composition through distillation, we investigated the impact of various coal tar components and reaction conditions on the properties of the resulting mesophase pitch. Techniques such as infrared spectroscopy, nuclear magnetic resonance, optical structure analysis, and family-component analysis were employed to analyze both the coal tar and mesophase pitch. The primary objective was to provide a comprehensive understanding of mesophase pitch preparation and the underlying transformation mechanisms of coal tar at the molecular, chemical, and functional group levels. Our findings revealed that mesophase pitch formation was driven by a combination of chemical reactions and physical processes. Increasing the distillation temperature reduced the number of alkyl substituents, shortened chain lengths, and promoted greater aromatic condensation. The optimal mesophase pitch content was achieved at a distillation temperature of 360 °C, a reaction temperature of 400 °C, and a holding time of 12 h, resulting in a predominantly inlaid structure. This work addresses a gap in the understanding of coal tar transformation, highlighting how the interplay between distillation temperature and reaction conditions affects the structural properties of mesophase pitch, with implications for improving its production and applications in carbon materials. Full article

The laws of thermal degradation of the mixture of the heavy fraction of low-temperature coal tar and coal shale were investigated using dynamic thermogravimetry. The kinetic characteristics of the process were determined using various methods, including the Ozawa–Flynn-Wall, Friedman, non-parametric kinetics and Šesták–Berggren methods. It is shown that coal shale initiated changes in the kinetic parameters and decomposition rate of the heavy fraction of coal tar. It was found that a 13% content of coal shale in the mixture led to the maximum rate of weight loss of the heavy fraction of coal tar. A hydrodemetallization kinetic model of the mixture of the heavy fraction of low-temperature coal tar and coal shale is proposed. The kinetic parameters of the hydrodemetallization process were determined; in addition, the rate constants at various temperatures were estimated. The study shows that the distribution of trace elements in the hydrogenate from the initial mixture and in the hydrogenate from the solid residue was characterized by relatively low values of reaction rate constants. The maximum microelement distribution rate was achieved in the hydrogenate solid residue. Energy indicators of activation processes indicated that hydrodemetallization at low temperatures is advantageous from an energy point of view. Full article

Catalytic pyrolysis of low-rank coal is currently an effective method for producing high-quality tar and gas. In this study, catalytic upgrading of volatiles from Naomaohu (NMH) coal pyrolysis has been conducted in a two-stage fixed-bed reactor using combined CaO and Ni/olivine (Ni-loaded olivine) catalysts. The effect of catalyst distribution modes and catalytic temperature on the tar and gas quality has been investigated. Simulated distillation and GC-MS analysis have been used to investigate the distribution of tar components. The results indicated that the light oil fraction in tar dramatically increased due to the combination of CaO and Ni/olivine. The CaO-Ni/olivine mode is especially better compared to the layouts of the Ni/olivine-CaO mode and the mixed mode. The CaO-Ni/olivine mode ensures a higher light fraction in tar at 69.3% and a light oil fraction at 29.8% at a catalytic temperature of 450 °C, while the heavy tar fraction decreased to 30.7%. Meanwhile, the contents of benzene (heteroatomic substituents) in tar significantly increased from 2.55% to 6.45% compared with the blank test. In this scenario, CaO breaks down macromolecular compounds in tar and cleaves long-chain esters to produce aliphatic hydrocarbons. These hydrocarbons are then dehydrogenated to produce lighter aromatic hydrocarbons over the CaO surface. Subsequently, the volatiles pass through the Ni/olivine catalysis, where ether compounds are produced by means of dehydration reactions. In addition, the CaO absorbs the CO₂ in the pyrolysis gas, leading to an elevation of CH₄ and H₂ concentration. Particularly, the concentration of H₂ significantly increased from 16.2% to 30.37%, while the concentration of CO₂ significantly decreased from 37.9% to 10.57%. These findings suggest that the usage of combined CaO and Ni/olivine catalysts is beneficial for improving both the tar and gas quality. Full article

In order to achieve the high-value utilization of heavy tar for the production of enhanced-performance graphite foam carbon, the carbon mesophase was ready from the heavy component of low-temperature coal tar, and the coal tar was modified by styrene-butadiene-styrene (SBS), polyethylene (PE) and ethylene-vinyl-acetate (EVA) copolymers. The order degree of the carbonite mesophase was analyzed using a polarizing microscope test, Fourier transform infrared spectroscopy and X-ray diffraction to screen out the most suitable copolymer type and addition amount. Furthermore, the mechanism of modification by this copolymer was analyzed. The results showed that adding SBS, PE and EVA to coal tar would affect the order of carbonaceous mesophase; however, at an addition rate of 10.0 wt.%, the linear-structure SBS copolymer with a styrene/butadiene ratio (S/B) of 30/70 exhibited the optimal degree of ordering in the carbonaceous mesophase. Its foam carbon prepared by polymer modification is the only one that forms a graphitized structure, with d₀₀₂ of 0.3430 nm, and the maximum values of Lc and La are 3.54 nm and 2.22 nm, respectively. This is because, under elevated pressure and high-temperature conditions, SBS underwent chain scission, releasing a more significant number of methyl and other free radicals that interacted with the coal tar constituents. As a result, it reduced the affinity density of heavy coal tar molecules, enhanced fluidity, promoted the stacking of condensed aromatic hydrocarbons and increased the content of soluble carbonaceous mesophase, ultimately leading to a more favorable alignment of the carbonaceous mesophase. Full article

