煤和煤矸石及其燃烧产物中稀土元素赋存形态研究

吴国强; 汪涛; 王家伟; 张永生; 潘伟平

煤和煤矸石及其燃烧产物中稀土元素赋存形态研究

吴国强^{1, 2},
汪涛^1, ,,
王家伟¹,
张永生¹,
潘伟平¹

1.
华北电力大学电站能量传递转化与系统教育部重点实验室, 北京 102206
2.
北方民族大学, 宁夏银川 750021

详细信息

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).
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出版历程
- 收稿日期: 2020-08-17
- 修回日期: 2020-10-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2020-12-10

Occurrence forms of rare earth elements in coal and coal gangue and their combustion products

1.
Key Laboratory of Power Station Energy Transfer Conversion and System, Ministry of Education, North China Electric Power University Changping District, Beijing 102206, China
2.
North Minzu University, Yinchuan 750021, China

More Information

Corresponding author: WANG Tao, Tel:010-61772831, E-mail:wangtao0420@163.com

摘要

摘要: 针对中国三个典型电厂的煤和煤矸石及其燃烧产物(渣和飞灰)，采用逐级提取-电感耦合等离子体质谱法测定各级提取物的稀土元素浓度，进而研究煤和煤矸石及其燃烧产物中稀土元素的赋存规律。结果表明，煤和煤矸石中，稀土元素主要以酸溶态、硅酸盐&铝硅酸盐态赋存，煤矸石中分别占42.54%和45.62%，褐煤中分别占32.85%和57.13%，烟煤中分别占18.10%和75.46%；而煤和煤矸石燃烧产物中，稀土元素主要赋存在硅酸盐&铝硅酸盐态中，占稀土元素总量的80%左右；燃烧过程中，煤矸石、褐煤和烟煤中其他各形态(水溶态、离子交换态、酸溶态、硫化物结合态和有机物结合态)稀土元素分别有36%、23%和5%转变到燃烧产物中的硅酸盐&铝硅酸盐态。同一赋存形态中，各稀土元素在不同原料中的占比不同，但稀土元素从La到Lu，在不同原料中的变化特性相同；渣和飞灰中，因飞灰在烟气中暴露时间更长，导致同一赋存形态中，稀土元素从La到Lu，在渣和飞灰中的变化特性不同。
- 煤 /
- 煤矸石 /
- 渣 /
- 飞灰 /
- 稀土元素 /
- 赋存形态
Abstract: Distribution of rare earth elements (REEs) in six speciations extracted from coal and coal gangue and their combustion products (slag and fly ash) generated by three different power plants in China were determined by sequential extraction procedure combined with inductively coupled plasma mass spectrometry method. The results show that the REEs mainly occurred as acid soluble and silicate & aluminosilicate fraction, e.g., approximately 42.54% and 45.62% in coal gangue, 32.85% and 57.13% in lignite, and 18.10% and 75.46% in bituminous coal, respectively. However, REEs in the combustion products were mainly presented in silicate & aluminosilicate fraction regardless of coal or coal gangue, reaching up to approximately 80% of the total REEs content. During combustion, around 36%, 23%, and 5% from the other five fractions (water soluble, ion-exchangeable, acid soluble, organic, and sulfide) were transformed to silicate & aluminosilicate fraction from coal gangue, lignite, and bituminous coal, respectively. In the case of coal or coal gangue, the amount of each REEs in the same extracted fraction was different, but the distribution trend of REEs from La to Lu in each fraction was followed in the same rule. In the case of slag and fly ash generated from coal or coal gangue, distribution of REEs from La to Lu in each fraction showed the different trend between fly ash and slag. This was due to the fly ash exposed in flue gas system was much longer than the time for slag formation.
- coal /
- coal gangue /
- slag /
- fly ash /
- rare earth elements /
- occurrence forms
注释:

1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).

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图 1 逐级提取流程示意图

Figure 1 Diagram of sequential extraction procedure

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图 2 煤和煤矸石中总稀土元素的赋存形态

Figure 2 Occurrence forms of total REEs in coal and coal gangue

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图 3 煤和煤矸石中各稀土元素的赋存形态

Figure 3 Occurrence forms of individual REEs in coal and coal gangue

: water soluble; : ion-exchangeable; : acid soluble; : sulfide; : organic; : silicate & aluminosilicate

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图 4 渣中总稀土元素的赋存形态

Figure 4 Occurrence forms of total REEs in slags

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图 5 飞灰中总稀土元素的赋存形态

Figure 5 Occurrence forms of total REEs in fly ashes

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图 6 燃烧产物中各稀土元素的赋存形态

Figure 6 Occurrence forms of individual REEs in raw material by-products

: water soluble; : ion-exchangeable; : acid soluble; : metal oxide; : organic / sulfide; : silicate & aluminosilicate

