Determination of High Content of Molybdenum in Molybdenum Ore by Emission Spectrometry with Solid Sampling Technique
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摘要:
全面、系统地建立钼矿石、钼矿粉分析方法，对钼元素研究开发和保障钼矿工业发展具有重要意义。目前多采用酸溶或碱熔样品后进行分析，其不足是测定钼含量的范围窄，消耗样品量大，还需使用大量酸碱，且受仪器限制，分析高含量钼时多需对样品溶液进行数次稀释，使分析步骤更加繁琐。发射光谱法则可避免上述问题，但用之准确分析高含量钼矿石钼矿粉尚有测试方法的瓶颈需要突破。本文研究通过内标元素、分析线对、缓冲剂配比、电流程序等环节的实验分析，建立了固体进样-交流电弧发射光谱法测定钼矿石中高含量钼的分析方法：优化样品与光谱缓冲剂质量比至1∶2，优化分析线对，截取曝光时间35s，采用以国家一级合成硅酸盐光谱分析标准物质和国家一级矿石标准物质组成的自研标准系列制作标准曲线，由全谱交直流电弧发射光谱仪自动扣除分析线和内标线背景后以对数坐标二次曲线拟合计算，使测定范围扩展为500～500800μg/g，检出限为27.38μg/g，相对标准偏差（RSD）为3.28%～8.30%，相对误差为-0.43%～0.73%。结果表明，本文方法在实现绿色分析的同时，在检出限相当、精密度合格的条件下，一次性分析高含量钼的上限从5%提高至50%。
Abstract:BACKGROUNDThe majority of current molybdenum ore analysis techniques use absorbance, gravimetric methods, ICP-MS, ICP-OES, XRF, etc., which are primarily based on liquid injection, with a lengthy analytical procedure, complex steps, and a measurable range of 0.01%-5.17%[16]. The joint technologies of EPMA, SEM, and X-ray spectroscopy are more expensive, and the results may not be reproducible[18-21]. Compared with the above methods, AC-Arc atomic emission spectrometry (Arc-AES), which does not call for the use of acids and bases, has the potential to be applied to the analysis of molybdenum ore and molybdenum powder with a high content of Mo over 5%.
OBJECTIVESTo improve the current analytical techniques for determining high content of molybdenum in molybdenum ore.
METHODSThe mixed sample was loaded into the lower electrode after being ground at 2400Hz for 30min with the different sample-to-buffer ratio in a 5mL crucible. Two drops of a 2% mass fraction sucrose-ethanol solution were added and dried at 70℃ for 1h. The samples were mounted on an AES-8000 direct-reading atomic emission spectrometer using the vertical electrode method. The internal reference method was used to fit the quadratic curve in logarithmic coordinates by subtracting the background spectral lines of the analyzed elements and the internal reference elements. The experiments were conducted by choosing the internal reference element types and spectral lines, selecting the Mo spectral lines, deciding the sample-to-buffer ratio, optimizing the current loading procedure, setting the spectral uptake time, and other conditions. A set of national-level reference materials and national-level synthetic silicate spectral analysis reference materials were used for calibration. The relative standard deviation and logarithmic deviation were utilized for quality control.
RESULTS(1) The analytical line pair is chosen to be Mo 277.54nm/Ge 326.9494nm. The uniformity of internal reference elements is ensured by the excessive addition of germanium dioxide. Mo 277.54nm and Ge 326.9494nm evaporation curves exhibit good consistency when GBW07142 is used as the sample (Fig.1). (2) The sample-to-buffer ratio is selected as 1∶2. It is discovered that the evaporation behavior is significantly improved when it reaches 1∶2; simply increasing the buffer, is not conducive to the analysis of actual samples. (3) Primary current is 4A for 5s, secondary current is 15A for 30s, and the total interception exposure time is 35s. The results show that the intensity of Mo and Ge greatly increases before 30s and slows down after 35s (Fig.2). (4) The reference series components are shown in Table 1 with the content range between 500 to 500800μg/g. The reference curve equation is y=−0.077x2+1.3077x+1.2725, with a coefficient of determination (R2) of 0.999 (Fig. E.1）. The detection limit of Mo in this method is 27.38μg/g, which is slightly higher than that of alkali fusion-inductively coupled plasma spectrometry (0.002%)[9] and X-ray fluorescence spectrometry (0.0026%)[16]. The RSD ranges from 3.28% to 8.30%, and the RE ranges from −0.43% to 0.73% (Table 2). The results are consistent with the reference values, with significant precision and accuracy, which meets the requirements (△lgC≤0.05, RSD≤10%) listed in Specification of Multi-Purpose Regional Geochemical Survey (DZ/T 0258—2014).
CONCLUSIONSThis method can be employed to determine the high Mo content in molybdenum ore and molybdenum powder without dilution. Moreover, it is suitable for a wider determination range with the upper limit rising to 50%. It can solve possible problems, such as large sample demand, large chemical reagent use, cumbersome operation and contamination in other analytical methods.
