SO<sub>2</sub>和H<sub>2</sub>O(g)对新疆高钠煤中钠挥发和形态迁移的研究

孙鑫; 赵斌; 王子兵; 梁精龙; 李慧

SO₂和H₂O(g)对新疆高钠煤中钠挥发和形态迁移的研究

华北理工大学冶金与能源学院, 河北唐山 063009

基金项目:

国家自然科学基金 514740013

河北省自然科学基金 E2016209163

详细信息

通讯作者:
孙鑫, Tel:18532536865;E-mail:sunxin8835@163.com

中图分类号: TQ534
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- 被引次数: 0
出版历程
- 收稿日期: 2017-04-25
- 修回日期: 2017-08-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2017-10-10

Effect of H₂O(g) and SO₂(g) on the volatilization and transformation of sodium during Xinjiang high-sodium coal combustion

School of Metallurgy and Energy, North China University of Science and Technology, Tangshan 063009, China

Funds:

the National Natural Science Foundation of China 514740013

Natural Science Foundation of Hebei Province E2016209163

摘要

摘要: 在水平管式炉上进行了400-1 100℃新疆高钠煤恒温燃烧实验，并利用逐级提取的方法分析煤及煤灰中钠的赋存形态，研究煤中钠的释放和形态迁移特性。重点考察700和1100℃下H₂O（g）和SO₂（g）单因素及双因素对煤中无机钠挥发和形态迁移的影响。结果表明，随着温度的升高，煤中钠的释放比例逐渐增大，其中，有机态钠最先析出，其次是水溶态无机钠，硅铝酸盐形式的无机钠则由于高热稳定性不易分解或挥发。低温下（700℃）H₂O（g）的存在降低了钠的挥发，而较高温度下（1 100℃）焦炭与水蒸气反应生成的局部还原性气氛促进煤中钠的挥发，但当入口气氛中H₂O（g）浓度高于20%时，促进作用减小。SO₂的存在抑制了煤中钠的挥发，随着燃烧温度升高，SO₂对钠的抑制作用减弱。H₂O和SO₂双因素作用下，低温下（700℃）抑制了煤中钠的挥发，而较高温度下（1 100℃）钠的挥发特性取决于两者在入口气氛中的浓度。对于选取的高钠煤，20% H₂O和2.0×10^-3 SO₂入口气氛下，1 100℃煤燃烧钠的挥发比例由86%提高到了87.1%。
- 新疆高钠煤 /
- SO₂ /
- H₂O (g) /
- 挥发 /
- 形态迁移
Abstract: Combustion experiment of Xinjiang coal with high sodium content was carried out in a horizontal tube furnace at 400-1 100℃. The occurrence of sodium in coal and ash was analyzed by sequential extraction method to study the release and transformation characteristics of sodium, especially the effect of H₂O(g) and SO₂(g) at 700℃ and 1 100℃. The results show that, the release ratio of sodium in coal increases gradually with the increase of temperature. The sodium in organic form vaporizes first, followed by water-soluble inorganic sodium, while the inorganic sodium in the form of aluminosilicate is difficult to vaporize due to high thermal stability. At lower temperature (700℃), H₂O(g) has a negative effect on the volatilization of sodium, while at higher temperature (1 100℃), the reductive atmosphere formed by the reaction of char and H₂O(g) promotes the volatilization of sodium. When the proportion of H₂O(g) is larger than 20% in inlet gas, the promotion effect of H₂O(g) is weakened. SO₂ can inhibit sodium volatilization, while the inhibiting effect of SO₂ becomes less significant as the temperature increases from 700℃ to 1 100℃. In the presence of both H₂O(g) and SO₂, the sodium volatilization at 700℃ is inhibited. The combination effect of H₂O(g) and SO₂ at 1 100℃ depends on its concentration. Under the atmosphere containing 20%H₂O and 2.0×10^-3 SO₂ the total volatilization ratio of sodium increases from 86% to 87.1%.
- Xinjiang high-sodium coal /
- SO₂ /
- H₂O(g) /
- volatilization /
- speciation transformation

