锡盟锗矿褐煤中金属元素地球化学特性与锗分析方法的研究
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摘要
由于锗的光学特性及其化合物的催化特性，预计该元素将在未来高科技领域中扮演越来越重要的角色，因此近年来在内蒙古锡林郭勒盟镜内发现的与褐煤共生的特大型锗矿床受到了广泛的关注。为了今后能尽快展开全面综合开发利用锡盟锗矿褐煤的工作，本论文主要作了以下一些基础研究：
(1)利用X射线荧光光谱定性及半定量的分析方法调查了锡盟锗矿褐煤中金属元素的分布富集状况，结果表明，该煤中Ge、W、As、Cd相对于地壳克拉克值发生明显的富集，其它元素均发生不同程度的亏损。研究认为盆地基底花岗岩提供了形成锗矿化的锗。
(2)建立了两种测定锡盟锗矿褐煤中锗的新方法。第一种方法是5′-硝基-水杨基荧光酮—TritonX-100荧光熄灭法，我们研究了该测定体系的荧光光谱，同时进行了条件实验。按本法设计的最佳方案，在抗坏血酸掩蔽下可不经分离直接测定锡盟褐煤中的微量锗，方法简便、实用，灵敏度、选择性、准确度均有一定优势。第二种方法是双向视ICP-AES法，利用新型的双向视全谱直读ICP-AES可直接测定具有复杂成份的褐煤样品中的微量元素Ge和主要成狄金属元素Al、Fe、Ca、Mg、K、Na、Ti。本文优化了仪器的工作参数并合理地选择了无干扰的分析谱线和等离子体测视方式，合理地扣除了光谱背景，样品灰化后采用HNO_3／HF／HClO_4混合酸消解，测定结果与国标方法测定值吻合。该方法高效、灵敏、线性范围宽且能进行多元素同时测定，能满足大批量试样的分析要求。
(3)改进了Querol逐级化学提取方法并利用改进后的方法在ICP-AES辅助测定下分5步提取了锡盟锗矿褐煤中Ge和主要成灰金属元素Al、Fe、Ca、Mg、K、Na、Ti的化学形态，五种形态分别是：水溶态、可交换态、碳酸盐和表面氧化物结合态、有机物和硫化物结合态及残渣态。提取结果主要为合理的、有针对性的选择提锗工艺流程提供理论依据和数据基础。本实验结果显示锗元素主要以有机物和硫化物结合态形式存在锡盟褐煤当中。
Foresee germanium will act as more and more important role in the advanced science and technology field in the future because of its wide-ranging optical properties and chemical catalyst properties, therefore, the super-large germanium deposit paragenesis with lignite discovered in Xilinguole League, Inner Mongolia has received considerable attention. Some base researches was done in this article in order to carry out ail-roundly work of generalized exploitation and utilization of lignite in Xilinguole League germanium deposit henceforth.
(i) Distribution and enrichment of metal elements of lignite in Xilinguole League germanium was investigated with qualitative and half-quantitative X-ray fluorescence spectrometric (XRF) method, and the results indicate that Ge, W, As, Cd enrich obviously and other elements want comparing with Clarke value. The research deduces that Ge mainly came from granites in the basement of the sedimentary basin.
(ii) Two kinds of new determination methods of germanium in Xilinguole League lignite were established. The first kind of method was fluorescence quenching method with 5' -nitro-salicylfluo -rone-TritonX-100, and fluorescence spectrum of determination system was studied, condition of experimentation was searched out as well. In the optimal conditions, germanium in Xilinguole League lignite could be directly determined in the present of masking reagents. The method is simple, utility, sensitive, selective and accurate. The second kind of method was inductively coupled plasma atom emission spectrometric (ICP-AES) methods, minor germanium and major ash forming metal elements Fe, Al, Ca, Mg, K, Na, Ti in lignite could be simultaneous determined using a new type of ICP instrument equipped with a dual-view plasma torch and detectors that cover nearly all spectra at the same time. In the experimentation, the operation condition of the instrument was optimized, analytical wavelength lack of interference from element
s in the sample matrix was selected, and the spectral background was automaticly eliminated. The obtained coal ashes were dissolved in mixtures of nitric acid, hydrofluoric acid and perchloric acid after coal samples were cinerated. The analytical results were in good agreement with those provided by national standard methods. The method offers such distinctive advantages as fast, sensitive, effective, wide dynamic range and multi-element capabilities.
(iii) The speciation of Ge and major ash forming metal elements Fe, Al, Ca, Mg, K, Na, Ti in Xilinguole League lignite was investigated using modified Querol five-step sequential chemical extraction procedures. The extraction sequence was as follows: (a)water-extractable; (b)readily exchangeable ions; (c)carbonate-bound, surface oxide-bound ions; (d)organically and sulfide-bound ions; (e)residual. The results of the extraction can offer theoretical basis and data in order to rationally select craft of extracting germanium. The results of this experiment show germanium mainly exists in form of organically and sulfide-bound ions in Xiliguole League lignite.
