准东煤热解过程中不同赋存形态钠变迁规律的研究

郭帅; 蒋云峰; 熊青安; 宋双双; 赵建涛; 房倚天

准东煤热解过程中不同赋存形态钠变迁规律的研究

郭帅^{1, 2},
蒋云峰¹,
熊青安^{1, 2},
宋双双¹,
赵建涛^1, ,,
房倚天¹

1.
中国科学院山西煤炭化学研究所, 山西太原 030001
2.
中国科学院大学, 北京 100049

基金项目:

家自然科学基金 21576276

家自然科学基金 21506241

中国科学院战略性先导科技专项 XDA07050100

详细信息

通讯作者:
赵建涛, Tel/Fax:0351-2021137, E-mail:zhaojt@sxicc.an.cn

中图分类号: TQ530.2
计量
- 文章访问数: 159
- HTML全文浏览量: 29
- PDF下载量: 18
- 被引次数: 0
出版历程
- 收稿日期: 2016-11-28
- 修回日期: 2017-02-12
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-03-10

Release and transformation behaviors of sodium species with different occurrence modes during pyrolysis of Zhundong coal

1.
Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds:

the National Natural Science Foundation of Chin 21576276

the National Natural Science Foundation of Chin 21506241

Strategic Priority Research Program of the Chinese Academy of Sciences XDA07050100

摘要

摘要: 利用加压管式反应器对准东煤进行了一系列热解实验，并采用溶剂逐级萃取的方法研究了煤中各赋存形态钠在不同热解温度、停留时间及其压力下的变迁规律。研究发现，原煤中钠主要是以水合离子态和钠长石的形式存在，有机态钠含量较少。在500-700℃时，随着挥发分的释放，水可溶性钠结合到煤焦的碳基质上，转化为盐酸可溶但水不可溶性的钠，少量有机钠会挥发至气相中。在700-900℃时，可溶性钠与高岭土等矿物质反应生成盐酸不可溶性钠。1 000℃时，钠的挥发量显著增加；部分高岭土与方解石分解生成的氧化钙反应生成钙长石，抑制了可溶性钠与高岭土之间的反应。煤中各形态钠的变迁主要发生在热解初期，与挥发分的释放同时进行。提高热解压力对钠的变迁行为没有影响。
- 准东煤 /
- 热解 /
- 赋存形态 /
- 钠 /
- 变迁
Abstract: A series of pyrolysis experiments on Zhundong coal were conducted by using a pressurized tube reactor. Under different pyrolysis temperature, residence time and pressure, the release and transformation behaviors of sodium species with different occurrence modes were investigated by the method of sequential chemical extraction. The results indicate that sodium species are mainly in the form of hydrated ion and albite, and organic forms are quite less. At 500-700℃, water-soluble sodium would be combined with char matrix, forming hydrochloric acid-soluble but water-insoluble sodium. At 700-900℃, soluble sodium could react with minerals such as kaolin, forming insoluble aluminosilicate. At 1 000℃, release of sodium became intense; part of kaolin might be involved into reactions with lime, which inhibited its reactions with soluble sodium. Besides, it is found that release and transformation behaviors of sodium mainly take place at the initial stage of pyrolysis along with release of volatiles and raising pressure has negligible influence on those behaviors.
- Zhundong coal /
- pyrolysis /
- occurrence mode /
- sodium /
- release and transformation

HTML全文

图 1 加压热解装置示意图

Figure 1 Schematic diagram of the pressurized pyrolysis apparatus

1: mass flow meter; 2: reducing value; 3: nitrogen cylinder; 4: pressure meter; 5: magnetic injection system; 6: seal flange; 7: thermocouple; 8: corundum basket; 9: temperature controller; 10: electric furnace; 11: steel tube; 12: gas pocket; 13: coiler

下载: 全尺寸图片幻灯片

图 2 原煤中钠的赋存形态

Figure 2 Occurrence modes of sodium species in raw coal

下载: 全尺寸图片幻灯片

图 3 原煤灰XRD谱图 (a) 和原煤红外光谱谱图 (b)

