Clean Utilization Research Articles

Solubilization of K and P nutrients from coal gangue by Bacillus velezensis.

Coal gangue piles not only occupy significant amounts of arable land but also cause serious environmental pollution. Therefore, finding sustainable methods for the clean utilization of CG is imperative. Although previous studies have shown that bacteria can promote the solubilization of available phosphorus and available potassium from CG, their impact on promoting plant growth remains understudied. To our knowledge, this study is the first to demonstrate the potential of Bacillus velezensis in enhancing the effectiveness of CG as a mineral fertilizer to support alfalfa growth. The evidence presented in this study provides an ecological strategy for the utilization of CG.

The contribution of clean energy consumption and production to sustainable economic development: New insights from the PSTR model

Massive consumption of fossil fuels has posed significant threat to sustainable development. Therefore, clean energy is an urgent requirement for sustainable economic development (SED). There is no comprehensive assessment of the relationship between clean energy and the SED, signifying a research gap in understanding the non-linear effects between them. This study fills this gap by calculating the SED index for China and using a panel smoothed transformation regression model. The findings reveal that the impact of clean energy development and utilisation on SED is characterised by non-linearity, which manifests in two key aspects: (1) Clean energy consumption (CEC) positively influences SED, with its impact strengthening alongside improvements in industrial structure optimisation and economic growth. Notably, the threshold values for the industrial optimisation level, industrial structure level, and economic development are 1.0390, 0.4667, and 43730, respectively. (2) The relationship between clean energy production (CEP) and SED follows a U-shaped curve; once economic development surpasses 38,588 units, CEP transitions from a negative to a positive influence on SED. This study provides valuable insights into comprehensive measurement of SED, offering guidance for countries worldwide to formulate context-specific energy policies aligned with their respective industrial structures and stages of economic development to foster SED growth.

Analysis of difficult flotation mechanisms for coarse low-rank coal: Comparing fluidized-bed and mechanical flotation technologies

Efficient flotation of coarse low-rank coal is essential for enhancing energy utilization in the mineral processing industry. As the beneficiation equipment scales up, the precision of particle size classification before flotation decreases, leading to a higher coarse particle content in the feed, which poses significant challenges to traditional flotation processes. Recent advancements in fluidized bed flotation technology have demonstrated considerable advantages in the flotation of coarse-grained metallic minerals; however, its application to coarse low-rank coal remains relatively unexplored. This study investigates the potential of fluidized bed flotation technology for coarse low-rank coal, employing various analytical methods to elucidate difficult flotation mechanisms. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were utilized to comprehensively characterize the surface morphology and chemical composition of coal samples. The influence of increasing particle size on flotation performance was systematically assessed through measurements of induction time and critical detachment amplitude. Comparative flotation experiments were conducted to evaluate the efficacy of traditional mechanical flotation against fluidized bed flotation technologies. Results indicate that the presence of cracks and oxygen-containing functional groups on the coal surface significantly enhances hydrophilicity, hindering flotation recovery rates. With increasing particle size, the induction time between particles and bubbles lengthens, while the critical detachment amplitude decreases, weakening the attachment and increasing detachment likelihood. Although high-efficiency collectors enhance coal particle hydrophobicity, they cannot fully mitigate the turbulence disrupting bubble-particle interactions in mechanical flotation. Conversely, fluidized bed flotation effectively minimizes turbulence interference, leading to an approximate 40 % increase in the recovery rate of coarse low-rank coal (0.25–1.00 mm) compared to traditional mechanical flotation. This study presents a novel technological approach for the efficient recovery of coarse low-rank coal, contributing to the clean utilization of low-rank coal resources.

Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories

Gasification of furfural residue with coal can realize its efficient and clean utilization. But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory. Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study. The effects of furfural residue additions on corrosion of silica brick, corundum brick, high alumina brick and mullite brick were investigated by using XRD, SEM-EDS and Factsage Software, and the corrosion mechanism was analyzed. With increasing furfural residue addition, the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases, while the permeability on silica brick shows a slight decrease trend. Leucite (KAlSi2O6) with high-melting temperature is generated from the reaction of K2O and SiO2 in slag with Al2O3 in refractories after furfural residue is added, which hinders the infiltration of slag in refractories. Kaliophilite (KAlSiO4) of low-melting point is formed when K2O content increases, and this contributes to the infiltration of slag in refractories. The acid-base reaction between slag and silica brick is distinctly occurred, more slag reacts with SiO2 in the silicon brick, resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added. The corrosion of silica brick is mainly caused by the acid-base reaction, while the corrosion of three alumina based refractory bricks of corundum, mullite and high alumina brick is determined by slag infiltration. A linear correlation between the percolation rate and slag viscosity is established, the slag permeability increases with decreasing viscosity, resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.

Concurrent removal of Fe(II), Cu(II), and Zn(II) cations from acid mine drainage by an industrial solid waste - steel slag: Behaviors and mechanisms

Acid mine drainage (AMD) contamination poses a severe environmental threat and is a significant risk to human health. There is an urgent need to develop environmentally sustainable and technically viable solutions for water contamination caused by heavy metals. In this study, steel slag (SS) was used as a secondary resource to concurrently remove Fe(II), Cu(II), and Zn(II) from AMD. Because of the loose and porous structure, abundant functional groups, fast sedimentation velocity, and excellent solid-liquid separation, SS showed exceptional removal performance for heavy metal ions. The adsorption kinetic data of Fe(II), Cu(II), and Zn(II) showed good regression with the pseudo-second-order model. Besides, the adsorption of Fe(II) by SS conformed to the Freundlich model, whereas the adsorption of Cu(II) and Zn(II) followed the Langmuir model, with the maximum adsorption amounts of Cu(II) and Zn(II) being 170.69 and 155.98 mg/g. Furthermore, competitive adsorption was observed among Fe (II), Cu (II), and Zn (II) in a multi-component system, with the adsorption priority being Fe (II) > Cu (II) > Zn (II). The removal mechanism of Fe(II), Cu(II), and Zn(II) in AMD by SS mainly includes electrostatic attraction, chemical precipitation, and surface complexation. Interestingly, the leached concentrations of Fe(II), Cu(II), and Zn(II) from the spent slag after calcination were all within the detection limit of the Chinese emission standard, demonstrating excellent environmental stability. Theoretically, this renders it a viable candidate for use as an additive in construction materials. Meaningfully, the work offers a practical approach for energy-efficient and eco-friendly heavy metal ions adsorption, and the secondary utilization of SS also contributes to the sustainable development of the steel industry. It is beneficial to implement the development concepts of clean production and efficient utilization of industrial solid waste.

Heavy metal migration and enrichment in desulfurization wastewater during low-temperature triple effect evaporation process

Zero discharge of desulfurization wastewater from coal-fired power plants has become important. Desulfurization wastewater and gypsum from different stages of the low-temperature triple-effect evaporation process of a coal-fired power plant were collected and investigated. The results showed that after low-temperature triple-effect evaporation, the concentrations of Na+, Mg2+, K+, and Cl− in the desulfurization wastewater increased by 7.91, 7.15, 8.49, and 8.35 times, respectively. With the progress of low-temperature triple effect evaporation process, the concentrations of As, Cd, Co, Cr, Cu, Mn, Se, and Zn in the wastewater after the triple effects were 5.85, 75.44, 1.28, 2.34, 13.66, 5.58, 8.59, and 4.35 times higher than those in the raw wastewater. Mn and Se exceeded the emission limits by 40 and 10 times, respectively. After triple-effect evaporation, the concentrations of As, Cd, Co, Cr, Cu, Pb, Se, and Zn in gypsum decreased to 46%, 26%, 66%, 41%, 35%, 97%, 39%, and 51% of the raw gypsum, respectively. Compared with that of other metal sulfates, the solubility of PbSO4 was extremely low under low-temperature conditions, and some PbSO4 precipitated during the triple-effect evaporation process, leading to a gradual decrease in the Pb concentration in the liquid phase. The mercury compounds in gypsum after the first and second effects were the same as those in raw gypsum, both of which were HgS and HgO. After third effect, the mercury compound in gypsum also included HgSO4. In addition, owing to the promoting effect of the pH of desulfurization wastewater approaching 5.50 on the generation of HgS, the proportion of HgS gradually increased, and the proportion of HgO gradually decreased from the raw gypsum to the third effect gypsum. Therefore, the stability of the mercury compounds in gypsum was enhanced. It can provide a good reference for the migration and enrichment of heavy metals in the low-temperature triple-effect evaporation process, which is beneficial for the clean production and efficient utilization of coal.

