2020, Vol. 36
引用本文
廖仁强, 刘鹤, 李聪颖, 孙卫东. 2020. 从铼的地球化学性质看我国铼找矿前景. 岩石学报, 36(1): 55-67, doi: 10.18654/1000-0569/2020.01.07
Liao RQ, Liu H, Li CY and Sun WD. 2020. Rhenium resource exploration prospects in China based on its geochemical properties. Acta Petrologica Sinica, 36(1): 55-67(in Chinese with English abstract)
从铼的地球化学性质看我国铼找矿前景
1. 中国科学院海洋研究所, 深海研究中心, 青岛 266071;
2. 青岛海洋科学与技术试点国家实验室, 海洋矿产资源评价与探测技术功能实验室, 青岛 266237;
3. 中国科学院大学, 北京 100049;
4. 中国科学院海洋大科学研究中心, 青岛 266071
2. 青岛海洋科学与技术试点国家实验室, 海洋矿产资源评价与探测技术功能实验室, 青岛 266237;
3. 中国科学院大学, 北京 100049;
4. 中国科学院海洋大科学研究中心, 青岛 266071
摘要: 铼是生产涡轮发动机耐高温超级合金的核心元素，被誉为改变航空业的金属。斑岩铜矿伴生的辉钼矿和还原性沉积岩中的硫化物是铼的主要赋存矿物。从目前铼的产量来看，全球近一半的铼产出于智利的斑岩铜钼矿床。据美国地质调查局估计，智利的铼探明储量在1300吨。其他国家依次是美国、俄罗斯、秘鲁等国，均在300吨左右。从现有的数据估算我国目前的铼储量约为250吨，以辉钼矿伴生为主。从地球化学的角度来看，铼是地球上最稀有的金属之一；作为中度不相容的亲铜、亲铁元素，铼倾向于在岩浆中富集；铼对硫逸度、氧逸度敏感，在表生过程中可以通过氧化还原过程富集于黑色页岩等还原性沉积物中。封闭、半封闭的海湾是其常见的富集位置。在埃迪卡拉纪和寒武纪，大气中的氧气含量大幅度上升，是表生过程中铼迁移、富集的最佳时期。我国华南广泛分布形成于近海环境的埃迪卡拉纪-寒武纪黑色页岩，仅鄂西分布范围就有数千平方千米，厚度可以达到200m，其中铼的含量达到0.1×10-6~0.6×10-6，远景资源量在万吨以上，是寻找铼矿的最佳选区之一。
关键词:
铼 辉钼矿 寒武纪 黑色页岩 华南
Rhenium resource exploration prospects in China based on its geochemical properties
1. Center of Deep Sea Research, Institute of Oceanology, Chinese Academy of Sciences, Qingdao 266071, China;
2. Laboratory for Marine Mineral Resources, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266237, China;
3. University of Chinese Academy of Sciences, Beijing 100049, China;
4. Center for Ocean Mega-Science, Chinese Academy of Sciences, Qingdao 266071, China
2. Laboratory for Marine Mineral Resources, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266237, China;
3. University of Chinese Academy of Sciences, Beijing 100049, China;
4. Center for Ocean Mega-Science, Chinese Academy of Sciences, Qingdao 266071, China
Abstract: Rhenium (Re) is the crucial element in the production of heat resistant superalloys for turbine engines, and it is known as the aviation industry transforming metal. The rhenium deposits predominantly occurred in molybdenites of porphyry copper-molybdenum deposits and sulfides in the reducing sedimentary rocks. At present, nearly half of the rhenium reserves in the world were contained by the porphyry copper-molybdenum deposits in Chile. The total rhenium reserves in Chile estimated by the United States Geological Survey are ca. 1300 tons. The following countries include United States, Russia, Peru and other countries, totaling 300 tons. It is estimated from the available data that the proved rhenium reserves in China are about 250 tons, mainly associated with molybdenites. In geochemical perspective, rhenium is one of the rarest metals on the Earth. As a moderately incompatible chalcophile and siderophile element, rhenium is enriched in magmas. Rhenium is sensitive to sulfur fugacity and oxygen fugacity, which prefer to be enriched in sediments under the reducing conditions, e.g. black shale, during the surface process. Enclosed and semi-enclosed bays are the common places for rhenium concentration. During the Ediacaran and Cambrian periods, the atmospheric oxygen increased greatly, which was the most favorable period for the migration and enrichment of rhenium during the Earth's surface processes. The Ediacaran-Cambrian black shales, formed in offshore environments, are widely distributed in South China. The western Hubei has included several thousand square kilometers of black shale, of which the thicknesses is up to 200 meters and the rhenium concentration reaches 0.1×10-6~0.6×10-6. The predicted resource of contained rhenium in this area is more than 10, 000 tons, which is potential to be one of the best target for rhenium exploration.