Figure 3 XRD pattern of low temperature ash (a) and FT-IR pattern of raw coal (b)

Q: Quartz (SiO₂); C: Calcite (CaCO₃); K: Kaolin (Al₂Si₂O₅(OH)₄); A: Anorthite (CaAl₂Si₂O₈) or Albite (NaAlSi₃O₈)

下载: 全尺寸图片幻灯片

图 4 不同热解温度下钠的挥发量

Figure 4 Release of sodium at different pyrolysis temperatures

下载: 全尺寸图片幻灯片

图 5 热解温度对焦产率和煤焦中钠含量的影响

Figure 5 Effect of pyrolysis temperature on the char yield and total sodium in the char

下载: 全尺寸图片幻灯片

图 6 热解温度对煤中各赋存形态钠转化的影响

Figure 6 Effect of pyrolysis temperature on the transformations of sodium species in different forms

下载: 全尺寸图片幻灯片

图 7 不同热解温度下煤焦灰的XRD谱图

Figure 7 XRD patterns of char ashes prepared at different pyrolysis temperatures

Q: Quartz (SiO₂); C: Calcite (CaCO₃); A: Albite (NaAlSi₃O₈) or Anorthite (CaAl₂Si₂O₈); N: Nepheline (NaAlSiO₄)

下载: 全尺寸图片幻灯片

图 8 热解停留时间对焦产率及其钠挥发量的影响

Figure 8 Effect of residence time on the char yield and sodium release

下载: 全尺寸图片幻灯片

图 9 热解停留时间对煤中各赋存形态钠转化的影响

Figure 9 Effect of residence time on the transformations of sodium species in different forms

下载: 全尺寸图片幻灯片

图 10 热解压力对煤中各赋存形态钠转化的影响

Figure 10 Effect of the pyrolysis pressure on the transformations of sodium species in different forms

下载: 全尺寸图片幻灯片

表 1 工业分析和元素分析

Table 1 Proximate and ultimate analysis

Proximate analysis w_ad/%				Ultimate analysis w_ad/%
M	A	V	FC	C	H	O^a	N	S
8.97	17.33	21.70	52.00	56.97	2.95	13.11	0.54	0.13
^a: by difference; ad: air-dried base

下载: 导出CSV

表 2 灰成分分析

Table 2 Ash chemical compositions

Composition w/%
SiO₂	Al₂O₃	Fe₂O₃	CaO	MgO	TiO₂	SO₃	K₂O	Na₂O	P₂O₅
55.39	14.34	7.02	11.2	3.57	0.64	1.35	1.25	4.64	0.19

下载: 导出CSV

表 3 热解压力对焦产率和煤焦中钠含量的影响

Table 3 Effect of pyrolysis pressure on the char yield and sodium content in char

	0.1 MPa	1.0 MPa	2.0 MPa
Char yield w/%	80.7	81.6	82.8
Sodium content w/(mg·g^-1)	8.56	8.43	8.33

下载: 导出CSV

参考文献(30)

