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摘要:
铜矿床中的伴生元素通常具有较高经济价值，其矿物颗粒细小，往往从微米级到纳米级，因此难以被发现和获得利用，进而导致无法系统地对其赋存状态进行研究。本文以“里伍式”铜矿床中的矿石矿物为研究对象，通过背散射图像、二次电子像观察以及X射线光谱点、线与面分析技术的相互佐证，获得铜矿床伴生元素矿物物相、形貌特征、赋存状态、定性/定量及分布规律等信息。实验中选取扫描电镜的加速电压20kV、发射电流10μA、能谱脉冲处理活时间100s，同时对样品前处理、测试过程中的关键技术进行详细探讨，形成了一套有效的分析铜矿床中有关伴生元素的能谱-扫描电镜（EDX-SEM）微区分析方法。应用该方法分析查明四川里伍铜矿床中金、银、钴、铋、硒等元素的赋存状态，这些元素以独立矿物存在或类质同象的形式分布在其他矿物中。通过对这些伴生元素赋存状态的研究，为矿物工业价值的认定、矿床资源评价、伴生元素的回收利用提供了微观依据，为矿山的开采、选矿以及冶炼工艺过程的制定提供了技术支撑。
Abstract:BACKGROUND Associated elements in copper deposits are of high economic value. However, they are difficult to locate and utilize because of their fine (micrometer to nanometer) size.
OBJECTIVES To develop a method for determining the occurrence of associated elements in copper deposits.
METHODS Backscatter image, secondary electron image, X-ray spectrum point, line and mapping analysis technology were used to determine the mineral phases, morphological characteristics, occurrence, qualitative/quantitative and distribution laws of the associated elements of the copper deposit. The acceleration voltage of the scanning electron microscope was 20kV, the emission current was 10μA, and the energy spectrum dwelling time was 100s.
RESULTS The key technologies in the sample pretreatment and analysis were discussed in detail to form a set of effective analyses of copper deposits. The energy spectrum-scanning electron microscope (EDX-SEM) microanalysis method of associated elements was established. Gold, silver, cobalt, bismuth, and selenium were all distributed in other minerals in the form of independent minerals or isomorphic substitution.
CONCLUSIONS Through the study of the occurrence of the associated elements, a micro basis for the identification of mineral industrial value, mine resource evaluation, and the recovery and utilization of associated elements has been established, and provides technical support for mining, beneficiation and smelting formulation.
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Key words:
- EDX-SEM /
- copper deposit /
- associated elements /
- occurrence /
- isomorphism
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表 1 矿石样品采集信息及化学分析结果
Table 1. Collection information and chemical analysis results of ore samples