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表 1 煤、煤矸石的工业分析和元素分析^[30]

Table 1 Proximate and Ultimate analysis results of coal and coal gangue samples^[30]

Sample	Proximate analysis w_ad/%				Ultimate analysis w_ad/%
Sample	M	V	A	FC	C	H	N	S	O
P1-coal gangue	4.99	18.19	49.65	27.17	35.21	2.98	1.06	0.19	11.39
P2-lignite	3.79	38.70	13.48	44.03	55.96	4.06	0.63	0.58	18.96
P3-bituminous coal	4.20	29.54	15.54	50.72	67.86	4.44	0.92	0.73	11.49

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表 2 煤和煤矸石及其燃烧产物中主量元素测定

Table 2 Analytical results for major elements of coal, coal gangue, slag and fly ash samples

Element	P1 w/(mg·g^-1)			P2 w/(mg·g^-1)			P3 w/(mg·g^-1)
Element	coal gangue	slag	fly ash	lignite	slag	fly ash	bituminous coal	slag	fly ash
Na	6.65	10.54	10.75	1.97	16.85	21.81	1.42	5.52	8.40
Mg	5.41	9.83	10.53	1.43	17.93	19.11	0.96	5.16	4.94
Al	53.10	88.90	80.99	13.62	93.65	96.58	22.94	142.69	139.79
Si	163.42	357.66	275.26	52.37	287.62	288.04	52.59	302.63	315.57
Ca	3.38	31.74	49.99	8.57	44.11	38.05	8.45	57.35	56.58
Mn	0.19	0.57	0.51	0.21	1.42	0.83	0.22	0.98	1.14
Fe	19.87	33.73	38.56	7.64	60.31	39.79	6.61	44.82	43.43
Ba	0.44	0.74	0.91	0.23	1.45	1.76	0.22	0.92	1.23

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表 3 煤和煤矸石及其燃烧产物中稀土元素测定

Table 3 Analytical results for REEs of coal, coal gangue, slag and fly ash samples

Element	P1 w/(μg·g^-1)			P2 w/(μg·g^-1)			P3 w/(μg·g^-1)
Element	coal gangue	slag	fly ash	lignite	slag	fly ash	bituminous coal	slag	fly ash
La	21.60	43.08	53.93	6.63	56.60	66.88	10.02	61.76	106.25
Ce	50.07	92.46	116.55	13.44	141.56	158.91	20.38	134.47	207.54
Pr	5.70	11.23	13.89	1.65	15.31	18.16	2.61	14.49	23.09
Nd	20.15	40.20	47.64	6.34	52.59	65.08	10.38	43.87	74.03
Sm	4.21	7.92	10.37	1.23	12.07	14.22	1.99	10.02	15.43
Eu	0.95	1.83	2.42	0.26	2.31	2.86	0.37	2.11	3.13
Gd	4.11	7.68	10.32	1.26	11.92	13.44	1.89	10.91	15.53
Tb	0.52	1.01	1.47	0.18	1.62	1.87	0.28	1.64	2.27
Dy	3.19	5.58	8.58	1.16	9.19	10.89	1.80	9.69	13.30
Y	17.71	32.59	53.25	7.04	52.08	64.67	11.15	54.52	77.39
Ho	0.55	1.02	1.63	0.21	1.74	2.04	0.32	1.83	2.51
Er	1.85	3.02	4.96	0.72	5.34	6.26	1.09	5.53	7.48
Tm	0.23	0.41	0.69	0.09	0.74	0.87	0.14	0.75	1.02
Yb	1.67	2.69	4.64	0.66	5.00	5.87	1.03	4.87	6.88
Lu	0.24	0.40	0.70	0.09	0.77	0.92	0.15	0.73	1.04

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参考文献(35)

