三类煤阶煤中汞的赋存形态分布特征

doi:10.11949/j.issn.0438-1157.20181311

化工学报 ›› 2019, Vol. 70 ›› Issue (4): 1559-1566.DOI: 10.11949/j.issn.0438-1157.20181311

三类煤阶煤中汞的赋存形态分布特征

苏银皎¹(),刘轩¹,李丽锋²,李晓航¹,姜平²,滕阳¹,张锴¹()

1. 华北电力大学热电生产过程污染物监测与控制北京市重点实验室，北京 102206
2. 山西河坡发电有限责任公司，山西阳泉 045011

收稿日期:2018-11-12 修回日期:2019-01-11 出版日期:2019-04-05 发布日期:2019-04-05
通讯作者: 张锴
作者简介:<named-content content-type="corresp-name">苏银皎</named-content>（1991—），女，博士研究生，<email>suyinjiaosu@163.com</email>|张锴（1968—），男，博士，教授，<email>kzhang@ncepu.edu.cn</email>
基金资助:
国家自然科学基金联合基金项目(U1610254);中央高校基本科研业务费(2017MS020, 2017MS018, 2018ZD03)

Distribution characteristics of mercury speciation in coals with three different ranks

Yinjiao SU¹(),Xuan LIU¹,Lifeng LI²,Xiaohang LI¹,Ping JIANG²,Yang TENG¹,Kai ZHANG¹()

1. Beijing Key Laboratory of Emission Surveillance and Control for Thermal Power Generation, North China Electric Power University, Beijing 102206, China
2. Shanxi Hepo Power Generation Company Limited, Yangquan 045011, Shanxi, China

Received:2018-11-12 Revised:2019-01-11 Online:2019-04-05 Published:2019-04-05
Contact: Kai ZHANG

摘要/Abstract

摘要：

采用逐级化学提取方法与程序升温热解方法研究了两个煤田三类煤阶六个样品中汞的赋存形态及其热稳定性。煤中汞分为可交换态（F1）、碳酸盐+硫酸盐+氧化物结合态（F2）、硅酸盐+硅铝酸盐结合态（F3）、硫化物结合态（F4）和残渣态（F5），其中F2、F4和F5约占煤中汞总量的90%以上，且F4是煤中汞最主要的赋存形态，占比达45.2%~82.1%。煤中汞的赋存形态与煤阶密切相关，随样品煤化程度加深F4的比例显著提高，但F2和F5逐渐降低，其原因可能是汞在煤变质过程中由碳酸盐、硫酸盐或有机物中逐渐迁移至硫化物中。煤中汞的热稳定性依赖于其赋存形态，其中F1热稳定性最差，在150℃以下全部释放；F3热稳定性最强，析出温度在600℃以上；其余三种结合态汞的释放温度界于以上两者之间，依次为F1 < F5 < F2 < F4 < F3；尽可能多地使汞转化为硫化物结合态中较为稳定的形态是煤燃烧及其相关过程液、固副产物中汞稳定化处理的有效方法之一。

关键词: 汞, 赋存形态, 煤阶, 热解, 稳定性, 浸取, 分布

Abstract:

The occurrence and thermal stability of mercury in six samples of three coal ranks in two coal fields were studied by stepwise chemical extraction method and temperature programmed pyrolysis method. The results show that mercury in coal can be divided into five fractions: exchangeable mercury (F1), carbonate+sulfate+oxide bound mercury (F2), silicate+aluminosilicate bound mercury (F3), sulfide bound mercury (F4) and residual mercury (F5). Among them, F2, F4 and F5 account for over 90%, especially F4 ranges from 45.2% to 82.1%. Mercury speciation is heavily related to coal rank in this study. The proportion of F4 is significantly increased with increasing the degree of coalification, whilst both F2 and F5 are gradually decreased, which can be inferred that mercury combined with carbonate, sulfate and organic matter transfer to the sulfide during the metamorphic process of coal. The thermal release characteristics of mercury in coal depend on its speciation. F1 has the weakest thermal stability which completely releases when the temperature is lower than 150℃, but F3 is the strongest with the release temperature above 600℃. The release temperature of the other mercury species is between F1 and F3. As a result, the order of release temperature is F1 < F5 < F2 < F4 < F3. Based on the above findings, it should be an effective method to transform mercury into much more sulfide with stable state for stabilizing mercury speciation in liquid and solid by-products of coal combustion and other related processes.

Key words: mercury, speciation, coal rank, pyrolysis, stability, leaching, distribution

中图分类号:

TQ 53

苏银皎, 刘轩, 李丽锋, 李晓航, 姜平, 滕阳, 张锴. 三类煤阶煤中汞的赋存形态分布特征[J]. 化工学报, 2019, 70(4): 1559-1566.

Yinjiao SU, Xuan LIU, Lifeng LI, Xiaohang LI, Ping JIANG, Yang TENG, Kai ZHANG. Distribution characteristics of mercury speciation in coals with three different ranks[J]. CIESC Journal, 2019, 70(4): 1559-1566.

图/表 6

表1 样品的工业分析和汞含量

Table 1 Proximate analysis and mercury content of samples

样品	煤田	产地	工业分析/%(质量)				汞含量/ (ng/g)
样品	煤田	产地	M_ad	A_ad	V_ad	FC_ad	汞含量/ (ng/g)
L1	宁武煤田	朔州王坪	1.18	35.67	27.72	35.43	292.6
L2		朔州安太堡	3.29	28.23	28.18	40.30	228.7
B1		原平轩岗	2.94	22.57	21.23	53.26	175.3
B2	沁水煤田	阳泉盂县	1.33	18.24	11.52	68.91	138.5
A1		阳泉上社	1.42	18.18	10.26	70.14	186.3
A2		阳泉上社	1.43	15.50	8.49	74.58	105.1

图1 程序升温热解实验台示意图

Fig.1 Schematic diagram of temperature-programmed-decomposition experimental system

图2 逐级化学提取流程示意图

Fig.2 Schematic diagram of sequential-chemical-extraction procedure

图3 三类煤阶煤中汞的热释放曲线

Fig.3 Thermogram of Hg in coals with three different ranks

图4 五种结合态汞在三类煤阶煤中的分布特征

Fig.4 Distribution characteristics of five Hg species in coals with three different ranks

图5 五种结合态汞的热释放谱图

Fig.5 Thermogram for five Hg species

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三类煤阶煤中汞的赋存形态分布特征

Distribution characteristics of mercury speciation in coals with three different ranks

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