Low-temperature Stage Research Articles

The Effect of CO on the Exothermic Characteristics of Low-Temperature Oxidation in Coal

ABSTRACT In recent years, abnormally high concentrations of CO gas have often been detected in goaf areas of coal mines in China, which have posed a serious threat to safe production in coal mines and the life and safety of underground personnel. The effect of CO on the exothermic characteristics of low-temperature oxidation in coal was studied by analyzing the exothermic characteristics, heat release, oxidation stages, and activation energy of coal at different CO concentrations using a C600 microcalorimeter. The experimental results indicated that CO promoted the coal oxidation at low temperature, but inhibited it after reaching 144°C. When the CO concentration is 30%, the exothermic characteristics of coal in low-temperature oxidation adsorption stage were significantly affected, with the heat flow value decreased by 27.0% and the initial exothermic temperature point moved forward by 3.9 K. In the later stage of the oxidation reaction, the heat release of coal was linearly negatively correlated with CO concentration. The higher the concentration, the lower the heat release. These findings contribute to understanding the combustion mechanism of coal in high-concentration CO atmosphere and provide valuable insights for designing and optimizing coal utilization technologies.

Enhancing the safety and thermal stability of polyurethane filling materials in the mining industry through expanded graphite-based hydrated salts

The utilization of Polyurethane foaming materials (PUF) to seal coal fissures presents a significant challenge due to the substantial heat generated during the reaction process, potentially accelerating fires. In order to study this issue, we propose a novel low-heat polymerization mechanism by incorporating a hydrated salt phase change composite that efficiently absorbs polymerization heat while encapsulating liquid water using expanded graphite (EG). Our findings demonstrate that integrating 10 % EG-6 leak-free phase change material effectively reduces the reaction temperature to a safer 91.4 °C, ensuring minimal impact on the inherent properties of the material. Thorough analyses via TGA and in-situ IR experiments reveal a noteworthy 17 °C elevation in the modified PUF's thermodynamic characteristic temperature point. Additionally, we developed a mixed combustion model of PUF and coal to investigate the gas generation pattern of polyurethane in the mine-filled state where fire occurs. Specifically, the introduction of PUF reduced O2 consumption and CO production while increasing CO2 and C2H4 production, which is consistent with the reality of increased carbon hydrocarbon gases being monitored downhole. These findings suggest a synergistic, mutually beneficial relationship between the two during the low-temperature oxidation stage. This research offers perspectives for the development of polymer materials for coal mines and the safe application of actual filling.

Pore Morphology and Oxidation Behaviour of Deep-Loaded Granular Coal at High Initial Temperatures

ABSTRACT As coal mining proceeds deeper, fragmented coal is subjected to high geostress and elevated thermal environments, causing changes in its micro-physical properties and spontaneous combustion (SC) risks. Deep mining operations entail significant risks of coal fires. In order to investigate the effects of high stress and high thermal environments on the microstructural and physicochemical damage of fragmented coal, and to elucidate the mechanisms influencing oxidation behavior, we conducted experiments including low-temperature nitrogen adsorption, synchronous thermal analysis, and in-situ diffuse reflectance spectroscopy. These experiments aimed to explore the pore morphology and oxidation characteristics of high initial temperature unloading granular coal (HITU-GC) unloading conditions. The results indicate that with increasing initial temperature, characteristic point temperatures initially rise and then decrease, while both the mass loss and heat release during the low-temperature oxidation stage decrease. After pressure-unloading composite treatment, the oxidation process accelerates with more intense reactions, resulting in an overall increase in heat release. The pore shapes of HITU-GC show no significant difference compared to the original coal, mainly comprising non-rigid aggregates of micropores, platy or layered matrix particles, including numerous slit-shaped pores. The coal surface also exhibits ink bottle-shaped pores and cone-shaped pores. Higher pre-oxidation temperatures correlate with higher specific surface areas. Higher stress levels from pressurized unloading correlate with lower specific surface areas. The specific surface area of sample O60-P16 is reduced by 0.879 m2/g compared to sample O60-P0. Pressurized unloading treatment disrupts mesoporous pores. Following thermal environment and pressure-unloading, the coal’s aromatic hydrocarbon content decreases, while the contents of hydroxyl, aliphatic hydrocarbons, and oxygen-containing functional groups (FG) all increase. Sample O60-P4 shows the highest content of active FG. While thermal environments enhance coal oxidation activity, pressure-unloading treatment increases the extent of coal surface fragmentation. The synergistic effect of both significantly increases the SC risk of coal. This study provides a theoretical basis for controlling thermal hazards associated with high-initial-temperature unloading fragmented coal in deep goaf areas.