[1]	BLISSETT R S, SMALLEY N, ROWSON N A. An investigation into six coal fly ashes from the United Kingdom and Poland to evaluate rare earth element content[J]. Fuel, 2014, 119(1): 236-239.
[2]	BAUER D, DIAMOND D, LI J. U. S. Department of energy critical materials strategy[R]. United States: Office of Scientific & Technical Information Technical Reports, 2010.
[3]	HUMPHRIES M. Rare earth elements: The global supply chain[R]. Washington, DC: CRS Report for Congress, 2013.
[4]	COMMISSION E. Report on critical raw materials for The EU[R]. Brussel, Belgium: Report of the Ad hoc Working Group on Defining Critical Raw Material, 2014.
[5]	LIN R H, HOWARD B H, ROTH E A, BANK T L, GRANITE E J, SOONG Y. Enrichment of rare earth elements from coal and coal by-products by physical separations[J]. Fuel, 2017, 200: 506-520.
[6]	PARK D M, BREWER A, REED D W, HAGEMAN P L, LAMMERS L N, JIAO Y Q. Recovery of rare earth elements from low-grade feedstock leachates using engineered bacteria[J]. Environ Sci Technol, 2017, 51(22): 13471-13480.
[7]	LIANG Y, LIU Y X, LIN R D, GUO D D, LIAO C f. Leaching of rare earth elements from waste lamp phosphor mixtures by reduced alkali fusion followed by acid leaching[J]. Hydrometallurgy, 2016, 163: 99-103.
[8]	DAI S F, FINKELMAN R B. Coal as a promising source of critical elements: Progress and future prospects[J]. Int J Coal Geol, 2017, 94: 67-93.
[9]	FOLGUERAS M B, ALONSO M, FERNáNDEZ F J. Coal and sewage sludge ashes as sources of rare earth elements[J]. Fuel, 2017, 192: 128-139.
[10]	苗晓鹏, 田亚峻, 许德平, 曹建飞.煤灰中提取稀土元素及产业化展望[J].稀土, 2018, 39(3): 124-131. MIAO Xiao-peng, TIAN Ya-jun, XU De-ping, CAO Jian-fei. Extraction of rare earth elements from fly ash and industrial prospects[J]. Chin Rare Earths, 2018, 39(3): 124-131.
[11]	黄文辉, 久博, 李媛.煤中稀土元素分布特征及其开发利用前景[J].煤炭学报, 2019, 44(1): 287-294. HUANG Wen-hui, JIU Bo, LI Yuan. Distribution characteristics of rare earth elements in coal and its prospects on development and exploitation[J]. J China Coal Soc, 2019, 44(1): 287-294.
[12]	ESKENAZY G M. Rare earth elements in a sampled coal from the Pirin deposit, Bulgaria[J]. Int J Coal Geol, 1987, 7(3): 301-314.
[13]	HU J, ZHENG B S, FINKELMAN R B, WANG B B, WANG M S, LI S H, WU D S. Concentration and distribution of sixty-one elements in coals from DPR Korea[J]. Fuel, 2006, 85(5): 679-688.
[14]	PAZAND K. Rare earth element geochemistry of coals from the Mazino Coal Mine, Tabas Coalfield, Iran[J]. Arab J Geosci, 2015, 8(12): 10859-10869.
[15]	WANG W F, YONG Q, SANG S X, ZHU Y M, WANG C Y, WEISS D J. Geochemistry of rare earth elements in a marine influenced coal and its organic solvent extracts from the Antaibao mining district, Shanxi, China[J]. Int J Coal Geol, 2008, 76(4): 309-317.
[16]	DAI S F, JIANG Y F, WARD C R, LANDING G U, SEREDIN V V, LIU H D, ZHOU D, WANG X B. Mineralogical and geochemical compositions of the coal in the Guanbanwusu Mine, Inner Mongolia, China: Further evidence for the existence of an Al (Ga and REE) ore deposit in the Jungar Coalfield[J]. Int J Coal Geol, 2012, 98(7): 10-40.
[17]	李焕同, 陈飞, 邹晓艳, 左晓峰, 张卫国, 莫佳峰, 王楠.湘中南地区二叠系龙潭组煤中稀土元素地球化学特征[J].稀土, 2019, 40(2): 28-34. LI Huan-tong, CHEN Fei, ZOU Xiao-yan, ZUO Xiao-feng, ZHANG Wei-guo, MO Jia-feng, WANG Nan. Geochemistry characteristics of rare earth elements in the permian longtan formation coals from south central Hu'nan province[J]. Chin Rare Earths, 2019, 40(2): 28-34.
[18]	ZHENG L G, LIU G J, CHOU C L, QI C C, YING Z. Geochemistry of rare earth elements in Permian coals from the Huaibei Coalfield, China[J]. J Asian Earth Sci, 2008, 31(2): 167-176.