Key words:
Rhenium Molybdenite Cambrian Black shale South China
铼(Re)，自然界中最难熔的元素之一，最初主要用于催化剂和高温加热电离带等。由于具有难熔难蚀及良好的塑性等物化条件，目前，铼的最重要的用途是制造在高温下保持足够机械强度的超级合金，其价格也因此飞涨至每吨数百万乃至千万美元。超级铼合金是高性能飞机发动机涡轮的核心材料，其目的是保证飞机发动机叶片在高温下不变形。自二十世纪中后期开始，铼合金被陆续应用于F-22、F-35的发动机中。因此，铼被誉为改变航空业的金属。
迄今为止，斑岩型铜钼金矿床是世界铼产量的主要来源。从目前探明储量看，全球近一半(约55%)的铼产出于智利的斑岩铜钼矿床，据美国地质调查局估计智利的铼探明储量约1300吨(Polyak, 2013; John et al., 2017)。其他国家依次是美国、俄罗斯、秘鲁等国，均在300吨左右。从前景储量看，美国地质调查局估计美国铼的前景储量在5千吨，全球其他国家总的前景储量在6千吨(Polyak, 2013; John et al., 2017)。在哈萨克斯坦和波兰，大部分铼矿产量主要来自受沉积物影响的层控铜矿床(Bartlett et al., 2013)。我国铼资源储量目前并没有较为明确的统计数据，截止2003年，我国铼的储量为237吨，有铼矿11处，分布于9个省，主要分布于江西德兴、湖南宝山、陕西洛南和金堆城、河南栾川及吉林大黑山等地。据前人估计，陕西金堆城钼矿、河南栾川钼矿、吉林大黑山钼矿、黑龙江多宝山铜(钼)矿等矿床中，合计占全国铼总储量的近90%(吴贤等, 2008)。但是，实际上秦岭钼矿带斑岩钼矿中铼的品位很低(约十万分之一)，急需寻找更好的铼矿资源。
铼的地球化学性质与钼接近，在地表风化过程中容易被氧化成钼酸盐而溶解于水，随地表径流运移，在还原条件下被固定，进入富含有机质的还原性沉积物中(孙卫东等, 2015; Sun et al., 2016; Liao et al., 2019)。研究表明，在寒武纪(~550Ma)以后，由于大气氧的大幅度升高，氧化还原敏感元素的活化迁移加强，富含有机质的沉积物中钼含量大幅度升高(Kump, 2008; Scott et al., 2008; Saltzman et al., 2011; Lyons et al., 2014; Smit and Mezger, 2017)。相应地，其铼含量也应该有较大幅度的升高。
本文尝试通过对Re的地球化学性质的分析，探讨我国铼成矿前景，为进一步指导铼矿找矿提供依据。
1 铼的地球化学性质与富集铼的原子序数为75，原子质量为186.2mol/g。在元素周期表中，铼位于锰和锝下方，与钨和铂族元素(PGE)相邻，并且在钼的斜下方。铼的密度为21.02g/cm3，是第四密度元素(铱、锇和铂的密度较高)。它具有六角密排晶体结构。
铼的价态范围变化宽，总共有9个，从-1到+7，其中+7、+6、+4和+2是最常见的离子，对硫逸度、氧逸度敏感。铼形成三种稳定的氧化物，分别是七氧化铼(Re2O7)、三氧化铼(ReO3)和二氧化铼(ReO2)，其中ReO3是最常见的氧化物。七氧化铼，又名铼庚醚，是一种明亮的黄色挥发性固体(Colodner et al., 1995)，溶于水中形成高铼酸(HReO4)和高铼酸盐。铼对硫有很强的亲和力，同时因Re4+与Mo4+的半径相似，故铼经常类质同象置换钼而富集于辉钼矿中。铼化合物的不寻常特征，包括七氧化铼异常高的挥发性及其在水中的高溶解度等，都有助于将铼从辉钼矿精矿焙烧产生的烟尘中回收。
在硅酸盐地球中，铼通常以+4和+6价存在，表现为中度不相容元素的特征。铼是长半衰期的放射性元素中唯一的中度不相容的亲铜、亲铁元素(Shirey and Walker, 1998；Sun et al., 2003a)。铼有两种主要的天然同位素，185Re(稳定，占天然Re的37.4%)和187Re(具有放射性，占天然Re的62.6%)。铼有多种衰变体系，目前最常利用的是187Re通过β衰变为187Os，半衰期约为4.1×1010y (Bosch et al., 1996)。铼-锇同位素系统常被用来测定矿床中硫化物矿物(最常见的是辉钼矿)的年龄(McCandless and Ruiz, 1993；Stein et al., 2001)以及示踪壳-幔相互作用(杜安道等, 1994, 2009; 孙亚莉等, 1997; Gao et al., 2002; Du et al., 2018, 2019a, b)。