Preparation of strontium hexaferrite based materials by solution combustion: the effect of charges arising in precursors and an external magnetic field

The formation of electric charges during the synthesis of complex oxide materials based on strontium hexaferrite SrFe12O19, including doped with lanthanum and cobalt ions, via the combustion of nitrate-organic precursors has been established. Precursors included polyvinyl alcohol or glycine as organic component. The intensity of charge generation was lower for precursors containing a larger amount of organic component. Data on the magnetic characteristics of the samples were obtained: magnetization, coercive force. The influence of an external magnetic field during the synthesis of hexaferrites significantly affected the coercive force of the samples and allowed to increase its values due to the formation of extended ensembles of nanoparticles. At the same time, such an effect on samples with a relatively low level of charge generation during precursor combustion was more effective. The relationship between the factors influencing the formation of extended aggregates is analyzed. The Sr0.8La0.2Fe11.8Co0.2O19 samples had the maximum coercive force. One of the techniques for increasing the coercive force is a two-stage thermomagnetic treatment, including a low-temperature stage. The formation of branched extended structures at the macro- and micro-levels was found during the combustion of glycine-containing precursors.

Waste glass powder as a high temperature stabilizer in blended oil well cement pastes: Hydration, microstructure and mechanical properties

Recycling waste glass for diversified utilization has received increasing attention in recent years. This work aimed to reuse waste glass powder (GP) as a high temperature stabilizer to replace silica flour (SF) in blended G class oil well cement (GOWC) pastes. Blended pastes containing 40 % and 66.7 % GP were prepared and compared to pure GOWC paste and blended paste containing 40 % SF commonly used in the oil industry. Under simulated field conditions in a steam injection well, these pastes were cured at 50 °C for seven days, followed by three rounds of thermal cycling curing at high temperature and high pressure (HTHP, 300 °C/13 MPa) conditions. The effects of GP on the hydration kinetics, hydration products, microstructure, and mechanical properties of hardened pastes were evaluated. The results demonstrated that the addition of GP or SF reduced the compressive strength of the pastes at 50 °C due to dilution effect. Compared with SF, GP exhibited higher pozzolanic activity, prolonged the induction period, and promoted the formation of more C-(N)-S-H gels with lower Ca/Si ratios, which led to an increase in the gel pores content of the matrix and partially compensated for the loss of compressive strength due to the dilution effect. Additionally, due to the pozzolanic reaction of GP, the content of CH in the matrix decreased and its crystal size became smaller. After three rounds of thermal cycling curing, the incorporation of GP significantly increased the compressive strength of the hardened pastes. The compressive strengths of the hardened pastes with 40 % and 66.7 % GP were 20.33 MPa and 22.25 MPa, respectively, which were 7.62 % and 17.79 % higher than those of the hardened paste containing 40 % SF. In addition, the compressive strengths of hardened pastes containing 40 % and 66.7 % GP after three rounds of thermal cycling curing decreased by 22.49 % and 5.52 %, respectively, compared to the pastes at the low-temperature stage, while that of the pure GOWC pastes decreased by 83.8 %. Characterization analyses indicated that GP could further reduce the Ca/Si ratio of the system, modulate the crystallization of the gels at high temperatures, and generate foshagite or xonotlite phases with high polymerization structure and thermal stability, instead of reinhardbraunsite. These products effectively refined pore structure and enhanced microstructure densification. Furthermore, the precipitation of Na+ ions during hydration did not affect the microstructure of the matrix. This study offers some guidelines for recycling waste glass, conserving raw materials, and producing sustainable blended cement pastes.

Effect of different freezing conditions on ice crystal formation behavior and ice-growth inhibition by cryoprotectants.