[1]	齐晓宾, 宋国良, 宋维健, 吕清刚.准东高碱煤气化过程中碱金属迁移与结渣特性实验研究[J].燃料化学学报, 2015, 43(8):906-913. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18670.shtml QI Xiao-bin, SONG Guo-liang, SONG Wei-jian, LÜ Qing-gang. Alkali metal migration and slagging characteristic during Zhundong high-alkali coal gasification[J]. J Fuel Chem Technol, 2015, 43(8):906-913. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18670.shtml
[2]	刘大海, 张守玉, 涂圣康, 金涛, 施登宇, 裴育峰.五彩湾煤中钠在热解过程中的形态变迁[J].燃料化学学报, 2014, 42(10):1190-1196. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18502.shtml LIU Da-hai, ZHANG Shou-yu, TU Sheng-kang, JIN Tao, SHI Deng-yu, PEI Yu-feng. Transformation of sodium during Wucaiwan coal pyrolysis[J]. J Fuel Chem Technol, 2014, 42(10):1190-1196. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18502.shtml
[3]	韩克鑫, 黄镇宇, 王智化, 周俊虎.准东煤灰渣烧结熔融过程中钠基化合物作用机理研究[J].燃料化学学报, 2015, 43(1):22-26. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18550.shtml HAN Ke-xin, HUANG Zhen-yu, WANG Zhi-hua, ZHOU Jun-hu. Action mechanism of sodium compounds in Zhundong coal ash on the process of sintering and fusion[J]. J Fuel Chem Technol, 2015, 43(1):22-26. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18550.shtml
[4]	翁青松, 王长安, 车得福, 付子文.准东煤碱金属赋存形态及对燃烧特性的影响[J].燃烧科学与技术, 2014, 20(3):216-221. http://www.cnki.com.cn/Article/CJFDTOTAL-RSKX201403004.htm WENG Qing-song, WANG Chang-an, CHE De-fu, FU Zi-wen. Alkali metal occurrence mode and its influence on combustion characteristics in Zhundong coals[J]. J Combust Sci Technol, 2014, 20(3):216-221. http://www.cnki.com.cn/Article/CJFDTOTAL-RSKX201403004.htm
[5]	赵冰, 王嘉瑞, 陈凡敏, 王小悦, 李小江.高钠煤水热脱钠处理及其对燃烧特性的影响[J].燃料化学学报, 2014, 42(12):1416-1422. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18533.shtml ZHAO Bing, WANG Jia-rui, CHEN Fan-min, WANG Xiao-yue, LI Xiao-jiang. Hydrothermal treatment to remove sodium from high sodium coal and its influence on combustion characteristics[J]. J Fuel Chem Technol, 2014, 42(12):1416-1422. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18533.shtml
[6]	杨光, 张彦威, 寇希文, 周志军, 王智化, 周俊虎, 岑可法.燃用准东煤电站锅炉灰沉积形成过程中的矿物演变与热力学模拟[J].燃料化学学报, 2015, 43(10):1182-1187. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18707.shtml YANG Guang, ZHANG Yan-wei. KOU Xi-wen, ZHOU Zhi-jun, WANG Zhi-hui, ZHOU Jun-hu, CEN Ke-fa. Mineral conversion and thermodynamic simulation of ash deposition during Zhundong coal combustion in boiler of thermal power plant[J]. J Fuel Chem Technol, 2015, 43(10):1182-1187. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18707.shtml
[7]	马岩, 黄镇宇, 唐慧儒, 王智化, 周俊虎, 岑可法.准东煤灰化过程中的矿物演变及矿物添加剂对其灰熔融特性的影响[J].燃料化学学报, 2014, 42(1):20-25. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18327.shtml MA Yan, HUANG Zhen-yu, TANG Hui-ru, WANG Zhi-hua, ZHOU Jun-hu, CEN Ke-fa. Mineral conversion of Zhundong coal during ashing process and the effect of mineral additives on its ash fusion characteristics[J]. J Fuel Chem Technol, 2014, 42(1):20-25. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18327.shtml
[8]	NARUSE I, MURAKAMI T, NODA R, OHTAKE K. Influence of coal type on evolution characteristics of alkali metal compounds in coal combustion[J]. Symp on Combust, 1998, 27(2):1711-1717. doi: 10.1016/S0082-0784(98)80011-8
[9]	VAN EYK P J, ASHMAN P J, ALWAHABI Z T, NATHAN G J. The release of water-bound and organic sodium from Loy Yang coal during the combustion of single particles in a flat flame[J]. Combust Flame, 2011, 158(6):1181-1192. doi: 10.1016/j.combustflame.2010.10.024