铼是地球陆壳中最稀有的元素之一，目前报道的铼在地壳中的丰度变化范围较大，在0.2×10-9~2×10-9之间(Taylor and McLennan, 1995；Rudnick and Gao, 2014)。铼具有很强的挥发性，通过火山岩获得的铼的丰度值偏低，而由于铼在表生过程中易于被氧化，所以根据黄土获得的铼的丰度也偏低。考虑到大洋玄武岩中铼的丰度为1×10-9，本文倾向认为铼的地壳丰度在2×10-9左右(Sun et al., 2003b)。铼在地幔中的丰度为50×10-12(McDonough and Sun, 1995)。
铼是极度分散元素，很少作为一种金属或其独立矿物存在，主要为辉铼矿、铜铼矿和锇铜铼矿(Kuleshevich et al., 2010)，但含铼矿物种类繁多，包括辉钼矿、铌铁矿、辉铜矿、白钨矿等61种，有的地区黑色岩系中也富集铼(Figueiredo et al., 2014; 田立强等, 2016)。辉钼矿是铼富集的矿物，不同类型的辉钼矿中铼的含量差别很大。已有报道中，辉钼矿中铼的含量最高可以含有百分之十(Ishihara, 1988; Bernard et al., 2003; 毛景文等, 2004; Yudovskaya et al., 2008; 魏庆国等, 2009; 应立娟等, 2009)。从矿床的角度看，斑岩铜金矿床中伴生的辉钼矿中铼含量最高，可以达到辉钼矿的千分之三的平均品位，是铼的主要来源。相比之下，斑岩钼矿中辉钼矿的铼含量普遍很低，可以低到百万分之一(杜安道等, 1994; 张兴国等, 2008; Li et al., 2012a; 聂凤军等, 2013; 卢志强等, 2016)，目前国际上一般不将其作为铼矿开采。此外，在同一矿床中，低温下形成的辉钼矿铼含量高。例如，在一些火山通道中形成的辉钼矿，随温度降低，铼含量升高，低温部位辉钼矿中铼的含量可以达到10%(Bernard et al., 2003; Yudovskaya et al., 2008)。
自然界中也发现了一些含铼量非常高的硫化物，如1986年首次在日本Usu火山的喷气孔中发现了辉铼矿显微晶体(ReS2) (Bernard and Dumortier, 1986)，1994年在俄罗斯千岛群岛地区Iturup岛上的Kudryavy火山的高温喷气孔中发现了铼矿石晶体，主要成分为ReS2 (Korzhinsky et al., 1994)，在希腊北部的帕戈里拉奇斑岩中也曾报道过(Voudouris et al., 2009)，在芬兰Nivala的Nivala镍-铜-PGE矿的硫化物精矿中发现了富含铼的(Cu, Fe)(Re, Mo)4S8的显微(≤75μm)晶体(Kojonen et al., 2004)，2008年在俄罗斯远东勘察加半岛的火山喷气口也发现有纯的硫化铼矿物(Kremenetsky and Chaplygin, 2010)。另外，美国南部的一些铀矿、俄罗斯的页岩及某些石油产品燃烧后的烟灰中也含有一定量的铼，但具体的含量数据未见报道(吴贤等, 2008)。
矿石中提取铼的方法主要包括溶剂萃取法、离子交换法、沉淀法、氧化还原法、碱浸置换法、电渗析法等，不同赋存矿物及赋存状态所采用的回收方法不同(曹冲等, 2014; 彭真等, 2012; 夏瑜等, 2017)。由于铼的氧化物Re2O7具有挥发性，且溶于水，辉钼矿冶炼的烟道气中可以提取铼，通常以高铼酸铵的形式产出。对于黑色页岩中铼的分离，目前还缺乏相关的研究。