Recycling of spent heat pack towards Fe-Fe3O4@NC based cathode for electrocatalytic ORR in direct methanol fuel cells and Al-air batteries

The effective repurposing of waste materials is crucial for sustainable development. The widespread use of disposable iron-based chemical warmers (IBCW) generates substantial solid waste annually. In this study, IBCWs were repurposed as raw materials to synthesize different electrocatalyst composites comprising metallic and oxide forms of iron embedded in nitrogen-doped carbon (NC). The composites were evaluated as oxygen reduction reaction (ORR) catalysts. The optimized Fe-Fe3O4@NC demonstrated enhanced ORR kinetics, with an onset potential of 0.92 V and a half-wave potential of 0.86 V vs. RHE. As an air cathode, Fe-Fe3O4@NC achieved a power density of 33.3 mW cm−2 at 88 mA cm−2, demonstrating its practical applicability. Additionally, a quasi solid-state aluminium-air battery (SAAB) was assembled using this catalyst as the air cathode with a PVA-KOH gel electrolyte as the separator. The quasi SAAB exhibited an open circuit voltage (OCV) of 1.46 V, a power density of 40 mW cm-2, and good rate capability compared to Pt/C. The combined effect of metallic and oxide iron with nitrogen doping enhances the overall catalytic activity. This study demonstrates that IBCWs can be effectively transformed into valuable catalysts for renewable energy applications, enabling clean and sustainable utilization of waste materials.

A new approach to collaborative resource utilization of biological sludge and zinc-bearing dust: Reduction characteristics and mechanisms

This paper proposes an innovative approach for co-processing zinc-bearing dust with biological sludge, using the organic matter in the sludge as a reducing agent to replace traditional fossil fuels (coal/coke). The results show that the reduction process of biological sludge-zinc-bearing dust pellets (BZP) is divided into two stages. In the first stage (25–620 °C), the breakdown of C = C, C-O-C, and C-O bonds present in biological sludge produced carbon oxide (CO) and hydrogen (H2), facilitating the conversion of zinc ferrite (ZnFe2O4) to magnetite (Fe3O4). The second stage (620–1300 ℃), the cleavage of C = C, C–C and C–H bonds and carbon gasification generate more CO and H2, further reducing magnetite (Fe3O4) to metallic iron (Fe) and zinc oxide (ZnO) to zinc monomers (Zn). The activation energy of BZP in the two stages was 32.86 kJ·mol−1 and 73.88 kJ·mol−1, respectively. The metallization rate and the zinc removal rate of BZP achieved 58.47 % and 86.74 %, respectively, indicating the effectiveness and feasibility of the propose of approach. This approach provides a clean and comprehensive utilization way out for zinc-bearing dust and biological sludge.

New Insights on the Understanding of Sulfur-Containing Coal Flotation Desulfurization

The clean and efficient utilization of coal is a promising way to achieve carbon neutrality. Coking coal is a scarce resource and an important raw material in the steel industry. However, the presence of pyrite sulfur affects its clean utilization. Nonetheless, this pyrite could be removed using depressants during flotation. Commonly used organic depressants (sodium lignosulfonate (SL), calcium lignosulfonate (CL), and pyrogallol (PY)) and inorganic depressants (calcium oxide (CaO) and calcium hypochlorite (Ca(ClO)2)) were chosen in this study. Their inhibition mechanism was discussed using FTIR, XPS, and molecular dynamics (MD) methods. The desulfurization ability of organic depressants was shown to be better than inorganic ones. Among the organic depressants, PY proved to be advantageous in terms of low dosage. Physical adsorption was identified as the main interaction form of SL, CL, and PY onto the surface of pyrite, as evidenced from FTIR and XPS analyses. Similarly, MD simulation results showed that hydrogen bonds played a proactive role in the interactions between PY and pyrite. The diffusion coefficient of water molecules on the pyrite surface was also observed to decrease when organic depressants were present, indicating an increase in the hydrophilicity of pyrite. This research is of great significance to utilize sulfur-containing coal and minerals.

