Determination of Sulfur in Fly Ash by High Frequency Combustion Infrared Absorption Spectroscopy with Matrix Matching
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摘要:
粉煤灰中的硫含量过高，会导致后续用作混凝土掺入料时，引起混凝土体积变化从而造成膨胀开裂等问题，准确测定粉煤灰中硫的含量，对实现粉煤灰的合理应用具有重要意义。目前采用硫酸钡质量法测定粉煤灰中硫含量，分析流程较长，且操作繁琐，对人员及操作要求严格，检测效率较低。本文利用扫描电镜-能谱技术(SEM-EDS)分析发现粉煤灰中的硫元素主要与钙结合，为有效地避免基体效应的影响，提出在粉煤灰样品基体中加入硫酸钙制备人工合成校准样品，采用高频燃烧红外吸收法测定粉煤灰中的硫含量。为探究最佳实验方案，设计了以助熔剂(纯铁、钨、锡)加入量，助熔剂和试样的加入顺序为考察因素的四因素三水平的正交试验；并考察分析时间、称样量等参数对硫含量测定的影响。结果表明，校准曲线方程为y=2194.4x+8.21，相关系数r=0.9998，方法检出限为0.00036%(质量分数)，定量限为0.0012%(质量分数)。按照实验方法测定实际粉煤灰样品中的硫含量，相对标准偏差(RSD)为0.6%～2.1%，测定值与硫酸钡质量法结果基本吻合。与硫酸钡质量法相比，该方法操作简便，可快速准确测定粉煤灰中的硫含量。
Abstract:Fly ash can be used as a concrete admixture. If the sulfur content in fly ash is too high, the volume of concrete will change, resulting in expansion cracking and other problems. Therefore, accurate determination of sulfur content in fly ash is of great significance for fly ash application. The sulfur content in fly ash is determined by the barium sulfate mass method, which has a complicated process, complicated operation, and strict requirements for personnel and operation. It was found that the sulfur in fly ash was mainly combined with calcium by SEM-EDS. In order to avoid the influence of the matrix effect, a synthetic calibration sample was prepared by adding calcium sulfate to the matrix of the fly ash sample. The sulfur content in fly ash was determined by the high frequency combustion infrared absorption method. To explore the best experimental scheme, the orthogonal test with 4 factors and 3 levels was designed. The 4 factors were quality of flux (iron, tungsten, tin), and the adding order of flux and sample. The influence of analysis time, sample weight and other parameters on the determination of sulfur content was also investigated. The calibration curve equation was y=2194.4x+8.21, the correlation coefficient was r=0.9998, the detection limit of the method was 0.00036% (mass fraction, the same below), and the limit of quantitation was 0.0012%. The relative standard deviation (RSD) of sulfur content in fly ash was 0.6%−2.1% and the results were consistent with those of the barium sulfate mass method. Compared with the barium sulfate mass method, this method is simple to operate and can be used to rapidly and accurately determine sulfur content in actual fly ash sample.
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Key words:
- high frequency combustion infrared spectroscopy /
- fly ash /
- sulfur /
- flux /
- sample weight
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表 1 粉煤灰校准样品组成及硫元素含量
Table 1. Composition and sulfur content of fly ash reference materials
校准样品
编号校准样品组成 硫含量
(%)0#粉煤灰质量(g) 硫酸钙质量(g) 1# 10 0 0.34 2# 10 0.72 1.85 3# 10 1.18 2.75 4# 10 1.71 3.67 5# 10 2.62 5.10 6# 10 3.27 6.00 
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表 2 各因素不同水平正交实验结果统计
Table 2. The statistical results of orthogonal experiment for different levels of each factor
四因素 三水平 分析指标K值（%） 纯铁质量 （g） 0.3 10.684 0.6 10.615 0.9 10.656 钨质量 （g） 1.2 10.575 1.4 10.818 1.6 10.562 锡质量 （g） 0.2 10.534 0.4 10.842 0.6 10.579 助熔剂和试样
加入顺序试样+钨、锡、纯铁 10.668 纯铁、钨、锡+试样 10.558 纯铁+试样+钨、锡 10.729 最佳方法 纯铁质量 0.3g，钨质量 1.4g，锡质量 0.4g，
助熔剂和试样加入顺序为：纯铁+试样+钨、锡注：K为每个因素各个水平的硫含量测定值之和。
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表 3 称样量对硫测定结果的影响
Table 3. The effect of sample mass on the results of sulfur determination
称样量(g) 硫含量6次测定值(%) 硫含量测定平均值 (%) RSD(%) 0.05 0.354 0.361 0.319 0.372 0.312 0.314 0.339 7.7 0.10 0.304 0.301 0.309 0.299 0.306 0.310 0.305 1.4 0.15 0.297 0.295 0.301 0.291 0.302 0.299 0.298 1.4 0.20 0.265 0.251 0.256 0.26 0.257 0.259 0.258 1.8 0.25 0.225 0.236 0.231 0.234 0.226 0.230 0.230 1.9
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表 4 本文方法的精密度及与相关方法比对结果
Table 4. The precision of this method and the comparison results with other methods
实际样品编号 本文方法硫含量6次测定值(%) 硫含量测定平均值
(%)RSD
(%)硫酸钡质量法
测定值(%)S1 0.109 0.110 0.115 0.114 0.113 0.113 0.112 2.1 0.111 S2 0.508 0.501 0.509 0.496 0.506 0.509 0.505 1.0 0.501 S3 1.574 1.585 1.562 1.583 1.563 1.566 1.572 0.6 1.569
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