国际上铼的储量主要来自斑岩铜金矿床中的辉钼矿。我国辉钼矿储量占全球的近一半，主要是斑岩钼矿，多数辉钼矿中铼含量低(1×10-9~10×10-9)。钼矿主要分布在秦岭-大别山钼矿带(陈衍景等, 2000, 2009; Mao et al., 2008; Li et al., 2012b; Mi et al., 2017)，按照该钼矿带探明斑岩钼矿中钼的储量(约800万吨)、其辉钼矿中铼的含量在十万分之一的量级计算，秦岭-大别山斑岩钼矿中的铼仅为80吨。由于含量太低，回收率很难保证。迄今为止，国际上没有从此类矿床中提取铼的案例。因此，我国急需寻找更好的铼矿资源。
不同类型含铼钼矿床中铼的含量不一，差别巨大。我国著名的特大型斑岩钼矿床，如陕西金堆城钼矿床的辉钼矿含铼17×10-6~20×10-6(符新科和尹孝刚, 2004)。特大型斑岩矽卡岩型钼钨矿床，如河南栾川地区钼矿床的辉钼矿含铼10×10-6~20×10-6(李永峰等, 2003)，铼总量约135.39吨(崔世俊和郭娜娜, 2013)。葫芦岛地区大型矽卡岩型钼矿床的辉钼矿含铼10×10-6~20×10-6。而江西德兴斑岩铜钼矿床的辉钼矿含铼近600×10-6~700×10-6(王诚华, 2006)，按照其钼储量20万吨和辉钼矿中600×10-6的品位计算，德兴斑岩铜矿的铼储量可以达到120吨。不过，这些钼矿大部分已被开采，铼回收量尚不清楚，剩余储量也不清楚。湖南宝山斑岩铜钼矿床的辉钼矿含铼300×10-6~450×10-6(路远发等, 2006)，陕西洛南地区钼矿床的辉钼矿中铼含量约为250×10-6~300×10-6、个别地段的辉钼矿含铼高达350×10-6~370×10-6(袁海潮等, 2014)。但是这些地区的钼储量较小。相应地，我国钼矿中铼资源分布也是不均匀的，铼与钼储量之间缺乏对应关系。本文根据文献统计结果显示(图 1)，我国钼矿床及其相关的矿床中铼资源总量超过1300吨，其中10吨以上的钼矿床主要分布在东北、兴蒙造山带、秦岭-大别造山带和冈底斯造山带，合计占全国铼总量的近90%，集中分布在陕西金堆城钼矿、河南栾川钼(钨)矿、吉林大黑山钼矿、黑龙江多宝山铜(钼)矿、西藏纳日贡玛钼铜矿、帮浦钼铜矿、新疆白山钼矿、内蒙古乌努格吐山铜钼矿等矿床中。另外，西部地区的一些斑岩钼矿和斑岩铜钼矿值得重点关注，如西藏南木铜矿、新疆东戈壁钼矿。此外，紫金山、玉龙等斑岩铜钼矿床有可能提供较多的铼。黄龙铺、杨家杖子等矽卡岩型钼矿，辉钼矿中铼的含量也可以达到万分之几，也值得重点关注
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图 1 我国典型辉钼矿的分布图及其估计铼资源量(底图据Zeng et al., 2013；范羽等，2014修改) 图中铼估计储量计算方法：根据钼矿床及钼相关矿床中辉钼矿的铼平均浓度、整个矿床的平均钼品位和矿床总吨位进行乘积计算.数据选自王召林等, 2008; 张绮玲等, 2003; 孟祥金等, 2003; 李孙雄等, 2014; 黄凡等, 2012; 刘晓煌等, 2007; 袁海潮等, 2014; 李诺等, 2007; 李永峰等, 2003; 李法岭, 2011; 晏国龙等, 2012; 周珂等, 2009; 黄典豪等, 1996; Dai et al., 2009; 黄超勇等, 2011; 邓刚等, 2004; 刘永慧等, 2014; 谭钢等, 2010; 聂凤军等, 2007a, b, 2011; 刘翼飞等, 2011; 崔根等, 2008; 赵元艺等, 1997; 邵军等, 2012; 王成辉等, 2009 Fig. 1 Schematic showing the distribution of the typical molybdenite ore-deposits in China and their estimated rhenium resources (base map modified after Zeng et al., 2013, Fan et al., 2014) The calculating method of rhenium reserves is based on the average rhenium concentration, molybdenum content and rhenium content of molybdenite in molybdenum ore-deposits