[10]	齐晓宾, 宋国良, 宋维健.准东高碱煤气化过程中碱金属赋存形态迁移转化[J].煤炭学报, 2016, 41(4):1011-1017. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201604029.htm QI Xiao-bin, SONG Guo-liang, SONG Wei-jian. Transformation and migration of alkali metal with different occurrence of Zhundong high-alkali coal during gasification[J]. J China Coal Soc, 2016, 41(4):1011-1017. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201604029.htm
[11]	汉春利, 张军, 刘坤磊, 徐益谦.煤中钠存在形式的研究[J].燃料化学学报, 1999, 27(6):19-23. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199906019.htm HAN Chun-li, ZHANG Jun, LIU Kun-lei, XU Yi-qian. Modes of occurrence of sodium in coals[J]. J Fuel Chem Technol, 1999, 27(6):19-23. http://www.cnki.com.cn/Article/CJFDTOTAL-RLHX199906019.htm
[12]	陈川, 张守玉, 刘大海, 郭熙, 董爱霞, 熊绍武, 施大钟, 吕俊复.新疆高钠煤中钠的赋存形态及其对燃烧过程的影响[J].燃料化学学报, 2013, 41(7):832-838. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18218.shtml CHEN Chuan, ZHANG Shou-yu, LIU Da-hai, GUO Xi, DONG Ai-xia, XIONG Shao-wu, SHI Da-zhong, LV Jun-fu. Existence form of sodium in high sodium coals from Xinjiang and its effect on combustion process[J]. J Fuel Chem Technol, 2013, 41(7):832-838. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18218.shtml
[13]	宋维健, 宋国良, 齐晓宾, 吕清刚.准东高钠煤气化过程中Na的迁移转化规律[J].燃料化学学报, 2016, 41(2):490-496. SONG Wei-jian, SONG Guo-liang, QI Xiao-bin, LÜ Qing-gang. Sodium transformation law of Zhundong coal during gasification[J]. J Fuel Chem Technol, 2016, 41(2):490-496.
[14]	宋维健, 宋国良, 张海霞, 范金龙, 吕清刚.准东高钠煤热解过程中钠的迁移特性实验研究[J].燃料化学学报, 2015, 43(1):16-21. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18549.shtml SONG Wei-jian, SONG Guo-liang, ZHANG Hai-xia, FAN Jin-long, LÜ Qing-gang. Experimental study on alkali metal transformation during high-sodium Zhundong coal pyrolysis[J]. J Fuel Chem Technol, 2015, 43(1):16-21. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18549.shtml
[15]	刘敬, 王智化, 项飞鹏, 黄镇宇, 刘建忠, 周俊虎, 岑可法.准东煤中碱金属的赋存形式及其在燃烧过程中的迁移规律实验研究[J].燃料化学学报, 2014, 42(3):316-322. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18373.shtml LIU Jiang, WANG Zhi-hua, XIANG Fei-peng, HUANG Zhen-yu, LIU Jian-zhong, ZHOU Jun-hu, CEN Ke-fa. Mode of occurrence and transformation of alkali metals in Zhundong coal during combustion[J]. J Fuel Chem Technol, 2014, 42(3):316-322. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18373.shtml
[16]	李勇, 肖军, 章名耀.燃煤过程中碱金属迁移规律的模拟研究与预测分析[J].燃料化学学报, 2005, 33(5):556-560. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16890.shtml LI Yong, XIAO Jun, ZHANG Ming-yao. Modeling and prediction of migration mechanism of alkali metals during coal-fired process[J]. J Fuel Chem Technol, 2005, 33(5):556-560. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract16890.shtml
[17]	王智化, 李谦, 刘敬, 黄镇宇, 周志军, 周俊虎, 岑可法.准东煤中碱金属的赋存形态及其在热解过程中的迁移规律[J].中国电机工程学报, 2014, 34(s1):130-135. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC2014S1018.htm WANG Zhi-hua, LI Qian, LIU Jing, HUANG Zhen-yu, ZHOU Zhi-jun, ZHOU Jun-hu, CEN Ke-fa. Occurrence of alkali metals in Zhundong coal and its migration during pyrolysis process[J]. Proc CSEE, 2014, 34(s1):130-135. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC2014S1018.htm
[18]	LI C Z, SATHE C, KERSHAW J R, PANG Y. Fates and roles of alkali and alkaline earth metals during the pyrolysis of a Victorian brown coal[J]. Fuel, 2000, 79(3):427-438. https://www.researchgate.net/publication/223921892_Fates_and_roles_of_alkali_and_alkaline_earth_metals_during_the_pyrolysis_of_a_Victorian_brown_coal
