Optimization of Sulfur Determination in Vanadium-Titanium Magnetite Ore in the Panxi Area
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摘要:
硫是钒钛磁铁矿中重要的质量和环保指标，准确测定其含量对后续工艺控制和污染评价具有重要意义。攀西地区钒钛磁铁矿中硫赋存形态多样且含量范围宽，采用高频燃烧红外吸收法测定硫时，部分矿区样品易出现积分延迟、低硫精密度差的问题。本文结合扫描电镜技术及红外碳硫仪的程序升温功能，通过大量实验，得出钒钛磁铁矿中硫化物形态及含量的差异是造成上述问题的主要原因，并通过优化仪器分析功率、助熔剂及添加顺序、样品质量等分析条件，实现高频燃烧红外吸收法对攀西地区钒钛磁铁矿中0.0004%～1.52%硫的测定。优化后的实验条件如下：样品质量0.30g、助熔剂为0.30g铁粒、0.20g铜粒和1.0g钨粒，助熔剂和样品的添加顺序为铁粒—铜粒—样品—钨粒，分析功率95%。采用不同硫含量的钒钛磁铁矿标准物质建立标准曲线，硫的质量分数为0.0004%～0.200%时(低硫)，标准曲线线性方程为y=1.0028x−1.35×10−6 (r=0.9998)；硫的质量分数为0.201%～1.52%时(高硫)，标准曲线线性方程为y=1.0062x−1.49×10−6 (r=0.9998)，方法检出限为0.0004%。采用本方法对标准物质及攀西地区钒钛磁铁矿实际样品进行测定，标准物质硫含量测定值在标准值的允许范围内，相对标准偏差(RSD)为0.72%～1.40%；实际样品硫含量测定值的RSD为0.40%～0.67%。
Abstract:Sulfur is an important quality and environmental indicator in vanadium-titanium magnetite ore, so the accurate measurement of sulfur is of great significance for subsequent process control and pollution evaluation. There are some problems such as integration delay and poor precision in low sulfur when measuring sulfur in vanadium-titanium magnetite ore with the high-frequency combustion infrared absorption method. To solve the problems, scanning electron microscope (SEM) and infrared absorption carbon-sulfur analyzer with programmed heating function were used, and the analysis conditions such as power, flux and addition sequence, and sample mass were optimized. The optimized experimental conditions were as follows: analysis power of 95%, iron particle flux of 0.30g, copper particle flux of 0.20g, and tungsten particle flux of 1.0g, sample mass of 0.30g. The order of addition is iron-copper-sample-tungsten. The optimized method was used to measure sulfur content, and the results of sulfur in the standard sample were within the allowable error, with satisfactory accuracy. The relative standard deviation (RSD) in samples was 0.40%−0.67%, with satisfactory precision. The range of the method was 0.0004%−1.52%, and the detection limit was 0.0004%.
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表 1 助熔剂选择实验
Table 1. Selection test of flux
铜粒助熔剂 铁粒助熔剂 钨粒助熔剂 质量
(g)硫含量分次测定值
(%)硫含量
平均值
(%)质量
(g)硫含量分次测定值
(%)硫含量
平均值
(%)质量
(g)硫含量分次测定值
(%)硫含量
平均值
(%)0 0.521 0.537 0.535 0.531 0 0.521 0.545 0.544 0.537 0.5 0.521 0.554 0.557 0.544 0.1 0.545 0.552 0.557 0.551 0.3 0.537 0.554 0.553 0.548 1.0 0.537 0.558 0.544 0.546 0.2 0.544 0.553 0.557 0.551 0.6 0.535 0.558 0.557 0.550 1.5 0.535 0.545 0.553 0.544 SDCu(%) − 0.012 SDFe(%) − 0.007 SDW(%) − 0.001 
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表 2 助熔剂添加顺序对硫测定的影响
Table 2. The influence of flux addition sequence on sulfur measurement
助熔剂添加顺序 硫含量测定值
(%)SD
(%)硫含量测定
平均值(%)硫含量标准值
(%)样品及助熔剂在坩埚内燃烧情况 铁粒+样品+
铜粒+钨粒0.372 0.381 0.373 0.005 0.375 0.382 坩埚内熔渣表面较平滑，坩埚壁有少量飞溅残渣 铁粒+铜粒+
样品+钨粒0.379 0.381 0.380 0.001 0.380 0.382 坩埚内熔渣表面平滑，坩埚壁飞溅残渣较少 钨粒+铜粒+
样品+铁粒0.377 0.383 0.382 0.003 0.381 0.382 坩埚内熔渣表面有少许鼓包，坩埚壁飞溅残渣较多且坩埚有开裂现象 钨粒+样品+
铜粒+铁粒0.374 0.378 0.382 0.004 0.378 0.382 坩埚内熔渣表面有少许鼓包，坩埚壁飞溅残渣较多且坩埚有开裂现象 铜粒+铁粒+
样品+钨粒0.382 0.379 0.370 0.006 0.377 0.382 坩埚内熔渣表面较平滑，坩埚壁有少量飞溅残渣
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表 3 不同矿区钒钛磁铁矿样品及标准物质重复测定结果(n=7)
Table 3. Repeated measurement results of vanadium-titanium magnetite ore samples from different mining areas and standard materials (n=7)
钒钛磁铁矿样品 硫含量分次测定值
(%)硫含量平均值
(%)SD
(%)RSD
(%)1#(攀枝花矿) 0.287 0.284 0.286 0.288 0.286 0.288 0.290 0.287 0.002 0.67 2#(红格矿) 0.308 0.311 0.312 0.309 0.307 0.311 0.310 0.310 0.002 0.58 3#(白马矿) 0.326 0.324 0.325 0.325 0.323 0.325 0.327 0.325 0.001 0.40 4#(太和矿) 1.38 1.39 1.39 1.37 1.38 1.39 1.38 1.38 0.008 0.55 YSBC19736-2017 0.204 0.203 0.206 0.208 0.204 0.204 0.211 0.206 0.003 1.4 GBW07227 0.441 0.443 0.442 0.443 0.448 0.449 0.447 0.445 0.003 0.72
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