乌兰图嘎富锗煤中微量元素在不同密度级煤中的分布特征

段飘飘; 王文峰; 马萌芽

doi:10.12363/issn.1001-1986.22.03.0204

乌兰图嘎富锗煤中微量元素在不同密度级煤中的分布特征

段飘飘^{1, 2,},
王文峰^{1, 2,*, ,},
马萌芽^{1, 2}

1.
中国矿业大学煤层气资源与成藏过程教育部重点实验室，江苏徐州 221008
2.
中国矿业大学资源与地球科学学院，江苏徐州 221116

基金项目: 国家自然科学基金面上项目(42072192)；中央高校基本科研业务费专项资金项目(2021YCPY0106)

详细信息

作者简介:
段飘飘，1987年生，女，河北邯郸人，博士，副教授，从事煤中微量元素地球化学研究工作. E-mail：duanpiaopiao@163.com

通讯作者:
王文峰，1970年生，男，安徽巢湖人，博士，教授，从事煤地质学研究工作. E-mail：wenfwang@vip.163.com

中图分类号: P595
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出版历程
- 收稿日期: 2022-03-28
- 修回日期: 2022-07-06
- 录用日期: 2022-11-24
- 网络出版日期: 2022-11-16
- 刊出日期: 2022-11-24

Distribution characteristics of trace elements in different density fractions of high-germanium coal from Wulantuga, Inner Mongolia, China

DUAN Piaopiao^{1, 2,},
WANG Wenfeng^{1, 2,*, ,},
MA Mengya^{1, 2}

1.
Key Laboratory of Coalbed Methane Resources and Reservoir Formation Process of the Ministry of Education, China University of Mining and Technology, Xuzhou 221008, China
2.
School of Resources and Geosciences, China University of Mining and Technology, Xuzhou 221116, China

摘要

摘要:
煤系关键金属的开发利用对于缓解我国战略性矿产资源紧缺具有重要意义。内蒙古胜利煤田乌兰图嘎低阶煤中除富集关键金属Ge以外，同时富集有害元素Be、F、As、Hg、Sb和W，出于对关键金属的提取利用及环境保护2个方面考虑，须对研究区煤炭进行洗选处理。基于前期研究认识，浮选对于乌兰图嘎煤中As、Sb和W脱除效果相对较好，对于F和Hg的脱除效果较差，基于此，采用浮沉实验(重选法)以及XRD、XRF、SEM-EDS和EMPA等实验方法和测试手段，研究关键金属Ge以及Be、F、As、Hg等有害元素在不同密度级煤中的分布特征，结果表明：(1) 乌兰图嘎煤中矿物主要包括石膏、石英、黄铁矿、高岭石等，矿物含量随煤密度级增大而增加，电子探针分析结果表明，Co、As、Sb和Hg赋存在黄铁矿中。(2) 经过重选，低密度精煤中Ge元素富集，表明Ge主要以有机态存在，Be、F、As等可能与有机质相关，或者赋存在嵌布于有机质中的微细粒矿物中，煤中Hg和大部分亲石性元素在高密度级煤中含量较高，表明其赋存在矿物中。(3) 重选对于Hg元素的脱除效果较好，对Be、F、As和一些亲硫或亲铁性元素浮选脱除效果优于重选。建议乌兰图嘎低阶煤使用重选−浮选联合脱除法进行有害元素的脱除。
- 微量元素 /
- 分布特征 /
- 富锗煤 /
- 重选 /
- 乌兰图嘎
Abstract:
The exploitation and utilization of critical metals in coal measures is of great significance to alleviate the shortage of strategic mineral resources in China. In addition to the critical metal germanium (Ge), the low-rank coal from Wulantuga Coal Mine of Shengli Coalfield in Inner Mongolia, China is enriched with the toxic elements Be, F, As, Hg, Sb and W. Considering the extraction and utilization of key metals and environmental protection, the coal in the study area must be washed. As shown in the previous study, flotation is relatively good for the removal of As, Sb and W inWulantuga coal, but relatively poor for the removal of F and Hg. Hence, the distribution characteristics of the critical metal Ge and the toxic elements, such as Be, F, As and Hg, in different density fractions of coal were studied with the experiment and test methods, including floating-sinking experiment (the gravity separation), XRD, XRF, SEM-EDS and EMPA. The results show the following: (1) The minerals in Wulantuga coal mainly include gypsum, quartz, pyrite and kaolinite, the mineral content increases with the increasing of coal density fraction, and the Co, As, Sb and Hg occurs in pyrite according to the results of electron probe analysis. (2) After gravity separation, Ge is enriched in the low-density cleaned coal, indicating that Ge mainly exists in organic state, and Be, F, and As may be associated with the organic matter or occur in the fine grained minerals embedded in organic matter. Hg and most lithophile elements have higher concentrations in coals at higher density fractions, which indicates they occur in minerals. (3) Gravity separation is good for the removal of Hg, and flotation has a better effect for the removal of Be, F, As and some sulfurophilic or siderophile elements than gravity separation. Therefore, the gravity separation and flotation combined process is recommended for the removal of toxic elements in Wulantuga low-rank coal.
- trace element /
- distribution characteristic /
- high-germanium coal /
- gravity separation /
- Wulantuga