The formation of ice crystals will have adverse effects on aquatic products, and the key to ensure the long-term preservation and better quality preservations of the product is to evaluate the intercellular ice crystal formation to find suitable refrigeration conditions and cryoprotectants. The ice crystal formation was successfully captured by using an inverted microscope cryomicroscopic system equipped with a low-temperature stage, the ice crystals formed under different freezing methods between tuna muscle cells were observed directly, the deformation degree of muscle tissue pores during crystallization was evaluated, and the effect of freeze-thaw times on tuna samples was analyzed. The effects of the use of cryoprotectant such as cellobiose and carboxylated cellulose nanofibers on ice-growth inhibition were investigated, and the reliability of the ice crystal observation results was further verified by the determination of physical properties. The results showed that carboxylated cellulose nanofibers had the best ice-growth inhibition effect, they prevented about 50% cell deformation compared with the control group, and also reduced the minimum size of ice crystal formation. In addition, the addition of cellobiose and sodium tripolyphosphate gave the ice crystals a more uniform size and roundness. The experiment proposed a stable and clear observation method for the process of intercellular ice crystal formation, and the accuracy of the observation method was further verified by some physical indicators. This may help in the selection of suitable measurement methods to directly observe ice crystal formation behavior and screen cryoprotectants. © 2024 Society of Chemical Industry.

Experimental analyses of CO2 sequestration potential in mineralized fly ash and its efficacy in mitigating coal spontaneous ignition risks in underground mine goafs

To effectively utilize fly ash solid waste and realize fly ash resource utilization, carbon sequestration and emission reduction, as well as mine fire prevention and suppression, this paper analyses the components of fly ash by X-ray fluorescence spectrometer (XRF), rheological experiments, the CO2 sequestration experiments by the mineralization of fly ash, thermogravimetric analysis experiments, and flame-retardant property experiments. Additionally, the changes in the physical structure and morphology of fly ash before and after mineralization were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). The carbon sequestration capacity and fluidity of fly ash slurry, as well as the ability of mineralized fly ash slurry to inhibit spontaneous coal combustion are comprehensively investigated. The research results indicate that CO2 is sequestered as calcite on the fly ash surface after mineralization. The optimal CO2 sequestration capacity of fly ash is 65.12 kg/t when 0.5 mol/L NaHCO3 is used as an additive. The fluidity of mineralized fly ash slurry is greater than that of fly ash slurry, and the lower the water-cement ratio is, the worse the fluidity. Mineralized fly ash slurry with a water-cement ratio of 3:1 has a strong carbon sequestration capacity and high fluidity, making it suitable for preventing coal spontaneous ignition in mine goafs. Mineralized fly ash slurry exhibits a regular trend where the better the mineralization effect, the lower the CO release during the low-temperature oxidation stage of coal, and the higher the cross-point temperature. Mineralized fly ash slurry has a stronger ability to inhibit spontaneous coal combustion than does ordinary fly ash slurry.

Experimental study on operating performances of the low and high temperature stages for cascade air source heat pumps

Previous studies on cascade air source heat pumps (CASHPs) mainly focused on overall performances, while impacts of the low temperature stage (LTS) and high temperature stage (HTS) on overall performances were paid less attention to. Therefore, operating performances of a CASHP in LTS and HTS were investigated in this paper, to provide a solution for the optimization of the CASHP. A CASHP unit with a variable speed compressor in LTS and a constant speed compressor in HTS was adopted, and its operating performances were investigated under 26 cases. Results showed that the pressure ratio and COP in LTS and HTS were affected differently by the compressor speed. Specifically, as the speed of the compressor in LTS increased from 30 rps to 90 rps, PrL increased by 151 % ∼ 178 %, and PrH reduced by 38 % ∼ 54 %. Meanwhile, COP in LTS reduced by 21 % ∼ 52 %, but the COP in HTS rose by 54 % ∼ 96 %. Besides, it was found that adjustments of the compressor speed in LTS could improve heating performances of the CASHP. However, when the ambient air temperature and the supply water temperature were consistent, COP changes of the CASHP were limited, only by 0.3 % ∼ 9 %. Furthermore, empirical models of the COP in LTS and HTS were established to predict the COP of the CASHP on different operating conditions. Results of this study were helpful in promoting the configurations and operation control optimization of CASHPs.

