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中国煤中22种环境敏感微量元素的地球化学研究
其他题名Research on geochemistry of 22 environmental sensitive trace elements in Chinese Coals
胡军
2007-05-31
学位授予单位中国科学院地球化学研究所
学位授予地点地球化学研究所
学位名称博士
关键词 微量元素 含量 分布 赋存状态 选煤
摘要本论文按照统一的采样和统一的分析测试方法对全国煤中22种环境敏感微量元素及全硫含量进行了系统的研究。通过统计学的方法不仅给出了中国煤炭部分环境敏感微量元素的分布范围、算术均值、标准差、几何均值、几何偏差,中位数,而且首次给出了95%置信度下算术均值、几何均值以及元素含量分布的置信区间等,并与前人大量样品的统计结果进行比较。还通过统计分析了部分环境敏感微量元素在我国煤中的主要赋存状态,以及选煤对这部分微量元素的脱除机理和脱除效果等,得到以下几点认识: 1. 通过与前人大量样品统计所得到的结果进行比较,进一步证明了论文中使用的这批样品是中国煤炭平均化学成分的良好代表。本次所分析的23种元素中,As、Be、Co、Cr、Cu、Hg、Pb、Se、Th、Tl、U、F、S等13元素与前人数10年研究的统计结果在分布范围、均值含量等上非常一致,但本次的结果更为可信,更接近中国煤炭平均化学成分的真实状况。此外,本次对这B、Sn这2种元素的分析数据也是目前反映我国煤中分布最具有代表性的数据。 2. 根据样品的无偏性,对平均值的置信区间进行计算。首次给出了全国煤中各元素在95%置信度下的算术均值的置信区间、几何均值的置信区间以及元素含量分布的置信区间等。可以为后人研究各元素在绝大多数煤中的含量及均值情况时作为参考。同时统计分析表明,按照95%置信度计算,16元素的真实平均值在我们所得到的平均值±11%范围之内,最大偏差为硒,在±20%之间。 3. 平均值作为最常用的统计量之一,中国煤中不同元素的不同均值之间有一定的差异,反映了元素在煤中不同的分布状态。论文中通过对23种元素在全国煤中的5种不同的均值比较,一般元素的产量加权均值与总体样品均值之间都比较接近;绝大多数元素的储量加权均值比较低,这与西北、华北地区未开采利用的煤炭资源量大,煤质好有关。 4. 通过与Swaine(1990)给出世界煤中元素的分布范围进行比较,22种环境敏感微量元素在我国煤中的分布处于世界煤的有限范围之内。其中,Cr、Cu、Mn、Mo、Se、Sn、Th、Tl、U、V、F等微量元素在我国煤中的分布与世界煤比较接近,而As、B、Ba、Be、Cd、Co、Cl、Hg、Ni、Pb、Sb等微量元素在我国煤中较世界煤低很多。 5. 与世界主要煤炭资源大国和Swaine(1990)给出的世界煤元素均值含量的比较显示,大部分环境敏感微量元素在我国煤中的均值含量与世界主要煤炭资源大国煤中的均值含量也比较接近。其中,我国煤中B、Co、Cu、Hg、Pb、U等6种元素含量均值与美国煤比较接近,As、Cd、Sb、Tl等4种元素含量均值与澳大利亚煤比较接近,Ba、Cr、Mo、Ni、V等4种元素含量均值与前苏联煤比较接近,Be、Mn、Se、Th、F等5种元素含量均值与世界煤比较接近。 6. 随着煤炭变质程度的增高,各元素均值含量没有表现出明显规律性的增高或降低。但22种环境敏感微量元素在褐煤、弱粘煤、不粘煤、气煤等较低变质程度煤中的含量整体水平不高,绝大多数微量元素主要在中高变质程度煤中较为更为富集。不同成煤时期以及不同聚煤区煤中各种环境敏感微量元素不同的富集程度,从总体上反应了绝大部分环境敏感微量元素在华南煤中更为富集,而占全国储量3/4的华北和西北煤中的总体水平相对较低。 7. 通过对环境敏感微量元素与灰分及主要灰成分之间的关系进行分析,初步了解了它们在煤中的主要赋存状态。煤中绝大部分环境敏感微量元素还是具有非常明显的无机亲和性,在煤中主要以矿物无机形态存在。主要与粘土矿物、黄铁矿及硫化物相结合,而与碳酸盐矿物关系不大。 8. 脱除率的分析显示,15种元素的脱除率与灰分的脱除率之间具有显著的正相关性,说明煤中绝大部分环境敏感微量元素主要以无机形态存在,因此提高原煤入洗率,降低原煤灰分的同时也可以在很大程度上降低环境敏感微量元素的燃煤排放。 9. 部分环境敏感元素的脱除率受到其在煤中的赋存状态、矿物形态、煤级以及选煤厂洗选工艺等诸多因素的影响,在不同样品中脱除率的差异较大。某些样品中微量元素的脱除率较高,最高脱除率可达到70%以上。从平均脱除率来看,灰分、硫分及绝大多数环境敏感微量元素处于30%-70%之间,只有少数几个元素不到20%。
其他摘要In this paper, we collected more than 300 nationwide coal samples with uniform sampling means, and determined some elements contents by most advanced analyzed techniques. According the analyzed data, we did some systemic research on 22 environmental sensitive elements and total sulfur in Chinese coals, and gave some important statistic parameters such as ranges, arithmetic and geometric means, median, standard deviation, and confident level (95%), etc.. We also studied on the main modes of their occurrence in coals, and mechanism, effects of reducing them by coal-cleaning techniques. Based on the study, some conclusions can be drawn: 1. By the comparison with the results from former researchers, it proved that these samples we studied are the good representative for reflecting the distributions and concentrations of elements in Chinese coals. The ranges and means of 13 environmental sensitive elements are closed to the results analyzed by former researchers in more than ten years. We think our analyzed results are more confident and more closed to the real status of average chemical composition of elements in Chinese coals. Moreover, the analytical data of B and Sn are the most representative in China for now. 2. On the base of no deviation, we calculated the confidence interval (95%) for arithmetic and geometric means, and the interval for elements concentration. And by the means of statistic analysis, the real-means calculated on 95% confident level of 11 elements are in the range of our statistic means±11%, and Se has the most deviation of ±20%. 