Chemical Phase Analysis of Arsenic Ores—A Study on Selective Separation Conditions of Orpiment and Realgar
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摘要:
雌黄和雄黄是两种含砷硫化物的共生矿物，具有相似的理化性质，砷矿石化学物相分析方法一直将雌黄和雄黄作为同一相态分析，无法获得各自的含量，影响该类矿石选冶研究。本文以湖南石门雌黄和雄黄砷矿石为研究对象，采用单矿物选择分离技术，对雌黄和雄黄样品的分离条件进行了研究。结果表明：雌黄和雄黄单矿物采用4mol/L氨水溶液，35℃水浴浸取6h，雌黄浸取率为92.2%，雄黄浸取率为2.4%。分离雌黄后，雄黄采用2mol/L氢氧化钠溶液浸取，雄黄浸取率最高为75.8%，基于雄黄空间结构易被氧化，加入碘可将雄黄氧化为易溶于碱的砷氧化物，使雄黄浸取率提高至92.2%，实现雌黄和雄黄的选择性分离。通过X射线衍射仪、全自动矿物仪分析验证在此条件下雌黄和雄黄化学物相分析结果的正确度，两种分析方法的测定值均与化学物相测定值的相对偏差小于14.0%，满足地质矿产实验室测试质量管理规范的要求。该选择性分离条件的确定，有效地提高了雌黄和雄黄的浸取率，对于以雌黄和雄黄为主的砷矿石化学物相分析方法制定奠定了基础。
Abstract:As a rich symbiotic mineral resource, orpiment (As2S3) and realgar (AsS/As2S2/As4S4) are common sulfide minerals of arsenic. However, due to their similar chemical properties, the chemical phase analysis method of arsenic has always taken these two minerals as the same phase analysis and determination, and cannot obtain their respective contents. In the research, the orpiment and realgar arsenic ores of Shimen in Hunan Province were taken as the object. The separation conditions of orpiment and realgar samples were studied by single-mineral selective separation technology. The single mineral of orpiment and realgar was leached with 4mol/L ammonia solution and a 35℃ water bath for 6h. The extraction rate of orpiment and realgar was 92.2% and 2.4% respectively. Realgar was leached with sodium hydroxide solution, the extraction of realgar was 75.8%. Due to the spatial structure of realgar being oxidized, the addition of iodine can oxidize it into arsenic oxide that is easily soluble in alkali, increasing the extraction rate to 92.2%. The building of the selective separation conditions lays the foundation for the development of chemical phase separation methods for arsenic ores mainly composed of orpiment and realgar. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202208050145 .-
Key words:
- orpiment /
- realgar /
- chemical phase analysis /
- ammonia /
- sodium hydroxide /
- selective separation conditions
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表 1 砷矿石中雌黄和雄黄化学物相分析数据与X射线衍射分析仪分析数据比对
Table 1. Comparison of the measured data obtained by chemical phase analysis and those of X-ray diffraction analyzer for orpiment and realgar in arsenic ores
样品编号 雌黄 雄黄 化学物相As测定值
(%)X射线衍射As测定值
(%)相对偏差
(%)化学物相As测定值
(%)X射线衍射As测定值
(%)相对偏差
(%)SY-1 6.36 6.5 −1.1 4.38 4.5 −1.4 SY-2 2.33 2.0 7.6 2.39 3.0 −11.3 SY-3 2.45 2.0 10.1 4.98 5.0 −0.2 SY-4 2.12 2.7 −12.0 8.83 9.0 −0.95 SY-5 4.69 5.0 −3.2 12.12 12.0 0.50 
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表 2 砷矿石中雌黄和雄黄化学物相分析数据与全自动矿物分析仪分析数据比对
Table 2. Comparison of measured data obtained by chemical phase analysis and those of automatic mineral analyzer for realgar and orpiment in arsenic ores
样品编号 雌黄 雄黄 化学物相分析As
测定值(%)MLA分析As
测定值(%)相对偏差
(%)化学物相分析As
测定值(%)MLA分析As
测定值(%)相对偏差
(%)SH-7 2.62 3.46×0.606=2.10 11.0 2.32 2.51×0.700=1.76 13.7 SH-6 3.01 5.23×0.606=3.17 −2.6 4.70 6.48×0.700=4.53 1.7 SH-3 3.23 5.85×0.606=3.54 −4.6 8.04 11.24×0.700=7.86 1.1 SH-2 4.94 8.37×0.606=5.07 −1.3 12.52 17.32×0.700=12.12 1.6 SH-9 17.01 25.99×0.606=15.75 3.8 9.30 12.71×0.700=8.89 2.3 注：雌黄电子探针分析结果w(As)=60.6%；雄黄电子探针分析结果w(As)=70.0%。
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表 3 砷矿石各矿物相数据加和与全量数据的相对偏差
Table 3. The relative standard deviation of the sum of the data of each mineral phase and the total data of arsenic ores
样品编号 全量As测定值
(%)相态加和As
测定值(%)相态加和与全量
的相对偏差(%)SH-7 5.70 5.84 −1.2 SH-6 8.71 8.65 0.35 SH-3 12.72 12.72 0.00 SH-2 18.95 18.87 0.21 SH-9 27.90 28.06 −0.29
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表 4 砷矿石各矿物相化学物相分析方法的重复性限和再现性限
Table 4. Repeatability and reproducibility limits of chemical phase analysis of arsenic ores
总砷及相关化学
物相中砷范围或水平
m(%)重复性限
r(%)再现性限
R(%)总砷 5.59～27.78 r＝0.26+0.0016m R＝−0.55+0.60ln(m) 砷华中砷 0.29～0.72 r＝0.019+0.087m R＝−0.0049+0.55m 雌黄中砷 2.74～17.13 r＝0.029+0.076m R＝0.74+0.061m 雄黄中砷 2.38～12.35 r＝0.19+0.023m R＝0.82−0.0007m 毒砂中砷 0.24～0.88 r＝0.038+0.080m R＝0.035+0.23m
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