光子学报, 2023, 52 (3): 0352109, 网络出版: 2023-06-21  

LIBS-XRF联用多光谱煤质分析仪的研制与应用(特邀)

Development and Application of LIBS-XRF Coupled Multi-spectrum Coal Quality Analyser(Invited)
作者单位
1 山西大学 量子光学与光量子器件国家重点实验室,太原 030006
2 山西大学 极端光学创新研究中心,太原 030006
3 中国石化石油加工研究院,北京 100089
4 山西格盟中美清洁能源研发中心有限公司,太原 030006
摘要
基于提出的激光诱导击穿光谱(LIBS)和X射线荧光光谱(XRF)的联用多光谱方法,设计了一种基于软件控制的煤质快速分析仪,该分析仪包括LIBS分析模块、XRF分析模块、送样模块、控制模块和操作软件。该仪器不仅发挥了LIBS全元素分析的长处,还继承了XRF高稳定分析的优点,可用于发电厂对压制煤饼进行快速连续的检测。此外,基于偏最小二乘回归方法对数百个煤样进行了光谱分析建模,并完成了工业测试与性能评价。评估结果表明,所建发热量、灰分、挥发分和硫分定标模型的R2分别为0.973、0.986、0.977、0.979,平均绝对误差分别为0.60 MJ/kg、1.24%、0.18%、0.19%,工业分析的平均SD分别为0.11%、0.49%、0.15%、0.09%。模型结果表现出不错的准确度和良好的稳定性,对所有煤炭工业指标的测量重复性均达到甚至优于国标要求。同时,实测结果表明,该仪器对煤炭发热量、灰分、挥发分、硫分的平均绝对误差分别为0.385 MJ/kg、0.830%、0.496%、0.230%,单次样品检测约需5.5 min,能够满足工业现场的实际需求,为煤炭性质的前瞻性预测开辟了道路。
Abstract
Thermal power plants in China have the dual tasks of energy security and energy conservation and emission reduction, with coal accounting for 50% to 70% of their operating costs. Faced with the implementation of energy conservation and emission reduction, low-carbon environmental protection, and energy transformation policies, promoting the clean and efficient utilization of coal has become the primary task of thermal power plants. Therefore, measuring the coal quality, pricing according to the quality, and optimizing combustion are the important ways for their production and development. However, China has a large variety of coal and a large difference in coal quality, so thermal power plant generally has the problem that the actual supply of coal and boiler design do not match each other, results in high power generation costs and low combustion efficiency. In order to achieve the optimal control of coal blending and combustion in thermal power plant, the key is to achieve rapid quality analysis and fine management of incoming coal and fired coal. The common methods of coal quality analysis in power plants include manual assay, robotic assay, neutron activation, Laser-Induced Breakdown Spectroscopy (LIBS) and X-Ray Fluorescence Spectroscopy (XRF). Both manual and robotic assay use traditional national standard chemical analysis methods, but the former requires multiple equipments and is time-consuming, while the latter is bulky. In addition, although the analysis results of the traditional national standard method are reliable, it is difficult to analyze the coal in each vehicle or on the belt online due to its long time consumption, which cannot be used for accurate blending and optimized combustion control. Neutron activation online monitor is highly sensitive, but radioactive and expensive. LIBS has the advantages of fast online and simultaneous detection of multiple elements, but the measurement repeatability needs to be further improved. XRF has high repeatability, but it is unable to analyze organic light elements in coal. In this study, based on the proposed coupled multi-spectrum method of LIBS and XRF, we designed a new software-controlled rapid coal quality analyzer, which includes LIBS analysis module, XRF analysis module, sample feeding module, control module, and operation software. This analyzer not only plays the strengths of LIBS for full elemental analysis, but also inherits the advantages of XRF for high stability analysis, which can be used in power plants for fast and continuous analysis of coal pellets. In addition, the spectrum analysis based on Partial Least Squares regression (PLS) method was modeled for hundreds of coal samples. The analysis process of the spectral data included pre-processing of LIBS and XRF spectrum, coupled LIBS-XRF modeling, and model testing, where the accuracy of the model was characterized by the correlation coefficient (R2) and the mean absolute error (Δ), and the repeatability was tested by the Standard Deviation (SD). The industrial testing and performance evaluation were also completed at Shanxi Sunshine Power Plant. We collected spectra of hundreds of coal samples and pre-processed them, then established prediction models using Partial Least Square (PLS) method, and finally completed industrial testing and performance evaluation in Shanxi Yangguang Power Plant. The test results showed that the R2 of the prediction models for calorific value, ash content, volatile matter, and sulfur content were 0.973, 0.986, 0.977, and 0.979 respectively, and the average standard deviations were 0.11%, 0.49%, 0.15% and 0.09% respectively. The model results showed good accuracy and stability, and the measurement repeatability meets the requirements of national standards. The average absolute errors of the analyzer in predicting the calorific value, ash content, volatile matter and sulfur content of coal were 0.39 MJ/kg, 0.83%, 0.50% and 0.23% respectively, and the single measurement takes about 5.5 minutes, which can meet the needs of industrial practical application. This XRF-LIBS coal quality quantitative analysis technology with excellent measurement repeatability is expected to be applied to power plants, coking plants, coal washing plants, cement plants, coal chemical industry and other industrial fields that need to pay attention to coal quality at all times.

田志辉, 王树青, 张雷, 张培华, 叶泽甫, 朱竹军, 董磊, 马维光, 尹王保, 肖连团, 贾锁堂. LIBS-XRF联用多光谱煤质分析仪的研制与应用(特邀)[J]. 光子学报, 2023, 52(3): 0352109. Zhihui TIAN, Shuqing WANG, Lei ZHANG, Peihua ZHANG, Zefu YE, Zhujun ZHU, Lei DONG, Weiguang MA, Wangbao YIN, Liantuan XION, Suotang JIA. Development and Application of LIBS-XRF Coupled Multi-spectrum Coal Quality Analyser(Invited)[J]. ACTA PHOTONICA SINICA, 2023, 52(3): 0352109.

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