and molybdenum related ore-deposits. The average grade of molybdenum and the total tonnage of the deposit are calculated by product. Data are selected from Wang et al., 2008, 2009; Zhang et al., 2003; Meng et al., 2003; Li et al., 2003, 2007, 2014; Huang et al., 2011, 2012, 2012; Liu et al., 2007, 2011, 2014; Yuan et al., 2014; Li, 2011; Yan et al., 2012; Zhou et al., 2009; Huang et al., 1996, Dai et al., 2009; Deng et al., 2004; Tan et al., 2010; Nie et al., 2007a, b, 2011; Cui et al., 2008; Zhao et al., 1997; Shao et al., 2012 |
表生沉积过程是铼富集的另一个重要途径(Sun et al., 2016; Liao et al., 2019)。我国华南地区广泛分布寒武纪黑色页岩，这些黑色页岩中富集铼。从已有的少量数据看，这些黑色页岩的铼品位可以达到0.1×10-6~0.6×10-6(Jiang et al., 2007)。由于这些黑色页岩中铼主要富集于硫化物(黄铁矿等)中，实际开采成本应该接近或低于同等品位的金矿。因此，这些黑色页岩很多可能都已达到可采品位，初步估计，黑色页岩中铼资源量可以达到万吨以上(图 2)。在上述地区寻找高品位铼矿是一个好的找矿方向。
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图 2 世界主要含铼矿床的品位-品级(据John et al., 2017修改) 华南寒武纪黑色页岩中铼金属量估算方法：黑色页岩分布范围、厚度及其平均铼含量三者的乘积 Fig. 2 Diagram showing the tonnages v.s. grades of the major rhenium-bearing ore-deposits in the world (modified after John et al., 2017) Estimating method for the amount of rhenium in the Cambrian black shale of the South China: The product of the distribution range, thickness and average rhenium content of the black shale |
我国华南广泛发育晚震旦世和早寒武世黑色岩系(范德廉等, 2004; 杨剑和易成发, 2005)，该页岩层地理上横跨云南、贵州、湖南、湖北、江西和浙江等地(图 3)(范德廉等, 1973; 陈南生和杨秀珍, 1987; Coveney et al., 1992; 毛景文等, 2001; Mao et al., 2002)，呈北东向展布，平均厚约数十米，绵延约1600km，如此大的规模为我国所独有(Mao et al., 2002)；现多采用“牛蹄塘组”命名发育这套黑色页岩的地层(罗超等, 2014; 吴陈君等, 2014; 李海等, 2016)。
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图 3 华南寒武纪黑色页岩构造背景及分布图(据Mao et al., 2002修改) Fig. 3 Tectonic background and distribution map of the Cambrian black shale in the South China (modified after Mao et al., 2002) |