HTML全文

图 1 乌兰图嘎原煤中矿物

(a) 石膏；(b) 石英和黄铁矿；(c) 黄铁矿；(d) 锐钛矿；(e) 高岭石；(f) 裂隙充填状石英和长石；(g) 方解石；(h) 白云石

Fig. 1 Minerals in Wulantuga feed coal

下载: 全尺寸图片幻灯片

图 2 精煤中黄铁矿中Fe、S、As、Co、Ni、Ga、Sb等的面扫描结果

Fig. 2 Map scanning results of Fe, S, As, Co, Ni, Ga, Sb, etc. in pyrite in cleaned coal

下载: 全尺寸图片幻灯片

图 3 重选产品中微量元素的分布

Fig. 3 Distribution of trace elements in gravity-separated products

下载: 全尺寸图片幻灯片

图 4 浮选精煤^[11]、重选精煤中微量元素的脱除率

Fig. 4 The removal rate of trace elements of flotated cleaned coal^[11] and gravity-separated cleaned coal

下载: 全尺寸图片幻灯片

表 1 原煤和重选产品中常量元素的含量

Table 1 Concentration of major elements in raw coal and gravity-separated products

样品	元素氧化物质量分数/%
样品	K₂O	TiO₂	Na₂O	CaO	MgO	Al₂O₃	SiO₂	Fe₂O₃	S
精煤	0.016	0.068	0.10	0.14	0.24	0.76	1.31	4.81	4.09
中煤	0.053	0.077	0.06	0.43	0.18	0.96	2.66	3.61	3.47
原煤^[11]	0.046	0.062	0.06	0.53	0.19	1.09	2.88	4.16	3.86
注：原煤中常量元素或常量元素氧化物质量分数数据来自文献[11]。

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表 2 原煤和重选产品中矿物分布

Table 2 Distribution of minerals in feed coal and gravity-separated products

样品	矿物质量分数/%
样品	石膏	石英	高岭石	黄铁矿	总量
精煤	bdl	3.22	bdl	bdl	3.22
中煤	3.11	4.29	bdl	bdl	7.40
尾煤	13.12	4.56	2.43	0.50	20.61
原煤^[11]	4.64	4.23	0.25	bdl	9.12
注：bdl表示低于检测限，无数据；原煤中矿物质量分数数据来自文献[11]。

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表 3 黄铁矿spot 1-4的定量结果和标样

Table 3 Quantitative results and standard samples of Spot 1-4 for pyrite

点号	元素质量分数/%							总计/%
点号	S	Fe	Co	Ni	As	Sb	Hg	总计/%
1	51.470	43.931	0.056	0	0.621	0.001	0	96.078
2	52.927	43.524	0.063	0	0.684	0	0	95.198
3	51.396	44.418	0.085	0	0.227	0	0.067	96.193
4	51.664	43.795	0.033	0	0.187	0.007	0.012	95.698
标样	FeS₂	FeS₂	FeAsS	(FeNi)₉S₈	FeAsS	Sb₂S₃	HgS

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表 4 原煤和重选产品的产率与灰分及微量元素含量

Table 4 Yield, ash content and concentration of trace elements in feed coal and gravity-separated products

样品	元素含量/(μg·g⁻¹)
样品	Li	Be	F	P	Sc	Ti	V	Cr	Mn	Co
精煤	1.89	22.26	1320	14.5	1.52	182.61	5.90	4.43	42.08	1.34
中煤	2.69	15.13	1050	20.3	0.77	185.77	4.21	4.52	20.83	0.84
尾煤	6.90	10.83	840	31.5	0.39	414.90	6.61	8.73	12.50	0.62
原煤^[11]	2.88	16.52	1010	29.1	1.19	205.71	4.83	5.21	27.35	0.94

样品	Ni	Cu	Zn	Ga	Ge	As	Se	Rb	Sr	Zr
精煤	5.86	5.72	21.79	9.36	393.38	696.36	0.120	1.01	17.8	6.54
中煤	3.65	3.23	14.10	5.67	226.48	435.58	<0.065	2.22	25.7	7.26
尾煤	4.73	3.01	8.29	4.92	99.60	313.72	<0.065	11.90	94.5	25.20
原煤^[11]	2.89	3.87	11.95	6.58	264.42	467.02	<0.065	2.58	24.5	7.97

样品	Nb	Mo	Cd	In	Sn	Sb	Cs	Ba	Hf	Ta
精煤	1.15	2.08	0.070	0.007	0.77	105.0	2.91	9.0	0.19	0.058
中煤	0.85	1.23	0.033	0.003	0.37	46.6	3.64	24.2	0.23	0.020
尾煤	1.64	0.38	0.019	0.004	0.46	15.3	7.70	782.0	0.75	0.087
原煤^[11]	1.00	1.68	0.019	0.005	0.58	134.0	3.78	44.2	0.26	0.088

样品	W	Hg	Tl	Pb	Bi	Th	U
精煤	334.40	2.19	1.60	13.89	0.027	0.66	0.20
中煤	246.95	6.81	2.01	11.49	0.034	0.48	0.21
尾煤	124.96	9.99	3.23	6.76	0.043	0.39	0.35
原煤^[11]	277.75	5.15	2.36	6.32	0.029	0.77	0.21

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