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图 1 煤燃烧实验系统示意图

Figure 1 Schematic diagram of coal combustion experimental system

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图 2 不同温度下准东煤燃烧钠的挥发特性

Figure 2 Volatilization of sodium during Zhundong coal combustion at different temperatures

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图 3 原煤及不同温度下灰中钠的形态分布

Figure 3 Speciation transformation of raw coal and ashes at different temperatures

: F1; : F2; : F3; : F4; : gas phase

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图 4 不同温度和水蒸气份额下煤中钠挥发比例

Figure 4 Volatilization ratio of Na with differentH₂O(g) fractions at 700℃ and 1100℃

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图 5 不同温度和气氛下的无机钠化合物的平衡组成

Figure 5 Equilibrium Na components at oxidative and reductive atmosphere

(a): oxidative atmosphere(O₂:C=1.2); (b): reductive atmosphere(O₂:C=0.8)

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图 6 不同温度和入口SO₂浓度下煤中钠挥发比例

Figure 6 Volatilization ratio of Na with different SO₂ fractions at 700℃ and 1100℃

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图 7 氧化性气氛下添加SO₂(g)无机钠化合物的平衡组成

Figure 7 Equilibrium Na components under the effect of SO₂(g) at oxidative atmosphere(O₂:C=1.2)

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图 8 H₂O(g)和SO₂同时存在时钠的挥发比例

Figure 8 Volatilization ratio of Na in the presence of both H₂O(g) and SO₂

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表 1 煤样的元素分析、工业分析和煤灰成分分析

Table 1 Ultimate, proximate and ash analysis of the coal tested

Ultimate analysis w_ad/%						Q_{ar, net} /(kJ·kg^-1)	Proximate analysis w_ad/%
C	H	O^a	N	S	Na	Q_{ar, net} /(kJ·kg^-1)	M	V	A	FC
72.18	3.47	18.29	0.72	1.36	0.35	19330	9.21	31.47	3.98	55.34
Ash composition w/%
SiO₂	Al₂O₃		Fe₂O₃	CaO	MgO	K₂O	Na₂O	TiO₂	P₂O₅	SO₃
23.76	15.42		7.31	8.74	3.09	1.33	6.87	0.54	0.77	19.41
^a: by difference

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表 2 实验温度和气氛工况

Table 2 Atmosphere and temperature the cases tested

Case	O₂ /%	H₂O(g) /%	SO₂ /10^-3	N₂ /%	Temperature t/℃
1	21	0	0.0		400-1100
2	21	10	0.0
3	21	20	0.0
4	21	30	0.0
5	21	0	0.5	balance gas
6	21	0	1.0		700; 1100
7	21	0	2.0
8	21	20	1.0
9	21	20	2.0

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表 3 钠形态分析的化学提取步骤

Table 3 Sequential chemical extraction procedure used for sodium speciation

Step	Sodium occurrence	Extraction(0.5g of dry solid)	Shaking time and temperature
F1	water soluble	60mL of distilled water	> 24h at 60℃ water bath
F2	ammonium acetate soluble	60mL of 1mol/L CH₃COONH₄	> 24h at 60℃ water bath
F3	hydrochloric acid soluble	60mL of 1mol/L HCl	> 24h at 60℃ water bath
F4	insoluble	9mL aqua regia	drying for 12h at 60℃, then microwave digestion

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参考文献(24)