Configuration optimization of a biomass chemical looping gasification (CLG) system combined with CO2 absorption

Biomass chemical looping gasification (CLG) combined with CO2 absorption in a dual circulating fluidized bed (DCFB) has emerged as an advanced technology for clean and efficient biomass utilization, yet the reactor design for achieving higher gasification performance and the in-depth understanding of physical-thermal-chemical characteristics is still lacking. This study presents an optimized design aimed at enhancing hydrogen production and carbon reduction in the biomass CLG process with a DCFB reactor by employing the multiphase particle-in-cell (MP-PIC) method integrated with thermochemical sub-models. The proposed reactor is comprehensively compared with the original reactor from the experimental setup in terms of particle mixing, heat transfer, and gasification behaviors. The results indicate that compared to the original setups, the proposed CLG system demonstrates: (i) an improved gas-solid mixing, as evidenced by the particle mixing index rising from 0.23 to 0.34; (ii) an enhanced particle heat transfer coefficient, which boosts heat and mass transfer process; (iii) a 10.11 % increase in H2 concentration alongside a 23.71 % decrease in CO2 concentration; (iv) a particle distribution characterized by higher concentration at the bottom and lower concentration at the top, along with intensified particle back-mixing. The pressure drop inside the combustor is higher than that in the gasifier. A smaller absorbent mean particle diameter and lower-positioned biomass feeding port contribute to the improvement of the CLG performance.

Analyzing the Impact of Internet Use on Peer Effects in Farmers’ Adoption of Clean Energy: Strengthening or Weakening?

Enhancing farmers’ adoption of clean energy is crucial for promoting sustainable rural development and ecological environmental protection. It not only reduces the consumption of traditional fossil fuels, greenhouse gas emissions, and environmental pollution but also optimizes the structure of rural energy consumption, improves farmers’ quality of life, and supports the goal of building a green countryside. This paper investigates the impact of internet use on farmers’ adoption of clean energy and the associated peer effects, further exploring how internet use influences these peer effects. The analysis is based on data from the 2018 and 2020 waves of the China Family Panel Studies (CFPS). The study’s findings reveal that (1) farmers’ adoption of clean energy exhibits a significant peer effect, and internet use also has a significant positive impact on this adoption. Both the peer effect and internet use effectively enhance farmers’ clean energy utilization, a conclusion that holds even after robustness checks. (2) Internet use significantly strengthens the peer effect, particularly when it is used for social and entertainment purposes, where this reinforcing effect is most pronounced. (3) The peer effect, the impact of internet use on clean energy adoption, and the strengthening of the peer effect by internet use vary according to farmers’ geographical location and household income. These findings provide valuable insights and recommendations for improving policies aimed at promoting clean energy adoption among farmers, ultimately fostering its broader diffusion and application in rural areas.

ADPA Optimization for Real-Time Energy Management Using Deep Learning

The current generation of renewable energy remains insufficient to meet the demands of users within the network, leading to the necessity of curtailing flexible loads and underscoring the urgent need for optimized microgrid energy management. In this study, the deep learning-based Adaptive Dynamic Programming Algorithm (ADPA) was introduced to integrate real-time pricing into the optimization of demand-side energy management for microgrids. This approach not only achieved a dynamic balance between supply and demand, along with peak shaving and valley filling, but it also enhanced the rationality of energy management strategies, thereby ensuring stable microgrid operation. Simulations of the Real-Time Electricity Price (REP) management model under demand-side response conditions validated the effectiveness and feasibility of this approach in microgrid energy management. Based on the deep neural network model, optimization of the objective function was achieved with merely 54 epochs, suggesting a highly efficient computational process. Furthermore, the integration of microgrid energy management with the REP conformed to the distributed multi-source power supply microgrid energy management and scheduling and improved the efficiency of clean energy utilization significantly, supporting the implementation of national policies aimed at the development of a sustainable power grid.