Fluid source and ore-forming process of the Lishupo Au deposit, NE Hunan: Constraints from fluid inclusions, SIMS oxygen isotope, LA-ICP-MS pyrite trace elements and fsLA-ICP-MS quartz trace elements

The Lishupo Au deposit (4.3 t @ 4.76 g/t) is located in the central Jiangnan Orogen. The processes and origins of regional gold mineralization, as well as the characteristics of the ore-forming fluids, continue to be poorly understood. This study integrates field geology, fluid inclusions, secondary ion mass spectrometry (SIMS) O isotope, femtosecond laser ablation inductively coupled plasma mass spectrometry (fsLA-ICP-MS) trace elements analysis for quartz, and LA-ICP-MS for trace elements study of pyrite to constrain the nature and source of ore-forming fluids, mechanism of gold precipitation, and ore genesis. Field investigations and microscopic observations reveal three mineralization stages at Lishupo: (1) the quartz-pyrite (Qtz1-Py1) stage; (2) the quartz-dolomite-polymetallic sulfides-gold (Qtz2-Py2) stage; and (3) the quartz-carbonate-pyrite (Qtz3-Py3) stage.Cathodoluminescence (CL) observations reveal that Qtz1 and Qtz2 have a homogeneous texture, while Qtz3 exhibits oscillatory zoning. Fluid inclusions in quartz suggest a CO2-H2O-NaCl ± N2 ± CH4 fluid system, which comprise H2O-CO2-NaCl, CO2-rich, and aqueous types. Microthermometry of fluid inclusions indicates low salinity (stage 1: 3.7–7.9 wt% NaCl equiv.; stage 2: 2.2–7.5 wt% NaCl equiv.; stage 3: 1.4–3.9 wt% NaCl equiv.) and medium to low temperature (stage 1: 313–341 °C; stage 2: 209–286 °C; stage 3: 139–198 °C) for ore-forming fluids, consistent with the low Ti content (<10 ppm) found in the quartz. The low Al content (7.99–20.7 ppm) of Qtz1 suggests that the ore-forming fluids were saturated with CO2 and had a near-neutral pH. The Al contents are higher and more variable in Qtz2 (10.7–1959 ppm) and Qtz3 (21.6–713 ppm), which may imply fluctuations in fluid pH. δ18OFluid values for various types of quartz (Qtz1: 9.02–10.95 ‰, Qtz2: 6.30–7.68 ‰, Qtz3: 3.45–3.94 ‰) indicate a metamorphic fluid origin for stages 1 and 2 fluids, which were mixed with the meteoric water during stage 3. The highest concentrations of Au and As in Py2 suggest that the Qtz2-Py2 stage is the primary ore stage. The Co/Ni ratios of all types of pyrite are less than 1, indicating that the ore-forming materials are derived from metamorphic sedimentary rocks. Fluid inclusion microthermometry suggests that fluid immiscibility was responsible for the gold deposition during the Qtz2-Py2 stage. Fluid immiscibility destabilizes Au(HS)2-, leading to the precipitation of native gold. These data strongly suggest that the Lishupo gold deposit is classified as an orogenic-type deposit. Integrating the existing geochronology data and geological context, we emphasize the presence of the Late Triassic orogenic gold deposit in the Jiangnan orogen. This highlights a significant exploration target area within this zone for future gold prospecting.

Superconducting heat switch made from a transition metal

High sensitivity astrophysics detectors such as transition edge sensor (TES) bolometers or microwave kinetic inductance detectors (MKIDs) require sub-Kelvin operating temperatures for observing low energy photons in infrared and x-ray ranges. Continuous Adiabatic Demagnetization Refrigerators (CADRs) are presently the state of the art solution for providing cooling to these detectors below as low as 50 mK. The CADR shuttles heat through a series of paramagnetic stages from a 50 mK heat load to a 1-6+ K heat sink, using heat switches between stages to “switch” between thermal isolation and thermal communication. A superconducting heat switch is required between the two lowest temperature stages and is considered a critical system component as it determines recycling time and cooling power of the lowest temperature stage. A figure of merit for this technology is the “switching ratio”: the ratio of the thermal conductivity in the on and off states. This ratio is a function of temperature, fixed material properties, and the purity and anneal state of the metal. Lead is most commonly used in this type of thermal switch because it is readily available as a high purity material. However, an analysis of the material properties of other superconducting material suggests that transition metals such as tantalum and vanadium could achieve a significantly higher switching ratio – as high as 5-10 times that of lead. Increasing the switching ratio could allow for shorter recycling times and reduce the parasitic load on the lowest temperature stage. This work discusses relevant properties of various potential heat switch material and compares predicted performance in the CADR against the presently used lead switch.