[1]	严陆光, 夏训诚, 吕绍勤, 吴甲春, 林闽, 黄常纲.大力推进新疆大规模综合能源基地的发展[J].电工电能新技术, 2011, 30(1):1-7. http://www.cnki.com.cn/Article/CJFDTOTAL-DGDN201101001.htm YAN Lu-guang, XIA Xun-cheng, LÜ Shao-qin, WU Jia-chun, LIN Min, HUANG Chang-gang. Great promotion of development of large scale integrative energy base in Xinjiang.[J] Adv Technol Electrical Eng Energy, 2011, 30(1):1-7. http://www.cnki.com.cn/Article/CJFDTOTAL-DGDN201101001.htm
[2]	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 Jing, WANG Zhi-hua, XIANG Fei-peng, HUANG Zhen-yu, LIU Jian-zhong, ZHOU Jun-hu, CEN Ke-fa. Modes 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
[3]	WANG X, XU Z, WEI B, ZHANG L, TAN H, YANG T, MIKUL ČIĆ H, DUIĆ N. The ash deposition mechanism in boilers burning Zhundong coal with high contents of sodium and calcium:a study from ash evaporating to condensing[J]. Appl Therm Eng, 2015, 80:150-159. doi: 10.1016/j.applthermaleng.2015.01.051
[4]	XU J, YU D, FAN B, ZENG X, LÜ W, CHEN J. Characterization of Ash Particles from Co-combustion with a Zhundong Coal for Understanding Ash Deposition Behavior[J]. Energy Fuels, 2013, 28(1):678-684.
[5]	WU X, ZHANG X, YAN K, CHEN N, ZHANG J, XU X, DAI B, ZHANG J, ZHANG L. Ash deposition and slagging behavior of Chinese Xinjiang high-alkali coal in 3MW th pilot-scale combustion test[J]. Fuel, 2016, 181:1191-1202. doi: 10.1016/j.fuel.2016.03.069
[6]	SONG G, QI X, SONG W, LU Q. Slagging characteristics of Zhundong coal during circulating fluidized bed gasification[J]. Energy Fuels, 2016, 30(5):3967-3974. doi: 10.1021/acs.energyfuels.6b00503
[7]	张守玉, 陈川, 施大钟, 吕俊复, 王健, 郭熙, 董爱霞, 熊绍武.高钠煤燃烧利用现状[J].中国电机工程学报, 2013, 33(5):1-12. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC201305001.htm ZHANG Shou-yu, CHEN Chuan, SHI Da-zhong, LÜ Jun-fu, WANG Jian, GUO Xi, DONG Ai-xia, XIONG Shao-wu. Situation of combustion utilization of high sodium coal[J]. Proc CSEE, 2013, 33(5):1-12. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC201305001.htm
[8]	GLAZER M P, KHAN N A, de JONG W, SPLIETHOFF H, SCHVRMANN H, MONKHOUSE P. Alkali metals in circulating fluidized bed combustion of biomass and coal:measurements and chemical equilibrium analysis[J]. Energy Fuels, 2005, 19(5):1889-1897. doi: 10.1021/ef0500336
[9]	OLESCHKO H, MÜLLER M. Influence of coal composition and operating conditions on the release of alkali species during combustion of hard coal[J]. Energy Fuels, 2007, 21(6):3240-3248. doi: 10.1021/ef700400j
[10]	TAKUWA T, NARUSE I. Detailed kinetic and control of alkali metal compounds during coal combustion[J]. Fuel Process Technol, 2007, 88(11):1029-1034.
[11]	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, LÜ 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
[12]	白向飞, 王越, 丁华, 朱川, 张宇宏.准东煤中钠的赋存状态[J].煤炭学报, 2015, 40(12):2909-2915. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201512022.htm BAI Xiang-fei, WANG Yue, DING Hua, ZHU Chuan, ZHANG Yu-hong. Modes of occurrence of sodium in Zhundong coal[J]. J China Coal Soc, 2015, 40(12):2909-2915. http://www.cnki.com.cn/Article/CJFDTOTAL-MTXB201512022.htm
[13]	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