(1)利用X射线荧光光谱定性及半定量的分析方法调查了锡盟锗矿褐煤中金属元素的分布富集状况，结果表明，该煤中Ge、W、As、Cd相对于地壳克拉克值发生明显的富集，其它元素均发生不同程度的亏损。研究认为盆地基底花岗岩提供了形成锗矿化的锗。
(2)建立了两种测定锡盟锗矿褐煤中锗的新方法。第一种方法是5′-硝基-水杨基荧光酮—TritonX-100荧光熄灭法，我们研究了该测定体系的荧光光谱，同时进行了条件实验。按本法设计的最佳方案，在抗坏血酸掩蔽下可不经分离直接测定锡盟褐煤中的微量锗，方法简便、实用，灵敏度、选择性、准确度均有一定优势。第二种方法是双向视ICP-AES法，利用新型的双向视全谱直读ICP-AES可直接测定具有复杂成份的褐煤样品中的微量元素Ge和主要成狄金属元素Al、Fe、Ca、Mg、K、Na、Ti。本文优化了仪器的工作参数并合理地选择了无干扰的分析谱线和等离子体测视方式，合理地扣除了光谱背景，样品灰化后采用HNO_3／HF／HClO_4混合酸消解，测定结果与国标方法测定值吻合。该方法高效、灵敏、线性范围宽且能进行多元素同时测定，能满足大批量试样的分析要求。
(3)改进了Querol逐级化学提取方法并利用改进后的方法在ICP-AES辅助测定下分5步提取了锡盟锗矿褐煤中Ge和主要成灰金属元素Al、Fe、Ca、Mg、K、Na、Ti的化学形态，五种形态分别是：水溶态、可交换态、碳酸盐和表面氧化物结合态、有机物和硫化物结合态及残渣态。提取结果主要为合理的、有针对性的选择提锗工艺流程提供理论依据和数据基础。本实验结果显示锗元素主要以有机物和硫化物结合态形式存在锡盟褐煤当中。
Foresee germanium will act as more and more important role in the advanced science and technology field in the future because of its wide-ranging optical properties and chemical catalyst properties, therefore, the super-large germanium deposit paragenesis with lignite discovered in Xilinguole League, Inner Mongolia has received considerable attention. Some base researches was done in this article in order to carry out ail-roundly work of generalized exploitation and utilization of lignite in Xilinguole League germanium deposit henceforth.
(i) Distribution and enrichment of metal elements of lignite in Xilinguole League germanium was investigated with qualitative and half-quantitative X-ray fluorescence spectrometric (XRF) method, and the results indicate that Ge, W, As, Cd enrich obviously and other elements want comparing with Clarke value. The research deduces that Ge mainly came from granites in the basement of the sedimentary basin.
(ii) Two kinds of new determination methods of germanium in Xilinguole League lignite were established. The first kind of method was fluorescence quenching method with 5' -nitro-salicylfluo -rone-TritonX-100, and fluorescence spectrum of determination system was studied, condition of experimentation was searched out as well. In the optimal conditions, germanium in Xilinguole League lignite could be directly determined in the present of masking reagents. The method is simple, utility, sensitive, selective and accurate. The second kind of method was inductively coupled plasma atom emission spectrometric (ICP-AES) methods, minor germanium and major ash forming metal elements Fe, Al, Ca, Mg, K, Na, Ti in lignite could be simultaneous determined using a new type of ICP instrument equipped with a dual-view plasma torch and detectors that cover nearly all spectra at the same time. In the experimentation, the operation condition of the instrument was optimized, analytical wavelength lack of interference from element
s in the sample matrix was selected, and the spectral background was automaticly eliminated. The obtained coal ashes were dissolved in mixtures of nitric acid, hydrofluoric acid and perchloric acid after coal samples were cinerated. The analytical results were in good agreement with those provided by national standard methods. The method offers such distinctive advantages as fast, sensitive, effective, wide dynamic range and multi-element capabilities.
(iii) The speciation of Ge and major ash forming metal elements Fe, Al, Ca, Mg, K, Na, Ti in Xilinguole League lignite was investigated using modified Querol five-step sequential chemical extraction procedures. The extraction sequence was as follows: (a)water-extractable; (b)readily exchangeable ions; (c)carbonate-bound, surface oxide-bound ions; (d)organically and sulfide-bound ions; (e)residual. The results of the extraction can offer theoretical basis and data in order to rationally select craft of extracting germanium. The results of this experiment show germanium mainly exists in form of organically and sulfide-bound ions in Xiliguole League lignite.