Qualification and test of space compatible superconducting current leads (REBCO) designed for adiabatic demagnetization refrigerators

Many astrophysics observations require space telescopes, either to reduce atmospheric perturbation or simply to make these detections possible (in the X-Ray spectrum for example). One of these missions, Athena, is led by the European Space Agency (ESA), with additional international contributions, dedicated to X-Ray observation. Two instruments will be part of this mission and among them, X-IFU, will use Transition Edge Sensors (TES) to detect and precisely measure the energy of X-Ray photons. These sensors require a temperature of 50 mK to reach their ambitious sensitivity goals. In space, this temperature can be reached using Adiabatic Demagnetization Refrigeration (ADR) and such a cooling system is currently being developed for the X-IFU instrument. ADR utilizes magnetocaloric materials which, upon variation in magnetic fields, can produce a cooling effect. The magnetic field of the order of 1 T in a volume of 10s of cm3 is produced by a superconducting coil with high winding number and current limited to approximately 2 A. Even though this current is low compared to most earth-based systems, metallic current leads to link the high- and low-temperature stages would cause high thermal loads, unacceptable for the limited capacity of the cryogenic cooling chain of the spacecraft. Therefore, a harness consisting of superconducting current leads is planned to reduce the thermal loads at the low-temperature stage. As part of an ESA contract, our team designed, built and tested such a space-compatible harness. This harness includes the electrical interfaces at both ends as well as mechanical support. Its development is capable of operating between interfaces at 80 K and 4 K. The harness is based on industrially available Rare-Earth-Barium-Copper-Oxide (REBCO) High-Temperature Superconductor (HTS) tapes. The tapes were laser-cut by our group to fulfill our specifications, Parylene coated and reinforced with Kapton laminate tape for mechanical and insulating purposes. After characterization of the single tapes, the assembled harness has been subjected to an extensive qualification sequence including thermal cycling and mechanical testing based on launch loads requirements. This paper will summarize the technical design choices for this HTS harness. It will discuss the test results and propose some perspectives for the next iteration of the development.

Viscosity and structure studies of iron-based quaternary melts: The effect of P

This study systematically investigates the underlying principles and mechanisms governing viscosity across the entire range for the Fe-4.5C-0.1Ti-xP (in wt.%) melts. The viscosity profile exhibits distinct variations in different phases. In the solid–liquid transition region, the primary determinant of viscosity is the presence of solid phase particles, while in the region characterized by liquid phase, the primary influencing factor is the number of clusters. Notably, the impact of P content demonstrates a contrasting effect on low-temperature solid phase precipitation and high-temperature liquid phase structure. During the low-temperature solid phase precipitation stage, an increase in P content serves as a catalyst for graphite precipitation, resulting in an increase in system viscosity and, by extension, impacting an increase in system viscosity. In contrast, within the high-temperature liquid phase, the interaction of P with iron (Fe) results in the breakdown of mid-range clusters in the original system, leading to the formation of smaller clusters with a reduced overall cluster volume. Consequently, an increase in P content is associated with a decrease in viscosity. These findings provide a nuanced understanding of the interplay between P content and viscosity throughout different phases of the melt.

Experimental Study on the Dielectric Properties of Coal In Situ with Variable Temperatures.

The aim of this study was to explore the mapping relationship between the temperature and the dielectric parameters of coal and rock under variable temperatures as well as to determine the characteristics of a dielectric anomaly response. Experiments were performed using lignite, nonstick coal, gas coal, coking coal, and anthracite. The evolution of pyrolysis characteristics, microcrystal structure, and dielectric properties with changing temperature was investigated, and the changes in the dielectric parameters of coal and rock were comprehensively analyzed. As such, the cause of the dielectric anomaly with changing temperatures of coal and rock was revealed. The results show that the dielectric properties of coal at different pyrolysis temperatures are closely related to the degree of intermolecular thermal motion, the evolution of microcrystal structure, and the mechanism of polarization response. In the low-temperature stage, the thermal motion of coal molecules is weak and exhibits electronic polarization, and the dielectric parameters change slightly with temperature while being dependent on the moisture content. In the high-temperature pyrolysis stage, the intense molecular thermal motion leads to the breaking of chemical bonds and the release of volatiles; moreover, the distance between aromatic layers of coal decreases, the order of aromatic structure increases, the dipole turning polarization is the main polarization type, and the dielectric response is obvious. When the pyrolysis reaction is basically complete, the dielectric constants of the five coal samples reach the maximum. As the temperature increases continuously, the coal structure is destroyed by the weakening of the thermal motion of the coal molecules and the accumulation of thermal stress; meanwhile, the dielectric constant decreases gradually, while the dielectric loss and tangent of dielectric loss increase rapidly. At the same temperature, the dielectric constant decreases with an increase in test frequency. These results lay a foundation for the inversion of dielectric data in fire areas of coal mines.