华南牛蹄塘组整体从下往上的典型层序为硅质岩、含磷结核和磷块岩的黑色页岩、Ni-Mo多金属硫化物矿层、黑色页岩，其下覆地层为新元古代灯影组白云岩或留茶坡组硅质岩(范德廉等, 2004; 蒋少涌等, 2008)，两者间为平行不整合接触。不同地区，牛蹄塘组及其中黑色页岩分布不一，如鄂西地区牛蹄塘组在剖面上可大致分为两段：下段主要为灰黑色-黑色炭质页岩和炭质泥岩，见灰岩透镜体；上段地层中灰岩比例增加，页岩逐渐减少。平面上，牛蹄塘组黑色页岩厚度基本呈环带状分布(图 4)，最高值位于宣恩-咸丰一线，平均厚度介于160~280m，以此为中心向四周逐渐减薄，向西北至建始、利川一带变为80~100m，向东则多在60m以下(李海等, 2016)。而黔东北地区牛蹄塘组暗色泥页岩厚度横向展布稳定，优质页岩平均厚度约40~50m，整体厚度大于30m，但平面分布不均(王玉芳等, 2016)。
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图 4 鄂西黑色页岩平均厚度图(据李海等，2016修改) Fig. 4 Average thickness map of black shale in the western Hubei (modified after Li et al., 2016) |
关于这套黑色页岩的沉积相，前人进行了大量研究。陈兰等(2006)通过生物标志化合物特征参数和碳同位素组成特征的研究，认为湘黔地区早寒武世黑色岩系沉积环境为贫氧-缺氧的还原环境，这与前人认为的华南黑色页岩属于滞留缺氧沉积环境一致(李任伟等, 1999; Steiner et al., 2001; 陈兰等, 2006; 杨兴莲等, 2008)。
华南寒武系黑色页岩素有“多元素富集层”之称，其底部赋存有一层极富各种金属元素的硫化物矿层，尤以富集Ni、Mo和PGE为特征，如湘西北Ni-Mo-PGE矿化带(Xu et al., 2013)、遵义Ni-Mo-PGE矿化带(Mao et al., 2002)等，这些黑色页岩也富集铼(图 5)。
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图 5 华南寒武纪黑色页岩中富集铼(底图孙卫东等, 2010; 华南黑色页岩数据选自Jiang et al., 2007) Fig. 5 Enrichment of rhenium in the Cambrian black shale of the South China (base map after Sun et al., 2010; data of the South China black shale from Jiang et al., 2007) |
对于黑色页岩中这些多金属矿床的形成机理及形成环境，主要有两种假说：①海底热液成因说(李胜荣和高振敏, 1995; Steiner et al., 2001; Coveney, 2003; 杨瑞东等, 2005; Jiang et al., 2006, 2007; Orberger et al., 2007; 蒋少涌等, 2008; Chen et al., 2009; Han et al., 2017)；②海水成因说(Mao et al., 2002; Lehmann et al., 2007; Yin et al., 2017)。最近，Lan et al.(2017)通过对湖南、贵州等地牛蹄塘组黑色页岩内Ni-Mo-PGE矿床地球化学特征的分析，认为其成矿物质具有海水、热液以及陆源碎屑三者混合成因。华南寒武系黑色页岩中另一类重要资源就是页岩气，目前的研究已经划定了一些页岩气勘探区和远景区(何金先等, 2011; 李海等, 2016; 王玉芳等, 2016)。