引文
[1]邾润蓉，：疗锡义，钮少冲．碳硅锗分族[M]．北京：科学出版社，1998，325—379
[2]邓忐杰．锗[J]．现代材料动态，2002，(8)：5—6
[3]李玉增，杨遇春．锗市场的调查研究与发展预测[J]．有色金属技术经济研究，1997，(4)：13—24
[4]郊能瑞．锗的应用与市场分析[J]．广东微量元素科学，1998，5(2)：12—18
[5]姜小波，…‘志镇．锗硅材料在微电子、光电子方面的应用[J]．材料科学与iI：程，1996，14(3)：18—21 ．
[6]州国元，韩兆忠．锗在空间太阳能电池中的应用[J]．功能材料(增刊)，1998，(10)：752—755
[7]褚7j林．锗在信息高速传输主体一光导纤维中的应用前景[J]．稀有金属，1998，4(5)：369—374
[8]周克瑜，陈中峻．有机锗合物的合成与应用[J]．化学世界．1993，34(8)：359—362
[19] Weber j N．Geochemistry of Germanium[M]．Pennsylvania：Dowden，Hutchinson and Ross Inc．，1973，301—447
[10]5miFnOV V I．Ore Deposits of the USSR．V01．Ill[M]．London：Pitman Publ．，1977，455—462
[11]Knellei W A．Geochemistry of germanium in coal：a Feview[J]．Abstracts with Programs，Geological Society of American，1986，18：133
[12]Kul i nenko 0 R．Telationship between germanium content and seam thickness in PaleozoiC paraliCcoal basins of Ukraine[J]．int．Geology Rev．，1977，19：1 179—1182
[13]Yonghun Li．The geological condition of a superlarge germanium deposit．Abstracts of the29t11 International Gelolgical Congress，t992，199
[14]汪毓煌．滇曲褐煤伴生元素锗的富集及评价[J]煤田地质与勘探，1992，(3)：24—30
[15]长淑苓，f淑英．云南临沧地区帮卖盆地含铀锗煤中锗矿的研究[J]．铀矿地质，1987，(5)：267 275
[16]兰明．内蒙古锡林郭勒盟乌兰图嘎锗矿地质特征及勘查工作简介[J]．大j蒙古地质，1999，(3)：16—20
[17]秦胜利．内蒙古胜利煤田锗矿床赋存规律及找矿方向[J]．中国煤田地质，2001，13(3)：18—19
[2]邓忐杰．锗[J]．现代材料动态，2002，(8)：5—6
[3]李玉增，杨遇春．锗市场的调查研究与发展预测[J]．有色金属技术经济研究，1997，(4)：13—24
[4]郊能瑞．锗的应用与市场分析[J]．广东微量元素科学，1998，5(2)：12—18
[5]姜小波，…‘志镇．锗硅材料在微电子、光电子方面的应用[J]．材料科学与iI：程，1996，14(3)：18—21 ．
[6]州国元，韩兆忠．锗在空间太阳能电池中的应用[J]．功能材料(增刊)，1998，(10)：752—755
[7]褚7j林．锗在信息高速传输主体一光导纤维中的应用前景[J]．稀有金属，1998，4(5)：369—374
[8]周克瑜，陈中峻．有机锗合物的合成与应用[J]．化学世界．1993，34(8)：359—362
[19] Weber j N．Geochemistry of Germanium[M]．Pennsylvania：Dowden，Hutchinson and Ross Inc．，1973，301—447
[10]5miFnOV V I．Ore Deposits of the USSR．V01．Ill[M]．London：Pitman Publ．，1977，455—462
[11]Knellei W A．Geochemistry of germanium in coal：a Feview[J]．Abstracts with Programs，Geological Society of American，1986，18：133
[12]Kul i nenko 0 R．Telationship between germanium content and seam thickness in PaleozoiC paraliCcoal basins of Ukraine[J]．int．Geology Rev．，1977，19：1 179—1182
[13]Yonghun Li．The geological condition of a superlarge germanium deposit．Abstracts of the29t11 International Gelolgical Congress，t992，199
[14]汪毓煌．滇曲褐煤伴生元素锗的富集及评价[J]煤田地质与勘探，1992，(3)：24—30
[15]长淑苓，f淑英．云南临沧地区帮卖盆地含铀锗煤中锗矿的研究[J]．铀矿地质，1987，(5)：267 275
[16]兰明．内蒙古锡林郭勒盟乌兰图嘎锗矿地质特征及勘查工作简介[J]．大j蒙古地质，1999，(3)：16—20
[17]秦胜利．内蒙古胜利煤田锗矿床赋存规律及找矿方向[J]．中国煤田地质，2001，13(3)：18—19