A CO2-emission free direct methanol fuel cell for simultaneous production of electrical energy and value-added chemicals

It remains challenges to efficiently convert carbon-based fuels such as methanol from CO2 into electrical energy while without CO2 greenhouse gas emission. Herein, a CO2-emission free direct methanol fuel cell (DMFC) has been realized through using unique Pt-CoOOH/nickel foam anode with high electro-catalytical selectivity, activity and stability. The DMFCs demonstrate simultaneous production of 18 mol of formate for every 1 kWh of electricity output with peak power density of 49.3 mW cm−2 and high selectivity of formate value-added chemicals up to 96 %. Moreover, this simple procedure does not consume energy while output electricity compared to the traditional formate production. It either does not use the toxic feedstock of CO and the reaction conditions are very mild. The in-situ Raman test indicates that CoOOH acts as an auxiliary active site to promote the conversion of *HCO to *HCOOH and improve the selectivity of formate. In-situ IR tests and density functional theory (DFT) calculations confirm that methanol tends to be oxidized selectively into formate rather than complete-oxidizing into CO2. This study achieves clean and efficient utilization of carbon-based fuels to co-generate electrical energy and value-added chemicals while no CO2 greenhouse emission, even realize the “negative carbon” cycle.

Insights into the role of A/B-site substitution in chemical looping gasification of cotton stalk for enhanced syngas production over La-Co-O based perovskite oxygen carriers

Biomass chemical looping gasification (BCLG) is an emerging technology for efficient and clean utilization of cotton stalk (CS) to produce high-quality syngas. Among various oxygen carriers, perovskite oxides are holding an ever-increasing position in BCLG due to their unique structural properties and compositional flexibilities. However, research on perovskite-type oxygen carriers mostly focused on Fe-based oxides, and there is little in-depth investigation of Co-based perovskite and the role of A/B site substitution in the BCLG process. Herein, the LaCoO3 perovskite is selected as the basic oxygen carrier, and Sr, Fe are further doped on the A/B-site to form LaCo1-xFexO3 (x = 0, 0.2, 0.4, 0.6, 0.8, 1) and La1-ySryCoO3 (y = 0, 0.2, 0.4, 0.6, 0.8) series. Effects of perovskite type, gasification temperature, steam volume fraction and oxygen carrier mass fraction of the BCLG performance are investigated. Results indicate that La0.6Sr0.4CoO3 and LaCo0.2Fe0.8O3 exhibit enhanced syngas production with the maximum of 1.304 m3/kg and 1.188 m3/kg, respectively, and outstanding cyclic stability at optimal reaction conditions. Further characterizations including H2-TPR, XPS and EPR analysis reveal that Sr substitution facilitate the formation of oxygen vacancies and adsorbed oxygen species, while Fe doping leads to the increasing concentration of oxygen vacancies and surface lattice oxygen species. Combined with the experimental and characterization results, it is deduced that the oxygen vacancies which promote the adsorption of reactants and accelerate the migration of bulk lattice oxygen, play the key role in the enhanced BCLG performance.

Particle Properties and Flotation Characteristics of Difficult-to-Float Lean Coal

The flotation effect of lean coal is crucial for its clean utilization. Therefore, the flotation characteristics of difficult-to-float lean coal were studied. The analysis results of the feed properties showed that the ash content of the feed was high and the particle size was very fine. The minerals in the gangue mainly included sericite, kaolinite, quartz, white mica, and other substances. After flotation, the functional groups of the coal particles in the tailings decreased, and the absorption peak intensity weakened. Furthermore, the results of multi-factor flotation experiments showed that the dosages of the collector and the frother were significant factors affecting the yield of clean coal. The clean coal yield gradually increased with an increase in the two factors. The ash content of the clean coal increased with an increase in the frother dosage. Within the range of feed concentrations used in this work, the feed concentration was not a significant factor affecting the clean coal’s yield and ash content. Prediction models for the clean coal yield and ash content were proposed. Under optimized experimental conditions, the clean coal yield and the flotation perfection index were 72.15% and 46.63%, respectively, indicating a good flotation effect.