Preparation of TiO2–SiO2–CaCO3 composite opacifier by hydrophobic agglomeration and mechanism of inhibiting glaze yellowing

This study investigates the preparation of TiO2–SiO2–CaCO3 composite opacifier (Ti–Si–Ca) and its application in sanitary ceramic glazes. This approach involved hydrophobic agglomeration through surface-induced hydrophobic modification of TiO2, SiO2 and CaCO3 particles, along with the interactions between the hydrophobic carbon chains of modifiers. The Ti–Si–Ca formed a uniform coating with well-dispersed TiO2 and SiO2 particles on the CaCO3 surface and strong bonds formed among TiO2, SiO2 and CaCO3 through interpenetration of the organic carbon chains on the surface. The Ti–Si–Ca was added to the basic glazes of sanitary ceramics at a proportion of 15.5 % and fired at 1125 °C for 4 h. The resulting white ceramic glazes had chromaticity values of L*, a*, and b* at 93.76, −0.73, and 3.89, respectively, demonstrating superior glaze opacity and whiteness compared to glazes made with a ZrSiO4 opacifier (L* 90.30, b* 4.50). Glass and titanite phase make up the majority of the Ti–Si–Ca ceramic glazing layer of, with titanite serving as the opacified phase. Elimination of organic groups in Ti–Si–Ca during glaze firing formed interfacial chemical bonds among TiO2, SiO2 and CaCO3, which facilitated the synthesis of titanite from the three components at high temperatures. The Ti–Si–Ca was a highly opaque glaze without yellowing because the organic groups of Ti–Si–Ca were removed and interfacial chemical bonds formed among the TiO2, SiO2 and CaCO3 in the low-temperature stage of glaze firing. This transformed the three phases into titanite at high temperature and eliminated free TiO2. The formation of rutile TiO2, which has a yellow hue, at high temperatures was inhibited. This study provides a novel approach for low-energy preparation of TiO2–SiO2–CaCO3 composite opacifiers and addresses the challenge of replacing ZrSiO4 with TiO2 in ceramic opacifiers.

Composition and paragenesis of daqingshanite from the Kamthai carbothermalite, Rajasthan, India

AbstractDaqingshanite in the Kamthai REE deposit (India) occurs as two paragenetic types: primary granular coarse grained crystals coexisting with primary carbocernaite, baryte and bastnäsite; and as aligned micro-ovoid globules within clasts of Sr-bearing calcite. Carbocernaite forming trellis-type lamellae in some of these calcite clasts do not represent exsolution and are considered as replacement textures as they formed subsequent to daqingshanite. The origins of the textural relations of the microglobules of daqingshanite to their host Sr-calcite cannot be unambiguously determined, although an exsolution origin is not considered feasible. The textures are similar to those of ‘chalcopyrite disease’ and as such could be interpreted as replacement features formed in a low temperature carbothermal environment which should facilitate replacement. Given that daqingshanite is an early crystallising phase it is also possible that cotectic crystallisation with Sr-calcite occurred, followed by subsolidus re-equilibration with recrystallisation along specific crystallographic planes in the calcite. The Kamthai REE deposit is best described as a low temperature carbothermalite microbreccia consisting of a wide variety of clasts resulting from the autobrecciation of rocks formed during, and after, the magmatic to carbothermal transition of an undetermined parental calcite carbonatite-forming magma. Many clasts have been replaced by late stage La-enriched carbothermal fluids mixed with exogenous water during the final low-temperature stage of evolution of the deposit.