样品编号 矿石性状或岩性 采样地点 Cu含量(×10-2) Au含量(×10-6) Ag含量(×10-6) KKLWB2-1 块状矿石 里伍本部B2矿体 12.92 0.30 < 10.0 KKLWB2-2 块状矿石 里伍本部B2矿体 21.70 0.31 < 10.0 KKLWB2-5 块状矿石 里伍本部B2矿体 3.70 < 0.10 16.8 KKLWB2-6 块状矿石 里伍本部B2矿体 1.56 < 0.10 < 10.0 JKLWB2-7 浸染状矿石 里伍本部B2矿体 4.15 0.17 16.8 WYLWB2-16 浸染状矿石 里伍本部B2矿体 - 0.15 < 10.0 WYLWB2-17 浸染状矿石 里伍本部B2矿体 - 0.15 < 10.0 KKLW-3 块状矿石 里伍本部 3.04 < 0.10 < 10.0 KKLWB1-1-1 块状矿石 里伍本部B1矿体 16.55 < 0.10 17.9 KKLWA2-3 块状矿石 里伍本部A2矿体 10.06 0.72 59.0 KKLWA2-8 块状矿石 里伍本部A2矿体 7.37 0.55 64.9 GKLWE1-8 网脉状-块状矿石 里伍本部E1矿体 5.45 0.14 123.0 GKLWA2-10 网脉状-块状矿石 里伍本部A2矿体 3.93 0.16 36.3 GKLWA2-11 网脉状-块状矿石 里伍本部A2矿体 10.98 2.38 16.5 KKHN-1 块状矿石 黑牛洞 19.99 0.11 < 10.0 KKHN-2 块状矿石 黑牛洞 14.74 0.18 < 10.0 KKHN-3 块状矿石 黑牛洞 15.61 < 0.10 < 10.0 KKHN-4 块状矿石 黑牛洞 15.88 0.15 < 10.0 KKHN-7 块状矿石 黑牛洞 15.35 0.87 51.1 KKHN-13 块状矿石 黑牛洞 19.10 0.12 - HWJG-6 块状矿石 挖金沟 10.77 0.13 34.4 WJG-7 块状矿石 挖金沟 1.58 0.23 11.6 JK207H141/6 浸染状矿石 黑牛洞 - 0.20 < 10.0 TK207H154/5 条带状矿石 黑牛洞 - 0.16 14.2 KK207H16-1 块状矿石 黑牛洞 - 0.11 < 10.0 KK207H222/6 块状矿石 黑牛洞 - 0.13 33.0 KK207H234/6 块状矿石 黑牛洞 - 0.20 20.5 TKZK20841H18 条带状矿石 黑牛洞 - 0.12 - KKZZ-5 块状矿石 中咀 4.37 < 0.10 29.0 KKZZ-6 块状矿石 中咀 4.97 < 0.10 29.6 KKZZ-7 块状矿石 中咀 17.72 < 0.10 15.4 WY1P-7 二云母石英片岩 中咀 - 0.10 10.8 
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表 2 能谱-扫描电镜工作条件
Table 2. Working conditions of EDX-SEM instrument
实验内容 加速电压(kV) 发射电流(μA) 工作距离(mm) 处理时间(s) 活时间(s) 死时间 扫描电镜的背散射电子(BSE)观察 20 10 15 - - - 二次电子(SE)影像观察 20 10 15 - - - EDX定性分析 20 10 - 6 100 20%~40% EDX定量分析 20 10 - 6 100 20%~40% EDX线分析 20 10 - 2 依据线扫描的长短和元素含量高低而定 20%~40% EDX面分析 20 10 - 2 依据面分析区域大小和元素含量高低而定 20%~40%
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表 3 矿物能谱分析结果
Table 3. Energy spectrum analysis results of the minerals
矿物名称 化学式 元素含量(%) S Fe Co Sb Te Zn Te Bi Au Ag W Ca O 硫锑钴矿 CoSbS 15.59 0.83 24.13 57.56 1.89- - - - - - - - - 赫碲铋矿 Bi7Te3 - 0.73 - - - 3.12 24.70 71.45 - - - - - 赫碲铋矿 Bi7Te3 - 1.04 - - - 2.26 25.19 71.50 - - - - - 自然金 Au - 1.26 - - - - - - 98.74 - - - - 银金矿 AgAu - 1.06 - - - - - - 76.51 22.43 - - - 类质同象金 Au 3.15 4.11 - - 34.93 - - - 5.60 52.22 - - - 银金矿 AgAu - 10.64 - - - - - - 86.53 2.83 - - - 碲银矿 Ag2Te 1.61 3.42 - - - 37.38 - 57.59 - - - 硫铋银矿 AgBiS2 17.31 1.54 - - - - 0.98 65.53 - 14.65 - - - 单质铋 Bi - 3.73 - - - - 96.27 - - - - - 单质铋 Bi - - - - - - 100 - - - - - 碲铋矿 Bi2Te3 - - - - - - 36.62 63.38 - - - - - 碲铋矿 Bi2Te3 - - - - - - 46.75 53.25 - - - - - 白钨矿 CaWO4 - - - - - - - - - - 63.14 13.97 22.89 白钨矿 CaWO4 - 0.98 - - - - - - - - 60.55 13.59 24.88 注：“-”表示未能检出该元素。
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