Synergic process of molybdenum recovery and ceramic preparation for clean and efficient utilization of industrial leaching residues

Ammonia-leaching residues of roasted molybdenite concentrates are intractable wastes and are mostly stockpiled in factories. Common treatments suffer from low Mo recovery and secondary pollution. This study has developed a synergistic process involving a single-step roasting with the addition of Al2O3 and MoO3 to recover Mo and simultaneously prepare porous refractories from the residues containing 5.6% Mo. The Mo separation efficiency, ceramic properties, and thermal behaviors—including chemical reactions, melting transformations, ceramic structure evolutions, and Mo species migrations—were comprehensively investigated. It was found that the addition of Al2O3 facilitated CaMoO4 decomposition to release volatile MoO3, thus promoting Mo recovery. The mullite started to form at about 900 °C, grew into whiskers, and further into interconnected clusters, under the catalytic effect of liquid MoO3 and the sintering effect of glassy melt. Liquid MoO3 was scattered on the outer surface of whisker clusters, achieving a high separation efficiency of over 98% after roasting at 1300 °C for 150 min. Meanwhile, a ceramic with a high porosity of 64.2% and a high compressive strength of 21.2 MPa was obtained, exhibiting promise for serving as a high-temperature insulation refractory. Overall, this study presents a novel approach for both the profound recovery of Mo and the value-added utilization of gangue minerals derived from CaMoO4-bearing wastes.

Insights on optimizing landfill site selection inspired by co-fermentation of weathered coal and landfill leachate

To develop new methods for transforming waste resources such as landfill leachate and weathered coal into clean energy, this research analyzed the co-fermentation effect and internal mechanism of methane production through gas chromatography, three-dimensional fluorescence, inducive coupling and metagenomics techniques. Our findings revealed that landfill leachate addition drives more than 70% increase in weathered coal biomethane production. Anaerobic fermentation collectively increased the tryptophan content in liquid-phase biodegradation, with the highest proportion reaching up to 72%. Paracoccus, Ralstonia, Aquamicrobium and other major microorganisms were in the range of 9–32%. Contamination of heavy metal diversity resistance genes has impacted microflora composition, with specialized heavy metal resistance genes such as NreB, CopD, NreB, and MerP altering the influence of heavy metals on anaerobic fermentation. The combined anaerobic fermentation of landfill leachate and weathered coal has expanded clean waste utilization and has broad application prospects.

Striding towards a greener future: Unlocking the potential of natural resources and employment dynamics in green energy transition in sub‐Saharan Africa

AbstractThe adoption and utilization of renewable energy offer potential benefits such as enhanced energy efficiency, cost savings, and ecological advantages. However, a key research question addressed in this analysis is whether natural resource rent and employment dynamics influence renewable energy consumption in Africa. Previous research has predominantly focused on the aggregate employment rate, overlooking the nuances of labor diversity across sectors and employment types. Hence, this study evaluates the importance of natural resource rent and employment in driving the transition to green energy in sub‐Saharan Africa from 1991 to 2022. It employs the innovative method of moments quantile regression (MMQR) model for this purpose. The findings reveal a positive connection between natural resource rent and the adoption of green energy. When considering employment types, the study observes that self‐employment and wages/salaried workers undermine clean energy utilization. Moreover, the study highlights that employment across key economic sectors also plays a role. While employment in the agriculture and service sectors fosters green energy utilization, employment in the industrial sector impedes renewable energy consumption. To advance the development of green energy in Africa, this study underscores a range of policy options.