Study on effects of ethylene or acetylene addition on the stability of ammonia laminar diffusion flame by optical diagnostics and chemical kinetics

Improvement of ammonia combustion characteristics by carbon-based combustion promoters is currently emphasized, but the impact of carbon‑carbon multi-bond structure on ammonia combustion characteristics and reaction mechanisms has not been sufficiently investigated. In order to investigate the mechanism of molecular structures (C=C and C≡C) of combustion promoters on the stability of ammonia flames, the flame morphology, flame structure, NH3-H2 cracking, and C-N cross-reaction of ammonia/ethylene and ammonia/acetylene laminar diffusion flame are investigated based on a Gu¨lder burner by utilizing high-speed photography, planar laser-induced fluorescence (PLIF) and laser spontaneous Raman scattering (SRS) techniques. The results show that acetylene addition is more effective than ethylene to improve the flame stability. Combined with the flame structure analysis, it is shown that C=C mainly enhances the low-temperature reaction stage intensity of laminar flame, while C≡C can both enhance the intensity of low-temperature and high-temperature reaction stages, thereby enhancing the flame combustion exothermic process. Besides, C=C mainly strengthens the exothermic reactions in the upstream of the flame whereas C≡C can strengthen the exothermic reactions in the upstream and downstream of the flame simultaneously. Investigation of the NH3-H2 cracking reactions reveals that C≡C promotes H2 generation mainly by increasing NH3→H2 cracking, whereas C=C promotes H2 generation mainly by increasing NH2→H2 and NH→H cracking, hence improving the flame stability. Further analysis through the reaction flows revels that C=C acts mainly on H-containing species HCN/HNCO whereas C≡C mainly acts on non-H-containing species CN/NCO to influence the reaction pathways, but C-N cross-reaction does not play an important role in the characteristics of ammonia composite combustion (ACC).

Geochemistry of hydrothermal and stream sedimentary rutile in the Tiegelongnan porphyry-epithermal Cu (Au) deposit, Tibet: A tool for exploration

Rutile is a common and stable mineral in porphyry Cu deposits, and morphology and geochemistry of rutile are recognized as a potential indicator mineral for exploration. In this study, we investigate physical features and chemical composition of hydrothermal rutile in the Tiegelongnan porphyry-epithermal system, as well as rutile in stream sediments nearby to establish a method to apply rutile as an exploration proxy. Four stages of hydrothermal rutile have been identified. Potassic alteration stage rutile (Rt1) is associated with biotite, with elongated and acicular shape and small grain size (20–50 μm). Rutile from lower temperature phyllic alteration (Rt2), quartz veins (Rt3), and advanced argillic alteration (Rt4), has characteristic sector zoning and larger grain size (50–150 μm). The sector zoning is more commonly present in Rt2, Rt3, Rt4, that are associated with high-grade Cu mineralization, and is associated with incorporation of W, Fe, V, Sn, and Zr. The earlier rutile (Rt1) also has a geochemical signature different from the other three types of rutile, characterized by significantly lower Al, Cu, Zr, Nb, Sn, Hf, and higher Sc and Fe contents. Low-temperature hydrothermal alteration stage rutile (Rt2, 3, 4) share many geochemical similarities, but Rt3 has higher Nb and Ta contents (median = 3371.0 and 176.0 ppm, respectively), whereas Rt4 has higher Sb content (median = 24.3 ppm).Rutile trace element data from this study and literature are integrated to develop a Partial Least Square-Discriminant Analysis (PLS-DA) multivariate statistics plots that can discriminate porphyry Cu deposit rutile from orogenic gold and VHMS deposits, as well as rutile from different alteration stages. The PLS-DA plots predict that stream sedimentary gold-bearing rutile (RtSAu) adjacent to the Tiegelongnan deposit are derived from the deposit, and mainly from low-temperature phyllic and advanced argillic alteration stages. This is consistent with geochemical similarity between the RtSAu and the Tiegelongnan low-temperature hydrothermal rutile (Rt2 + Rt4). This is further confirmed by a U-Pb age of 125.3 ± 4.7 Ma (n = 24, 2σ) for RtSAu, which is consistent with the main porphyry mineralization age of ∼ 120 Ma in the Tiegelongnan deposit. We infer that the RtSAu may have formed during the ∼120 Ma epithermal system at Tiegelongnan, which has already largely eroded. In general, our findings prove the capability of using rutile, by combing the texture, geochemical compositions, geochronology, PLS-DA tools, and their spatial distribution, as a proxy mineral for the exploration of porphyry Cu deposits.

