Research on the Composition and Distribution of Organic Sulfur in Coal.

The structure and distribution of organic sulfur in coals of different rank and different sulfur content were studied by combining mild organic solvent extraction with XPS technology. The XPS results have shown that the distribution of organic sulfur in coal is related to the degree of metamorphism of coal. Namely, thiophenic sulfur content is reduced with decreasing metamorphic degree; sulfonic acid content rises with decreasing metamorphic degree; the contents of sulfate sulfur, sulfoxide and sulfone are rarely related with metamorphic degree. The solvent extraction and GC/MS test results have also shown that the composition and structure of free and soluble organic sulfur small molecules in coal is closely related to the metamorphic degree of coal. The free organic sulfur small molecules in coal of low metamorphic degree are mainly composed of aliphatic sulfides, while those in coal of medium and high metamorphic degree are mainly composed of thiophenes. Besides, the degree of aromatization of organic sulfur small molecules rises with increasing degree of coalification.

Studies on the Low-Temp Oxidation of Coal Containing Organic Sulfur and the Corresponding Model Compounds.

This paper selects two typical compounds containing organic sulfur as model compounds. Then, by analyzing the chromatograms of gaseous low-temp oxidation products and GC/MS of the extractable matter of the oxidation residue, we summarizing the mechanism of low-temp sulfur model compound oxidation. The results show that between 30°C to 80°C, the interaction between diphenyl sulfide and oxygen is mainly one of physical adsorption. After 80°C, chemical adsorption and chemical reactions begin. The main reaction mechanism in the low-temp oxidation of the model compound diphenyl sulfide is diphenyl sulfide generates diphenyl sulfoxide, and then this sulfoxide is further oxidized to diphenyl sulphone. A small amount of free radicals is generated in the process. The model compound cysteine behaves differently from diphenyl sulfide. The main reaction low-temp oxidation mechanism involves the thiol being oxidized into a disulphide and finally evolving to sulfonic acid, along with SO2 being released at 130°C and also a small amount of free radicals. We also conducted an experiment on coal from Xingcheng using X-ray photoelectron spectroscopy (XPS). The results show that the major forms of organic sulfur in the original coal sample are thiophene and sulfone. Therefore, it can be inferred that there is none or little mercaptan and thiophenol in the original coal. After low-temp oxidation, the form of organic sulfur changes. The sulfide sulfur is oxidized to the sulfoxide, and then the sulfoxide is further oxidized to a sulfone, and these steps can be easily carried out under experimental conditions. What's more, the results illustrate that oxidation promotes sulfur element enrichment on the surface of coal.

Investigation of the effect of different distilled water, rainwater and seawater mass ratios on coal spontaneous combustion characteristics.

When water comes into contact with coal, the risk of coal spontaneous combustion should be reassessed. In order to analyze the effect of distilled water, rainwater and seawater on the coal self-heating, thermogravimetric analysis (TGA) was applied to investigate the differences between the macroscopic oxidation properties of raw coal and water-immersed coal. The risk of coal spontaneous combustion increases after water immersion, but different types of water have different degrees of influence on the spontaneous combustion of coal. The microscopic pore structure and elemental changes on the surface of coal samples before and after water immersion were studied by Scanning Electron Microscope (SEM), low-pressure nitrogen gas adsorption (LP-N2GA) and Energy Dispersive Spectroscopy (EDS) experiments. Fourier infrared spectroscopy (FTIR) was used to investigate the change of active groups. The results show that the pore structure of coal samples immersed in water is much more developed than that of raw coal. In the low-temperature oxidation stage, moisture evaporation consumes much oxidation heat and inhibits the coal self-heating. After the stage, it promotes the coal spontaneous combustion. The content of the hydroxyl group increases, and the content of carbonyl and carboxyl decreases. The alkali metal elements can act as catalysts and active carriers of oxygen, enhancing the oxidation activity of coal. The results are helpful to understand the mechanism of different distilled water, rainwater and seawater mass ratios on coal spontaneous combustion and avoid potential self-heating after immersion.

Mercury species and potential leaching in sludge from coal-fired power plants.