[14]	陶玉洁, 张彦威, 周俊虎, 景雪晖, 李涛, 刘建忠, 岑可法.准东煤在燃烧过程中的矿物演变过程及Na, Ca释放规律[J].中国电机工程学报, 2015, 35(5):1169-1175. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC201505018.htm TAO Yu-jie, ZHANG Yan-wei, ZHOU Jun-hu, JING Xue-hui, LI Tao, LIU Jian-zhong, CEN Ke-fa. Mineral conversion regularity and release behavior of Na, Ca during zhundong coal's combustion[J]. Proc CSEE, 2015, 35(5):1169-1175. http://www.cnki.com.cn/Article/CJFDTOTAL-ZGDC201505018.htm
[15]	LI G, WANG C A, YAN Y, JIN X, LIU Y, CHE D. Release and transformation of sodium during combustion of Zhundong coals[J]. J Energy Inst, 2016, 89(1):48-56. doi: 10.1016/j.joei.2015.01.011
[16]	BLÄSING M, MÜLLER M. Mass spectrometric investigations on the release of inorganic species during gasification and combustion of Rhenish lignite[J]. Fuel, 2010, 89(9):2417-2424. doi: 10.1016/j.fuel.2009.11.042
[17]	徐林林. 高岭土对高钠煤燃烧过程中碱金属的脱除效果研究[D]. 天津大学, 2015. XU Lin-lin. Effect of Kaolin on the removal of alkali metals during high sodium coal combustion[D]. Tianjin:Tianjin University, 2015.
[18]	KYI S, CHADWICK B L. Screening of potential mineral additives for use as fouling preventatives in Victorian brown coal combustion[J]. Fuel, 1999, 78(7):845-855. doi: 10.1016/S0016-2361(98)00205-1
[19]	ZHANG J, HAN C-L, YAN Z, LIU K, XU Y, SHENG C-D, PAN W-P. The varying characterization of alkali metals (Na, K) from coal during the initial stage of coal combustion[J]. Energy Fuels, 2001, 15(4):786-793. doi: 10.1021/ef000140u
[20]	陈安合, 杨学民, 林伟刚.生物质热解和气化过程Cl及碱金属逸出行为的化学热力学平衡分析[J].燃料化学学报, 2007, 35(5):539-547. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17226.shtml CHEN An-he, YANG Xue-min, LIN Wei-gang. Release characteristics of chlorine and alkali metals during pyrolysis and gasification of biomass by thermodynamical equilibrium analysis[J]. J Fuel Chem. Technol, 2007, 35(5):539-547. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17226.shtml
[21]	刘慧敏, 王春波, 黄星智, 张月, 孙鑫.富氧燃烧方式下煤中砷的挥发行为[J].化工学报, 2015, 66(12):5079-5087. http://www.cnki.com.cn/Article/CJFDTOTAL-HGSZ201512047.htm LIU Hui-min, WANG Chun-bo, HUANG Xing-zhi, Zhang Yue, Sun Xin. Volatilization of arsenic in coal during oxy-fuel combustion[J]. J Chem Ind Eng, 2015, 66(12):5079-5087. http://www.cnki.com.cn/Article/CJFDTOTAL-HGSZ201512047.htm
[22]	BECIDAN M L, SØRUM L, LINDBERG D. Impact of municipal solid waste (MSW) quality on the behavior of alkali metals and trace elements during combustion:a thermodynamic equilibrium analysis[J]. Energy Fuels, 2010, 24(6):3446-3455. doi: 10.1021/ef901144u
[23]	张晓羽, 张海霞, 那永洁.准东煤成灰过程中钠的迁移特性及形态变化[J].洁净煤技术, 2015, 21(2):45-50. http://www.cnki.com.cn/Article/CJFDTOTAL-JJMS201502012.htm ZHANG Xiao-yu, ZHANG Hai-xia, NA Song-jie. Migration characteristics and morphological changes of sodium during ashing process of Zhundong coal[J]. Clean Coal Technol, 2015, 21(2):45-50. http://www.cnki.com.cn/Article/CJFDTOTAL-JJMS201502012.htm
[24]	邢万丽. 生物质与煤混燃过程中硫与氯对碱金属迁移转化的竞争机制[D]. 沈阳航空航天大学, 2011. XING Wan-li. The competitive mechanism of sulfur and chlorine on the migration and transformation of alkali during biomass and coal co-combustion[D]. Shenyang:Shenyang Aerospace University, 2011.