Thermodynamic analysis of a coupled system based on total flow cycle and partially evaporated organic Rankine cycle for hot dry rock utilization

The total flow cycle (TFC) has a great potential to improve efficiency of geothermal energy utilization. However, it can not fully utilize the heat source due to the limited expansion ratio of the two-phase expander. To solve the problem, a coupled system of TFC and partially evaporated organic Rankine cycle (TFC-PEORC) is proposed. The thermodynamic model considering the pinch point location migration is developed, and the effects of operating parameters on the temperature matching and system performance are investigated. On this basis, system optimization is carried out. At the same time, the performance of TFC-PEORC was compared with the single-stage TFC, the coupled system of TFC and organic Rankine cycle (TFC-ORC), the coupled system of trilateral cycle and organic Rankine cycle (TLC-ORC), and the coupled system of TFC and Kalina cycle (TFC-KC) under optimal operating conditions. The results show that the net output power of TFC-PEORC has a 14.26 % increase compared to TFC, and that TFC-PEORC can provide excellent the temperature matching of the high temperature (HT) stage and the low temperature (LT) stage working fluids, thus providing the maximum net output power (84.36 kW) that is up to 1.93 % higher than TFC-ORC.

Study on the evolution characteristics of molecular surface active sites of low-rank coal in low-temperature oxidation stage

Compared with other coal types of coal, low - metamorphic coal contains numerous active sites, making it susceptible to spontaneous combustion and posing significant risks during production, transportation, and storage. To further reveal the evolution characteristics and laws of low-rank coal's active sites during the process of low-temperature oxidation of coal (LTOC), X-ray photoelectron spectroscopy (XPS), 13C nuclear magnetic resonance (13C NMR), and Fourier transform infrared (FTIR) experiments were used to determine the basic structural parameters such as the valence state of non-carbon features, types of carbon elements in coal macromolecules, and structure and quantity of functional groups. Combined with molecular modelling software (GaussView 6.0) and macromolecular calculation software (Grimme-XTB), macromolecular models of coal at different temperature points were constructed, and the surface energy field distribution was calculated. The number and energy change information of chemical and physical adsorption sites of low-rank coal during heating were obtained. The results show that during the LTOC, the chemical adsorption sites such as aliphatic hydrocarbons (-CH3/-CH2) have higher reactivity and can be converted into oxygen-containing functional groups (-CHO, –OH, –COOH); the number of physical adsorption sites increased first and then decreased, and reached the maximum at 50 °C. Coal exhibited a higher affinity for O2 at this temperature. The peroxide (-C-O-O-H) undergoes thermal decomposition, leading to H2O and weight loss of coal. The –CO and –COO structures undergo decarboxylation to generate CO, CO2, and other gases. This study comprehensively revealed the evolution of active sites through two key coal oxygen processes, physical and chemical adsorption, based on the gradual temperature elevation of low-rank coal. This holds immense significance for improving and enriching the understanding of the mechanism of coal spontaneous combustion(CSC), preparing more targeted CSC inhibition, and formulating efficient fire prevention and extinguishing measures.

Selection and validation of reference genes for RT-qPCR in ophiocordyceps sinensis under different experimental conditions.

The Chinese caterpillar mushroom, Ophiocordyceps sinensis (O. sinensis), is a rarely medicinal fungus in traditional chinese herbal medicine due to its unique medicinal values, and the expression stability of reference genes is essential to normalize its gene expression analysis. In this study, BestKeeper, NormFinder and geNorm, three authoritative statistical arithmetics, were applied to evaluate the expression stability of sixteen candidate reference genes (CRGs) in O. sinensis under different stress [low temperature (4°C), light treatment (300 lx), NaCl (3.8%)] and different development stages (mycelia, primordia and fruit bodies) and formation of morphologic mycelium (aeriasubstrate, hyphae knot mycelium). The paired variation values indicated that two genes could be enough to accurate standardization exposed to different conditions of O.sinensis. Among these sixteen CRGs, 18S ribosomal RNA (18S rRNA) and beta-Tubulin (β-TUB) showed the topmost expression stability in O.sinensis exposed to all conditions, while glutathione hydrolase proenzym (GGT) and Phosphoglucose isomerase (PGI) showed the least expression stability. The optimal reference gene in different conditions was various. β-TUB and Ubiquitin (UBQ) were identified as the two most stable genes in different primordia developmental stage, while phosphoglucomutase (PGM) with elongation factor 1-alpha (EF1-α) and 18S rRNA with UBQ were the most stably expressed for differentially morphologic mycelium stages and different stresses, respectively. These results will contribute to more accurate evaluation of the gene relative expression levels in O.sinensis under different conditions using the optimal reference gene in real-time quantitative PCR (RT-qPCR) analysis.