本文初步的研究认为华南寒武纪黑色页岩多种性质迥异的金属同时富集可能与埃迪卡拉纪大气氧突然升高(图 6a)(Smit and Mezger, 2017; Lyons et al., 2014; Saltzman et al., 2011; Scott et al., 2008; Sahoo et al., 2012)和生命大爆发(朱茂炎, 2010; Orberger et al., 2007)有关。在大气氧升高之前，铼在表生过程中被氧化的量很少。寒武纪时大气氧的突然升高到原来的100倍以上，导致大量的铼在表生过程中集中被氧化，聚集到水体中。而生命大爆发促进了还原性物质的累积(Butterfield, 2009, 2011)，形成黑色页岩，将水体中的铼富集到黑色页岩中(图 6b)。甚至铼可能与镍钼等金属一同参与了生命过程中。
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图 6 地球大气氧含量随时间演化图(a, 据Lyons et al., 2014; Smit and Mezger, 2017修改)及海洋体系铼的物质来源和主要的迁移和沉积过程简图(b, 据Jiang et al., 2006修改) PO2-大气氧分压；PAL-当前大气水平；左纵轴表示相对于当前大气水平的氧分压；右纵轴表示氧分压 Fig. 6 The evolution of the earth's atmospheric oxygen content over time (a, modified after Lyons et al., 2014; Smit and Mezger, 2017) and chematic diagram of the material sources and main migration and sedimentary processes of Re in marine systems (b, modified after Jiang et al., 2006) PO2-atmospheric partial pressure of oxygen; PAL-present atmospheric level; left longitudinal axis, partial pressure of oxygen relative to the present atmospheric level; right longitudinal axis, partial pressure of oxygen |
黑色页岩中的铼金属含量巨大。我国华南广泛分布寒武纪黑色页岩，仅鄂西分布范围就有数千平方千米，其中铼含量达到0.1×10-6~0.6×10-6，据保守估计，前景资源量在万吨以上(表 1)。但是，黑色页岩中的铼作为一种远景战略资源，目前的研究程度及勘查力度都相对薄弱，一方面是因为目前还缺乏将铼元素从页岩中进行工业分离、回收的工艺(于世昆和伍艳辉, 2010; 冯宝奇等, 2013; 邬建辉等, 2015)；另一方面则是由于目前的铼矿产量研究多集中在硫化物、铂族元素及铀矿物等伴生矿物(Mao et al., 2002; Aminzadeh et al., 2011; Xu et al., 2013)，对黑色页岩中铼的地球化学行为及其伴生矿物形式认识不足。基于我国目前面临的铼矿形势及未来对铼矿的需求，本文建议加大对黑色页岩中铼的研究，包括地质勘查、分离、回收等，以满足国家经济发展的需要。
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表 1 部分华南黑色页岩中铼含量及其中Ni-Mo硫化物层中铼含量 Table 1 Rhenium contents of the black shale and Ni-Mo sulfides from the South China |
铼因其具有耐高温、耐熔蚀的特性，在航空制造业中占有十分重要的地位。作为中度不相容的亲铜、亲铁元素，铼对地表环境敏感，在表生过程中强烈富集。斑岩铜矿伴生的辉钼矿和还原性沉积岩是铼的主要富集类型。我国斑岩钼矿床分布不均，辉钼矿中铼含量总体偏低，很多没有达到回收利用的伴生矿品位。我国华南广泛分布寒武纪黑色页岩，其中铼含量达到0.1×10-6~0.6×10-6，远景资源量在万吨以上，是寻找铼矿的最佳选区。
致谢 感谢四位匿名审稿人对本文提出的宝贵意见和建议。
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