3. The arithmetic mean is one of the most common variables. Different means have much difference when they are selected for statistic analysis. In the paper, we calculated five kinds of different means of 23 elements contents in coals for comparison. We found the means weighted by coal production are most closed to the arithmetic means of all samples. Most elements means weighted by coal reserves are lower than the others, which is associated with good coal quality and large quantity in Western and Northern China. 4. Most elements in Chinese coals have the ranges within the ranges in the Word given by Swaine (1990). Among them, these elements (Cr、Cu、Mn、Mo、Se、Sn、Th、Tl、U、V、F) have the ranges closed to World coals and the elements (As、B、Ba、Be、Cd、Co、Cl、Hg、Ni、Pb、Sb) have the ranges very lower than World coals. 5. In comparison with the arithmetic means of 22 trace elements in main coal resources countries and in World coals given by Swaine (1990), there are 6 elements (B、Co、Cu、Hg、Pb、U) with the means closed to American coals; 4 elements (As、Cd、Sb、Tl) with the means closed to Australian coals; 4 elements (Ba、Cr、Mo、Ni、V) with the means closed to former Soviet Union coals; and 5 elements (Be、Mn、Se、Th、F) have arithmetic means close to World coals. 6. With the coal ranks increasing, no element means have the significant increasing or decreasing. But from the whole levels of elements in coals with different ranks, the lignite, weak glued coals, no glued coals and gas coals have lower enrichment in environmental sensitive elements, and most elements are more enriched in coals with high ranks. The enrichment degrees of elements in the coals with different coal-forming ages and different coal-accumulated areas all show that most elements are mainly enriched in southern coals, and are very lower in northern and northwestern coals with the reserves more than 3/4 of national reserves. 7. By the analysis of correlation between the environmental sensitive elements and ash, main composition of ash, we preliminarily know the main occurrence forms of these elements in Chinese coals. Most elements are combined with clay minerals, pyrite and some sulfides, and no more relations with carbonates. 8. The analysis for reduction rates of elements during coal cleaning shows that the reduction levels of 15 elements have very significant positive correlation with the reduction levels of ash yields. It proved that in coals most environmental sensitive elements are inorganic forms. So, increasing the coal washing rate can largely decrease the emissions of hazardous elements during coal burning. 9. The reduction rates can be influenced by their occurrence modes, mineral forms, coal ranks and the techniques used by coal-washing plants, so the reduction rates have much difference in different coal samples. In some ones, the reduction rates can come to 70%. From the average, ash, pyritic sulfur and most environmental sensitive elements have the reduction rates between 30% and 70%, and a few with the reduction rates less than 20%.
页数155
语种中文
文献类型学位论文
条目标识符http://ir.gyig.ac.cn/handle/352002/3288
专题研究生_研究生_学位论文
推荐引用方式
GB/T 7714
胡军. 中国煤中22种环境敏感微量元素的地球化学研究[D]. 地球化学研究所. 中国科学院地球化学研究所,2007.
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