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碲和硒是稀散元素，在高新科技领域具有重要应用，已被中国和欧美国家列为战略性关键矿产资源［1-2］。一直以来全球碲、硒矿产资源主要采自斑岩-矽卡岩铜金矿床，如中国广东大宝山铜矿和江西城门山铜矿［3-4］，研究斑岩矿床中碲、硒的产出情况对国家资源战略保障具有重要意义。云南普朗斑岩型铜金矿床位于三江特提斯成矿域义敦岛弧南部，属于超大型斑岩矿床，已探明铜资源储量4.31Mt，金资源量113t［5］。矿区内出露的地层为中三叠统尼汝组和上三叠统图姆沟组，侵入岩为普朗复式岩体，由石英闪长玢岩（～216Ma）、石英二长斑岩（～215Ma）和花岗闪长斑岩（～206Ma）组成，岩体出露总面积约为11km2（图1）。前人对普朗矿床的地质特征、成岩成矿时代、成矿物质来源、成矿流体性质等作了大量工作，但对矿床中碲硒的含量和赋存状态等研究还较为薄弱。本文报道了普朗矿床中产出的碲化物和硒化物，以期为斑岩矿床中碲硒的勘查和综合利用提供资料。
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本次研究对象主要为普朗矿床中的铜精矿和钼精矿样品，测试分析均在东华理工大学核资源与环境国家重点实验室完成。样品的矿相学观察利用ZEISS Axio Scope A1光学显微镜及ZEISS Sigma 300场发射扫描电镜完成，扫描电镜的加速电压为20kV，发射电流为10μA［6］。矿物成分利用JXA-8530F Plus型电子探针分析完成，实验设定加速电压为15kV，电流为20nA，探针直径为1μm，使用ZAF方法对X射线强度进行校正。分析标样选择砷化镓（As），黄铜矿（Cu），黄铁矿（Fe、S），自然银（Ag），碲铋矿（Te、Bi），辉钼矿（Mo），自然铅（Pb），自然锑（Sb），硒化镉（Se），自然金（Au），自然铂（Pt），自然钯（Pd）。测试主量元素的精确度和准确度均小于2%。
普朗铜金矿床中的碲和硒含量高，并形成大量碲化物、硒化物和富硒矿物。矿床精矿中的碲和硒含量分别达74.3×10−6和270×10−6。碲在钾化带中的含量为0.3×10−6～0.43×10−6，较绢英岩化带中的高（0.02×10−6～0.12×10−6），由矿体中心向外，碲品位逐渐降低［7］。硒在钾化带和绢英岩化带的含量无明显差别，分别为1.49×10−6～2.44×10−6和1.04×10−6～3.00×10−6。矿石中的碲与金呈正相关关系，硒与银呈正相关关系。普朗铜矿床中，碲和硒主要以碲化物、硒化物和富硒矿物形式存在，形成辉碲铋矿、碲钯矿、硒银矿和富硒方铅矿等（图2）。辉碲铋矿是普朗含量最多的碲化物，反射光下为白色略带淡蓝色，矿物成分较均一，Bi含量为58.36%～61.24%，Te含量为31.03%～34.50%，S含量为3.76%～4.54%（图2e）。普朗辉碲铋矿中含有较高的Se（0.77%～3.63%）。辉碲铋矿的化学式为Bi2.02～2.08（Te1.74～1.93S0.85～1.01Se0.08～0.33）2.90～2.98。碲钯矿属于独立铂族元素矿物，在自然界很少见，中国斑岩矿床中仅江西德兴有报道［8］，在全球其他斑岩矿床中非常少见。普朗碲钯矿粒径为1～5μm，反射光下呈亮白色（图2a）。碲钯矿中Pd和Pt可以类质同象取代，因此含量变化较大，Pd含量为16.26%～25.69%，Pt含量为4.82%～17.66%，Te含量为61.25%～66.76%（图2f）。碲钯矿化学式为（Pd0.64～0.98Pt0.09～0.37）0.98～1.03Te1.97～1.02。硒银矿是普朗含量最多的硒化物，反射光下为白色带微蓝绿色（图2c）。硒银矿中普遍含S，含量为0.55%～2.65%，Ag含量普遍偏低，为70.22%～72.77%，Se含量为24.09%～27.31%（图2g）。硒银矿化学式为Ag1.89～1.98（Se0.87～1.01S0.05～0.24）1.02～1.11。富硒方铅矿属于PbS1-xSex矿物，其中x值可在0～1之间连续变化。普朗富硒方铅矿S和Se的含量变化大，分别为4.01%～12.52%和1.85%～19.13%，Pb含量为73.91%～82.52%，大多数样品中含有Ag，最高含量达1.61%。普朗富硒方铅矿形成了较完整的PbS-PbSe固溶体系列（图2h），化学式为Pb0.98～1.01（S0.35～0.97Se0.07～0.67）0.99～1.02。
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图 2 碲硒矿物显微照片及矿物元素含量三元图a—碲钯矿反射光镜下照片； b—碲钯矿BSE照片； c—硒银矿反射光镜下照片； d—硒银矿BSE照片； e— Bi-Te-S体系三元图； f— Te-Pd-Pt体系三元图； g—Ag-Se-S体系三元图； h—Pb-Se-S体系三元图。Mol—辉钼矿； Mrk—碲钯矿； Nau—硒银矿； Py—黄铁矿。