The quinoline-insoluble (QI) matter in coal tar and coal tar pitch is an important factor affecting the properties of subsequent carbon materials. In this paper, catalytic polycondensation was used to remove QI from heavy coal tar, and meso-carbon microbeads could be formed during the purification process. The results showed that AlCl₃ had superior catalytic performance to CuCl₂, and the content of QI and heavy components, including pitch, in the coal tar was lower after AlCl₃ catalytic polycondensation. Under the condition of catalytic polycondensation (AlCl₃ 0.9 g, temperature 200 °C, and time 9 h), AlCl₃ could reduce the QI content in heavy coal tar. The formed small particles could be filtered and removed, and good carbon materials could be obtained under the condition of catalytic polycondensation (AlCl₃ 0.9 g, temperature 260 °C, and time 3 h). Full article

A large number of aromatic substances can be found in so-called coal tar (containing >10,000 individual compounds), which is a mixture of heavy liquid fractions (dense viscous black liquor, tended to solidification) obtained after the pyrolysis of coal (solid product—coke, gas products, and light liquid products are also produced during the process). Volatile monocyclic aromatic hydrocarbons, which are naturally occurring in coal tar, can be exploited as premium raw materials for the production of graphene by chemical vapor deposition (CVD). Moreover, aromatic chemicals (compounds with benzene rings) can produce graphene at lower temperatures than other small-molecule gas feedstocks (for graphene growth via methane gas, the temperature must be at least 900 °C). The intermediate reaction mechanism involved in the creation of graphene from various temperature ranges of monocyclic aromatic hydrocarbons in benzene ring structures has long been a fascinating enigma. Accordingly, in this paper, we analyze the graphene growth pattern of benzene at different temperatures from 300 to 900 °C. For graphene synthesis in the lower temperature range (300~600 °C), analytical experiments show that benzene rings (almost) do not crack during the gas phase process. Thus, the structure of the benzene ring is directly coupled into graphene in the above temperature range. When benzene is more thoroughly transformed into tiny molecules that are deposited on the surface of copper foil at higher temperatures (700~900 °C), graphene is formed by a complex mixture of carbon sources, including gaseous small molecules (methane and ethane) and benzene. Based on the process above, we provide an alternative solution for the large-scale industrial preparation of graphene, with low energy consumption, via low-temperature synthesis of graphene by the CVD method using the coal tar carbon source at 500 °C, which is the optimal growth temperature of the benzene ring. Full article

The study of tar behaviors in underground coal gasification (UCG) is essential for pollution control, system safety and conversion efficiency; however, existing studies have only focused on tar in products without revealing tar evolution in the reaction zone, and the experimental conditions in reported work are far from those in the real situation. In this work, tar behaviors were studied with a self-developed apparatus to simulate the UCG process. During the experiments, the sampling method along the gasification channel was used to collect tar at different positions; the gasification object was a large raw coal block 460 mm × 230 mm × 230 mm in size, and the flow rate of the inlet gas was adjusted according to the composition of products. The tar samples were not only taken from the outlet, but also from the reaction zone, and then analyzed using gas chromatography mass spectrometry. For all the tar samples, C₁₅H₁₃N and its isomer were the most abundant compounds, with a total percentage greater than 14%. Most of the top five chemicals contained more than nine carbon atoms in their molecular formulae, indicating that more heavy tar than light tar is formed by low-temperature pyrolysis. Compared with the upstream tar, the downstream tar had fewer PAHs and a lower boiling point, due to the decomposition of the heavy tar. The downstream tar contained more of the element fluorine (F) than upstream and outlet tars, indicating that tar pollution remaining in the reaction zone cannot be evaluated by monitoring the outlet tar. Full article

Tar remaining in the gasification cavity during underground coal gasification (UCG) is an important pollution source, while the reported studies only focus on the tar behavior at the outlet. The present work aims to compare the tar properties from the reaction zone and the outlet, analyze the tar evolution during gasification, and discuss possible measures to control tar pollution. Tar was sampled with a self-developed equipment from an ex-situ underground coal gasification experimental system and analyzed by GC-MS. The gas composition, temperature, and PM10 were also compared for the reaction zone and the outlet. Compared with the tar from reaction zone, the tar from outlet has a smaller percentage of high boiling point content, PAHs, C, O, N, S, Cl, Si, and a larger percentage of H. The PAHs percentage in tar at the outlet in this work is closer to the field data than the lab data from literature, indicating the experimental system gives a good simulation of tar behavior in underground coal gasification. Condensation due to a fast temperature drop is one of the main reasons for PAHs decreasing. Tar cracking and soot formation also cause the decrease of heavy tar, proven by the light gas and particulate matter results. Full article

Conventional carbon black production occurs by pyrolysis after heavy aromatic feedstock is injected into the post-combustor region of furnace black reactors. The current work examines the conversion of the coal tar distillate in turbulent spray flames to demonstrate a more compact reactor configuration. Coal tar distillates diluted in toluene is atomized and burned in a standardized flame spray synthesis configuration, known as SpraySyn. Flame conditions are characterized by thermocouple, soot pyrometry and image analysis and product particle properties are examined by TEM and Raman spectroscopy. The measured flame temperature corresponds to the range of temperatures used in the furnace black process, but the current synthesis includes oxidizing conditions and faster residence times. The resulting carbon black particles are aggregates with primary particle sizes on the small end of the carbon black size spectrum, according to analysis of TEM images. Carbon black, formed under a range of flame temperatures, show Raman spectra with features resembling typical carbon black materials. Conversion of coal tar distillate to carbon black by direct flame synthesis may be a scalable method to produce high-surface area grades without a conventional pyrolysis reactor stage. Full article