[19]	邹建华, 刘东, 田和明, 刘峰, 李甜, 杨洪永.内蒙古阿刀亥矿晚古生代煤的微量元素和稀土元素地球化学特征[J].煤炭学报, 2013, 38(6): 1012-1018. ZOU Jian-hua, LIU Dong, TIAN He-ming, LIU Feng, LI Tian, YANG Hong-yong. Geochemistry of trace and rare earth elements in the late paleozoic coal from Adaohai Mine, Inner Mongolia[J]. J China Coal Soc, 2013, 38(6): 1012-1018.
[20]	ZHANG P P, ZHEN H, JIA J M, WEI C D, LIU Q Q, WANG X Q, JIAN Z, LI F F, MIAO S D. Occurrence and distribution of gallium, scandium, and rare earth elements in coal gangue collected from Junggar Basin, China[J]. Int J Coal Prep Util, 2017, 39(7): 389-402.
[21]	KOLKER A, SCOTT C, HOWER J C, VAZQUEZ J A, LOPANO C L, DAI S F. Distribution of rare earth elements in coal combustion fly ash, determined by SHRIMP-RG ion microprobe[J]. Int J Coal Geol, 2017, 184: 1-10.
[22]	LIN R H, STUCKMAN M L, HOWARD B H, BNAK T L, ROTH E A, MACALA M K, LOPANO C, SOONG Y, GRANITE E J. Application of sequential extraction and hydrothermal treatment for characterization and enrichment of rare earth elements from coal fly ash[J]. Fuel, 2018, 232: 124-133.
[23]	STUCKMAN M Y, LOPANO C L, GRANITE E J. Distribution and speciation of rare earth elements in coal combustion by-products via synchrotron microscopy and spectroscopy[J]. Int J Coal Geol, 2018, 195: 125-138.
[24]	PAN J H, ZHOU C C, TANG M C, CAO S S, LIU C, ZHANG N N, WEN M Z, LUO Y L, HU T T, JI W S. Study on the modes of occurrence of rare earth elements in coal fly ash by statistics and a sequential chemical extraction procedure[J]. Fuel, 2019, 237(1): 555-565.
[25]	HOWER J C, QIAN D L, BRIOT N J, HENKE K R, HOOD M M, TAGGART R K, HEILEEN H K. Rare earth element associations in the Kentucky State University stoker ash[J]. Int J Coal Geol, 2018, 189: 75-82.
[26]	DAI S F, ZHAO L, HOWER J C, JOHNSTON M N, SONG W J, WANG P P, ZHANG S F. Petrology, mineralogy, and chemistry of size-fractioned fly ash from the Jungar Power Plant, Inner Mongolia, China, with emphasis on the distribution of rare earth elements[J]. Energy Fuels, 2014, 28(2): 1502-1514.
[27]	MONTROSS S N, VERBA C A, CHAN H L, LOPANO C. Advanced characterization of rare earth element minerals in coal utilization byproducts using multimodal image analysis[J]. Int J Coal Geol, 2018, 195: 362-372.
[28]	RILEY K W, FRENCH D H, FARRELL O P, WOOD R A, HUGGINS F E. Modes of occurrence of trace and minor elements in some Australian coals[J]. Int J Coal Geol, 2012, 94: 214-224.
[29]	PAN J H, ZHOU C C, LIU C, TANG M C, ZHANG N N. Modes of occurrence of rare earth elements in coal fly ash: A case study[J]. Energy Fuels, 2018, 32(9): 9738-9743.
[30]	吴国强, 汪涛, 张永生, 王家伟, 潘伟平.燃煤电厂煤及其燃烧产物中稀土元素富集规律研究[J].中国电机工程学报, 2020, 40(6): 1963-1971 WU Guo-qiang, WANG Tao, ZHANG Yong-sheng, WANG Jia-wei, PAN Wei-ping. Study on the enrichment of rare earth elements between coals and their by-products at coal-fired power plants[J]. Proc CSEE, 2020, 40(6): 1963-1971.
[31]	SEREDIN V V. A new method for primary evaluation of the outlook for rare earth element ores[J]. Geol Ore Deposit, 2010, 52(5): 428-433.
[32]	代世峰, 任德贻, 李生盛.煤及顶板中稀土元素赋存状态及逐级化学提取[J].中国矿业大学学报, 2002, 31(5): 349-353. DAI Shi-feng, REN De-yi, LI Sheng-sheng. Occurrence and sequential chemical extraction of rare earth element in coals and seam roofs[J]. J China Univ Min Technol, 2002, 31(5): 349-353.
[33]	ESKENAZY G M. Aspects of the geochemistry of rare earth elements in coal: an experimental approach[J]. Int J Coal Geol, 1999, 38(3/4): 285-295.
[34]	KOLKER A, SCOTT C, HOWER J C, VAZQUEZ J A, LOPANO C L. Distribution of rare earth elements in coal combustion fly ash, determined by SHRIMP-RG ion microprobe[J]. Int J Coal Geol, 2017, 184: 1-10.
[35]	USHAKOV S, HELEAN K, NAVROTSKY A, BOATNER L. Thermochemistry of rare earth orthophosphates[J]. J Phys Chem, 2001, 16: 2623-2633.