Figure 2. Photomicrographs of tellurium and selenium minerals and ternary plots of element contents. a—Reflected light photomicrograph of merenskyite; b—BSE image of merenskyite; c—Reflected light photomicrograph of naumannite; d—BSE image of naumannite; e—Ternary plot of Bi-Te-S system; f—Ternary plot of Te-Pd-Pt system; g—Ternary plot of Ag-Se-S system; h—Ternary plot of Pb-Se-S system. Mol=Molybdenite, Mrk=Merenskyite, Nau=Naumannite, Py=Pyrite.矿床中的碲和硒可以指示物质来源和成矿过程。碲和硒具有亲硫特点，碲会部分进入硫化物晶格，但更易形成碲的独立矿物;硒属于强亲硫元素，在较高温的条件下易于进入硫化物晶格，在中低温条件下，硫含量较低时，可形成硒的独立矿物。洋壳中的铁锰结壳、页岩及浮游沉积物等是自然界中碲和硒的重要储库［9］，因此在洋陆俯冲过程中，大陆岩石圈地幔和洋壳的部分熔融会形成富碲、硒的岩浆［10-11］。碲和硒在硫化物熔体中的相容性很高（D硫化物/硅酸盐＞600），碲倾向于存在液相硫化物（SL）中，而硒则更易进入单硫化物固熔体（MSS）（DTe SL/硅酸盐/DSe SL/硅酸盐为5～9，DTe MSS/硅酸盐/DSe MSS/硅酸盐为0.5～0.8）［12］。当富碲、硒的岩浆到达下地壳，会结晶分异形成富Co、Ni的硅酸盐矿物，碲、硒存在硫化物熔体中继续向上运移；当岩浆到达中地壳，温度低于900℃时，硫化物熔体与Te-Se熔体发生相分离；当岩浆到达上地壳，侵位形成班岩体及Cu矿床，Ag-Pt-Pd则高度集中在富Te-Se熔体中，并最终形成贵金属矿物［13］。普朗铜金矿床中的碲和硒可能与区内晚三叠世的俯冲造山密切相关，富碲和硒的岩浆也促进了铂族元素的富集成矿。
普朗斑岩铜金矿床中碲化物和硒化物的发现，对资源的综合利用及矿床成因研究具有重要意义。矿床中碲和硒的资源量规模大，大部分以独立矿物形式存在，且常与Au-Ag-PGE共生，具有较好的经济回收利用价值。碲化物和硒化物的产出也为成矿物质来源及岩浆演化过程提供了新的研究方向。
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图 1 Mo （277.54nm）和Ge （326.9494nm）蒸发行为比较
Figure 1. Comparison of evaporation behaviour of Mo （277.54nm） and Ge （326.9494nm）.
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图 2 曝光时间选择
Figure 2. Choice of exposure time. When the exposure time is less than 30s, the evaporation intensity of Mo and Ge increases significantly; however, after 35s, the evaporation intensity of Mo reaches a plateau.
表 1 标准系列配比及钼含量
Table 1 Ratio of the standard series and concentration of Mo.
标准系列
编号标准系列配比成分 钼含量
（μg/g）1 GBW07711 500 2 GBW07141 660 3 GBW07142 1500 4 GBW07143 5400 5 GBW07144∶基体（GSES Ⅰ）=1∶50 10016 6 GBW07144∶基体（GSES Ⅰ）=1∶25 20032 7 GBW07144∶基体（GSES Ⅰ）=1∶5 100160 8 GBW07144 500800 
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表 2 方法精密度和准确度
Table 2 Accuracy and precision of the method.
测定次数 GBW07141 GBW07142 GBW07143 1 629.02 1554.30 5221.84 2 635.15 1574.90 5043.96 3 699.70 1429.01 5767.91 4 641.80 1448.65 5803.26 5 659.32 1498.60 5456.75 6 654.50 1336.90 5286.44 7 683.15 1350.19 5087.67 8 676.11 1713.88 5650.50 9 681.28 1643.03 5354.01 10 678.51 1605.32 5214.25 11 659.32 1386.38 5327.01 12 679.70 1381.34 5941.20 标准值（μg/g） 660.00±30 1500.00±100 5400.00±200 AVE（μg/g） 664.80 1493.54 5429.57 RSD （%） 3.28 8.30 5.43 相对误差（%） 0.73 −0.43 0.55 △lgC 0.003 −0.002 0.002
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