Imidazole ionic liquid effects on coal swelling behavior and pyrolysis characteristics: Experiment and molecular simulation

In view of low-rank coal conventional swelling solvent large pollution and the clean efficient utilization of coal, the effects of imidazole ionic liquid (IL) pretreatment with different anion groups as green solvent on coal thermal expansion and pyrolysis performance were investigated. IL interacts with coal molecules, destroying the hydrogen bonds, resulting coal expansion. Different anion groups have different modification effects, [Bmim]Cl has the best swelling effect, which is 17.37 % higher than raw coal, and the best modification time is 24 h. In addition, IL modification has a catalytic effect on coal pyrolysis, which can significantly reduce the maximum weight loss temperature and increase tar content. Coal solvent pretreatment provides a good theoretical basis for application of swelling and pyrolysis. The reduction of thermochemical reaction temperature not only reduces the content of heavy groups in pyrolysis products, but also provides new ideas for carbon emission reduction.

Kinetic characteristics and product distribution of tar-rich coal in-situ underground pyrolysis: Influence of heterogeneous coal seam

Tar-rich coal contains more hydrogen-rich structures such as aliphatic side chains and bridge bonds, which is a good raw material for coal to oil. In-situ underground pyrolysis of tar-rich coal has significant advantages such as environmental friendliness and high safety factor; it is an efficient, clean coal utilization technology. Due to the influence of geological structure and other factors in the formation process, underground coal seam was often heterogeneous, generally accompanied by coal gangue interlayers. Due to the coal gangue being relatively dense and has poor thermal conductivity, it is also rich in metal oxides, it would inevitably affect the pyrolysis characteristics and product distribution during the pyrolysis process of heterogeneous tar-rich coal seam. The pyrolysis characteristics of heterogeneous tar-rich coal seam with different positions and layers of coal gangue interlayer were investigated by the thermogravimetric analyzer, and related kinetic parameters were obtained by the distributed activation energy model (DAEM). Based on the fixed bed tube furnace reactor, the pyrolysis experiments of heterogeneous tar-rich coal seam with different positions and layers of coal gangue interlayer were also carried out, and the pyrolysis products were characterized and analyzed. The thermogravimetric results showed that in the pyrolysis process of heterogeneous tar-rich coal seam, the initial pyrolysis temperature and the temperature corresponding to the maximum weight loss rate shifted to the higher temperature range, and the pyrolysis characteristic index decreased significantly. Under the same conditions, the corresponding pyrolysis characteristic indexes of the upper coal gangue interlayer and 4 layers of coal gangue interlayer were lower, which were 11.69 (10−8·%·min−1·℃−3) and 11.65 (10−8·%·min−1·℃−3), respectively. Compared with homogeneous tar-rich coal seam, pyrolysis activation energies of heterogeneous coal seam generally showed the decreasing trend. Under the conditions of the upper part containing coal gangue interlayer and the upper-and-lower parts containing coal gangue interlayer, the pyrolysis activation energies were higher due to the hindrance of the cover layer of coal gangue to the volatile release, which were 555.88 kJ·mol−1 and 546.66 kJ·mol−1 respectively. The results of fixed bed pyrolysis experiments showed that compared with homogeneous tar-rich coal seam, the tar yield obtained was reduced, the degree of tar lightening was significantly improved, and the proportion of lighter tar was up to 70.00 wt%. The contents of aromatic hydrocarbons and phenolic compounds in tar increased, the contents of aliphatic hydrocarbons and oxygenated compounds decreased significantly, and the maximum reductions were nearly 4.50 wt% and 6.50 wt%, respectively. The gas yield increased, the proportions of H2 and CO2 in the gas increased, and the proportions of CO and CH4 decreased to varying degrees. The tar yields were lower under the conditions of upper gangue and 4 layers gangue, which were 6.53 wt% and 5.81 wt%, respectively, and the degrees of tar lightening were also more significant. From the relationship between pyrolysis characteristic parameters and tar properties of heterogeneous tar-rich coal seam pyrolysis, it was found that the existence of coal gangue interlayer was not conducive to the tar production, but it could promote the lightening of tar and improve the tar quality. Exploring the kinetic characteristics and pyrolysis product distribution of heterogeneous tar-rich coal seam could provide theoretical guidance for the site selection of in-situ underground pyrolysis engineering and the well arrangement.