[19]	王智化, 许东相, 何勇, 万凯迪, 朱燕群, 岑可法.温度对准东煤裂解特性及碱金属释放影响的试验研究[J].中国电机工程学报, 2015, 35(s1):113-117. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC2015S1018.htm WANG Zhi-hua, XU Dong-xiang, HE Yong, WAN Kai-di, ZHU Yan-qun, CEN Ke-fa. Effects of temperature on pyrolysis properties and sodium release during pyrolysis of Zhundong coal[J]. Proc CSEE, 2015, 35(s1):113-117. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC2015S1018.htm
[20]	QUYN D M, WU H., LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part Ⅰ. Volatilisation of Na and Cl from a set of NaCl-loaded samples[J]. Fuel, 2002, 81(2):143-149. doi: 10.1016/S0016-2361(01)00127-2
[21]	WANG C A, JIN X, WANG Y K, YAN Y, JIANG C, LIU Y H, CHE D F. Release and transformation of sodium during pyrolysis of Zhundong coals[J]. Energy Fuels, 2015, 29(1):78-85. doi: 10.1021/ef502128s
[22]	BLASING M, MULLER M. Mass spectrometric investigations on the release of inorganic species during gasification and combustion of German hard coals[J]. Combust Flame, 2010, 157(7):1374-1381. doi: 10.1016/j.combustflame.2010.01.003
[23]	JIANG L, HU S, XIANG J, SU S, SUN L S, XU K, YAO Y. Release characteristics of alkali and alkaline earth metallic species during biomass pyrolysis and steam gasification process[J]. Bioresour Technol, 2012, 116:278-84. doi: 10.1016/j.biortech.2012.03.051
[24]	WU H, QUYN D M, LI C Z. Volatilisation and catalytic effects of alkali and alkaline earth metallic species during the pyrolysis and gasification of Victorian brown coal. Part Ⅲ. The importance of the interactions between volatiles and char at high temperature[J]. Fuel, 2002, 81(8):1033-1039. doi: 10.1016/S0016-2361(02)00011-X
[25]	沈铭科, 邱坤赞, 黄镇宇, 王智化, 刘建忠.准东煤掺烧高岭土对固钠率及灰熔融特性影响研究[J].燃料化学学报, 2015, 43(9):1044-1051. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18688.shtml SHEN Ming-ke, QIU Kun-zan, HUANG Zhen-yu, WANG Zhi-hua, LIU Jian-zhong. Influence of kaolin on sodium retention and ash fusion characteristic during combustion of Zhundong coal[J]. J Fuel Chem Technol, 2015, 43(9):1044-1051. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract18688.shtml
[26]	XU L L, LIU J, KANG Y, MIAO Y Q, REN W, WANG T T. Safely burning high alkali coal with kaolin additive in a pulverized Fuel boiler[J]. Energy Fuels, 2014, 28(9):5640-5648. doi: 10.1021/ef501160f
[27]	KOSMINSKI A, ROSS D P, AGNEW J B. Reactions between sodium and silica during gasification of a low-rank coal[J]. Fuel Process Technol, 2006, 87(12):1037-1049. doi: 10.1016/j.fuproc.2005.06.007
[28]	LI X, BAI Z Q, BAI J, HAN Y N, KONG L X, LI W. Transformations and roles of sodium species with different occurrence modes in direct liquefaction of Zhundong coal from Xinjiang, Northwestern China[J]. Energy Fuels, 2015, 29(9):5633-5639. doi: 10.1021/acs.energyfuels.5b01138
[29]	GUO S, JIANG Y F, YU Z L, ZHAO J T, FANG Y T. Correlating the sodium release with coal compositions during combustion of sodium-rich coals[J]. Fuel, 2017, 196:252-260. doi: 10.1016/j.fuel.2017.02.004
[30]	SATHE C, HAYASHI J I, LI C Z, CHIBA T. Release of alkali and alkaline earth metallic species during rapid pyrolysis of a Victorian brown coal at elevated pressures[J]. Fuel, 2003, 82(12):1491-1497. doi: 10.1016/S0016-2361(03)00070-X