Abstract
To verify the feasibility of using radiocarbon detection for the measurement of the biomass-coal blending ratio in co-firing heat and power plants, 14C activity detection technology that uses benzene synthesis as the sample preparation method and a liquid scintillation counter as the detection instrument was studied. A benzene synthesis system was built to enrich carbon in the combustion flue gas in the form of benzene. The benzene sample was mixed with scintillator (butyl-PBD) and 14C activity was measured using a liquid scintillation counter (Quantulus 1220). Three kinds of coal and six kinds of biomass were tested repeatedly. The measured 14C activity was 0.3365 DPM/gC in Zhundong lignite, 0.2701 DPM/gC in Shenmu bitumite, and 0.3060 DPM/gC in Changzhi anthracite. These values were much higher than the instrument background activity. For the co-fired experiment, we used groups with biomass ratios (based on the carbon) of 6.51%, 12.95%, and 20.75%. A modified empirical expression to determine the biomass, coal blending ratio based on the 14C activity measured in the co-firing flue gas, was proposed by analyzing and verifying measurement accuracy. From the 14C measurements of the co-fired samples, the corresponding estimated biomass ratios were (5.54±0.48)%, (12.31±0.67)%, and (19.49±0.90)%. The absolute measurement error was around 1% for a typical biomass-coal co-firing application.
中文概要
目的:准确且可靠的生物质燃料掺混比例数据的缺失,阻碍了生物质/煤混燃发电技术在中国的发展。本文旨在建立以14C 法为基础的生物质掺混比例检测系统,并研究煤作为化石燃料的测试本底、不同生物质之间14C 含量的差异以及苯合成工艺中引入的现代碳污染对测试精度的影响,以验证该方法在混燃电站中实际应用的可行性。
创新点:1. 建立并使用适用于在工业混燃电站中应用的计算方法;2. 通过实验测试,获得了3 种由制样过程污染产生的煤中14C 含量;3. 通过对实际过程的经验拟合,提出更为合理的污染修正公式。
方法:1. 自主搭建苯合成系统(图2),并以液体闪光计数技术为核心形成样品14C 值测试体系;2. 通过 实验测试,获得6 种生物质与3 种煤的14C 测试 值(图3 和4),并验证混燃测试的可行性(图5); 3. 通过公式推导,在考虑煤中14C 含量后,更为 合理地修正苯合成过程中引入的污染,以减小混 燃测试的绝对误差(公式(9))。
结论:1. 光谱级纯苯的测试值为仪器的测试本底,而商 用SrCO3 制苯的测试值则反应了苯合成过程中引 入的污染本底。2. 对不同生物质的重复实验的测 试值落点均在理论计算误差范围内,证明了实验 中苯合成系统的可靠性。3. 运用研究中建立的计 算方法,获得了生物质混燃比例的测试值;14C 法应用于生物质/煤混燃电站的绝对测试误差在 1%左右。
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Project supported by the International Cooperation Foundation for China-USA, NSFC-NSF (No. 51661125012), the National Key Research and Development Program of China (No. 2017YFB0602802), the “Bao Yu Gang” Foundation for Foreign Guest Professor Program, and the Fundamental Research Funds for the Central Universities, China
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Yu-xing TANG wrote the first draft of the manuscript. Chun-jiang YU and Wen-nan ZHANG revised and edited the final version. Zhong-yang LUO managed the execution of research activity. Jian-meng CEN and Qian-yuan CHEN assisted in the experiments.
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Yu-xing TANG, Zhong-yang LUO, Chun-jiang YU, Jianmeng CEN, Qian-yuan CHEN, and Wen-nan ZHANG declare that they have no conflict of interest.
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Tang, Yx., Luo, Zy., Yu, Cj. et al. Determination of biomass-coal blending ratio by 14C measurement in co-firing flue gas. J. Zhejiang Univ. Sci. A 20, 475–486 (2019). https://doi.org/10.1631/jzus.A1900006
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DOI: https://doi.org/10.1631/jzus.A1900006