Wet flue gas desulfurization (WFGD) sludge, generated from the WFGD effluent treatment process, is suitable for multiple uses in various industries. However, risk assessments of its utilization are limited. Systematic study of Hg species occurrences, partitioning and risks of leaching is required, and these concerns were addressed in the present study. Hg temperature-programmed decomposition (Hg-TPD) and an improved European Community Bureau of Reference (BCR) method indicated residual Hg in WFGD sludge was related to HgS, and the content of this fraction was from 2 to 3%. HgCl2, HgO and HgSO4 were assigned to the water/acid-soluble fractions, and reducible Hg was related to Fe species in the sludge. Leachate evaluation of the WFGD sludge indicated potentially high Hg leaching risk. WFGD sludge with higher Hg concentrations and smaller particulate diameters exhibited greater leaching potential. Leaching of Hg from WFGD sludge in China into the environment was estimated at 7.46 t/yr.

The effect of high temperature environment on rock properties-an example of electromagnetic radiation characterization.

High temperature causes thermal damage to rock; the macrofracture and microfracture of rock can be produced under the action of temperature treatment. Under the influence of high temperature, the surrounding rock of deep underground engineering will suffer instability damage and cause serious harm to the people. In order to use the electromagnetic radiation (EMR) technology (a non-contact geophysical method) for evaluating the thermal stability of rock in underground thermal engineering applications, we established the EMR testing experimental system of rock under the action of a continuous heat source. The variation of EMR signals of rock under different temperatures was tested, and the EMR signals generates during the process of rock thermal deformation and thermal fracture, which were later analyzed. Under the action of a continuous heat source, the rock materials produced EMR signals with three kinds of frequencies. With the increase of rock temperature, the variation trends of EMR signals varied from the slow growth rate to the rapid growth rate, EMR signals can be divided into five stages. The increase of EMR signals is positively correlated with temperature, the Hurst exponent was higher than 0.7. The thermal stress was responsible for thermal deformation and fracture, thus generating the EMR signals. The research results have important guiding significance for the application of EMR technology to the evaluation of rock thermal stability.

A review on the mechanism, risk evaluation, and prevention of coal spontaneous combustion in China.

In recent years, the ecology, security, and sustainable development of modern mines have become the theme of coal mine development worldwide. However, spontaneous combustion of coal under conditions of oxygen supply and automatic exothermic heating during coal mining lead to coalfield fires. Coal spontaneous combustion (CSC) causes huge economic losses and casualties, with the toxic and harmful gases produced during coal combustion not only polluting the working environment, but also causing great damage to the ecological environment. China is the world's largest coal producer and consumer; however, coal production in Chinese mines is seriously threatened by the CSC risk. Because deep underground mining methods are commonly adopted in Chinese coal mines, coupling disasters are frequent in these mines with the coalfield fires becoming increasingly serious. Therefore, in this study, we analyzed the development mechanism of CSC. The CSC risk assessment was performed from the aspects of prediction, detection, and determination of the "dangerous area" in a coal mine (i.e., the area most susceptible to fire hazards). A new geophysical method for CSC determination is proposed and analyzed. Furthermore, the main methods for CSC fire prevention and control and their advantages and disadvantages are analyzed. To eventually construct CSC prevention and control integration system, future developmental direction of CSC was given from five aspects. Our results can present a reference for the development of CSC fire prevention and control technology and promote the protection of ecological environment in China.

Free radical reaction characteristics of coal low-temperature oxidation and its inhibition method.

Study on the mechanism of coal spontaneous combustion is significant for controlling fire disasters due to coal spontaneous combustion. The free radical reactions can explain the chemical process of coal at low-temperature oxidation. Electron spin resonance (ESR) spectroscopy was used to measure the change rules of the different sorts and different granularity of coal directly; ESR spectroscopy chart of free radicals following the changes of temperatures was compared by the coal samples applying air and blowing nitrogen, original coal samples, dry coal samples, and demineralized coal samples. The fragmentation process was the key factor of producing and initiating free radical reactions. Oxygen, moisture, and mineral accelerated the free radical reactions. Combination of the free radical reaction mechanism, the mechanical fragmentation leaded to the elevated CO concentration, fracturing of coal pillar was more prone to spontaneous combustion, and spontaneous combustion in goaf accounted for a large proportion of the fire in the mine were explained. The method of added diphenylamine can inhibit the self-oxidation of coal effectively, the action mechanism of diphenylamine was analyzed by free radical chain reaction, and this research can offer new method for the development of new flame retardant.