Abstract :
[en] The elemental composition of the coal is one of the necessary data for the thermal calculation and combustion adjustment of the boiler. The traditional coal analysis methods are usally off-line and couldn’t offer the real-time data of the coal, so they couldn’t satisfy the needs of the combustion adjustment and accident analysis of the boiler and have a lot of limitations. Therefore, it is necessary to develop a new technology which can analyze the coal rapidly. Laser-induced breakdown spectroscopy (LIBS) is a new technology which has the advantages of the quick and multi-elemental analysis, thus it can be applied for the coal analysis. The theoretical analysis and experimental research are used in the thesis, and they will provide the experimental basis and theoretical foundation for the coal analysis by LIBS.
The current researches both at home and abroad of the applications of the LIBS technique on the coal-fired field are analyzed in this thesis, and the key problems of the current researches are summarized. The mechanism of the production and evolution of the plasma of the coal is very important. The amounts of the main elements which need to be measured of the coal are more than ten, and it is hard to achieve the multi-elemental analysis. On the other hand, the C, H and O elements are hard to excite and ionize, but the canlibration and quantitative analysis of them are most important. However, these contents are closely related to the practical application of the LIBS technique on the coal analysis. According to these key problems, a series of researches will be carried on in this thesis:
The LIBS set-up for the coal analysis is established, and the typical Shenhua bituminous coal is chosen as the object. The time evolution process of the continuous spectrum and the atomic emission line of C I 247.9nm are analyzed, and the formation mechanisms of the spectral lines in each stages from the production to the annihilation of the plasma of the coal are discussed. Moreover, the difference of the evolution processes between the plasmas from the coal and the copper is compared, and the influence of the volatile in the coal to the plasma is discussed. These researches provide the experimental platform and theoretical basis for designing the coal analysis instrumentation by LIBS.
The influence of the excitation and ionization property of the elements on the plasma is analyzed. The suitable delay time and gate width are selected for the purpose of the multi-elemental analysis of the coal by means of a series of experimental researches on the time evolution processes of different emission lines. The experiments on the coal are performed by changing the parameters including the laser energy, the lens focal plane position and the number of averages, and the influence of the parameters on the intensity and repeatability of the emission lines are analyzed. On this basis, the optimum parameters are determined. Four bituminous coals from different mines in China are checked by using the optimum parameters, and the result shows that the line intensities are strong and the reproducibilities are high. These researches supply the experimental foundation and technical parameters for designing the coal analysis instrumentation by LIBS.
The C, H and O elements in the coal are closely related to the combustion, but the sensitivities of their emission lines are low and the results of the calibration curves are not good. In view of these problems, the atomic line of Si I 288.2nm is chosen as the internal standard line, and the internal standard curves of C I 247.9nm, H I 656.3nm and O I 777.4nm are obtained and the calibration results are good. Moreover, in order to avoid the disturbtion of the analysis of the O element from the air, the method of blowing the argon is used in this thesis. The result shows that the interference to the O element is inexistence and the line intensities of the coal are stronger when using the argon. It is found that the calibration results of the C, H and O elements in argon are better than in air. These researches provide the proper calibration method for the quantitative analysis of the C, H and O elements in the coal.
The quantitative analysis is the final purpose of the LIBS technique that applied to the coal-fired field. The conventional quantitative analysis methods are analyzed. The quantitative analysis of the minor elements in the coal is completed by using the calibration curve method, and the result shows the accuracies are high. The quantitative analysis of the C, H and O elements in coal is finished by using the internal standard curve method, and the result shows the accuracies are just passable. The quantitative analysis of the C elment in the coal ash is accomplished by using the internal standard curve method too, and the result shows that the LIBS technique has the applicability for the measurement of the C elment in the coal ashes which come from different coal samples. These researches supply the database for designing the coal analysis instrumentation by LIBS.
Finally, the research works in this thesis are summaried and some advices are given for the further research works.
