钙基添加剂对不同煤种解耦燃烧下硫释放的影响

doi:10.16085/j.issn.1000-6613.2022-0136

摘要/Abstract

摘要：

煤燃烧后排放的硫氧化物导致的环境污染问题已经引起人们的日益关注。基于一段式和两段式卧式炉，本文探究在传统燃烧和解耦燃烧条件下，温度、煤种以及CaO对燃煤释放SO₂规律的影响。试验结果表明：不同煤种的SO₂释放规律存在差异。随着温度的升高，不同煤种燃烧SO₂的释放量均不断增加，硫的动态析出曲线逐渐由单峰分布转化为双峰分布。传统燃烧模式下，添加的CaO对烟煤、无烟煤和褐煤脱硫效率可以达到70%以上，高氯煤脱硫效率则较低，仅有12.09%～20.45%；随温度升高，烟煤、褐煤和高氯煤的脱硫效率呈现先略微下降，后升高再下降的趋势，烟煤脱硫效率则逐渐降低。解耦燃烧模式下，CaO对烟煤、无烟煤脱硫效率在42.35%～76.23%，褐煤在21.35%～52.63%，高氯煤脱硫效率仍然较低，在8.93%～10.57%；随温度升高，烟煤、褐煤和高氯煤的脱硫效率呈现先增加后降低的趋势，烟煤脱硫效率逐渐降低。解耦燃烧模式下，不同煤种SO₂的总释放量大于传统燃烧模式，添加CaO后脱硫效率小于传统燃烧模式。

关键词: 燃煤, 解耦燃烧, 硫释放, 氧化钙, 干法脱硫

Abstract:

Sulfur oxides emitted by coal combustion have caused environmental pollution problems and attracted increasing attention. Based on one-stage and two-stage horizontal furnaces, the effects of temperature, coal type and CaO on the release of SO₂ were explored under traditional combustion and decoupling combustion. The results show that there are differences in the SO₂ release for different coals. Under both of combustion modes, when the temperature rises, the amount of SO₂ released from the combustion of different coals increases continuously, and the SO₂ release curve changes from a single-peak distribution to a double-peak distribution. In traditional combustion, after the addition of CaO, the desulfurization efficiencies of bituminous coal, anthracite and lignite can reach more than 70%, while the efficiency of high-chlorine coal is only 12.09% to 20.45%; with the increase of temperature, the desulfurization efficiencies of bituminous coal, lignite and high-chlorine coal slightly decrease at first, then increase and decrease, while the efficiency of bituminous coal gradually decreases. In decoupling combustion, after the addition of CaO, the desulfurization efficiencies of bituminous coal and anthracite coal are 42.35%—76.23%, it is 21.35%—52.63% for lignite, and the efficiency of high-chlorine coal is still low, ranging from 8.93% to 10.57%; with the increase of temperature, the desulfurization efficiencies of bituminous coal, lignite and high-chlorine coal increase at first and then decrease,while the desulfurization efficiency of bituminous coal gradually decrease. In decoupling combustion, the total release of SO₂ from different coals is more than that in traditional combustion, and the desulfurization efficiency with the addition of CaO is lower than that in the traditional combustion.

Key words: coal, decoupling combustion, sulfur release, calcium oxide, dry desulfurization

中图分类号:

X701.3

董琨, 赵旭, 杨富鑫, 谭厚章, 雷廷宙, 程占军. 钙基添加剂对不同煤种解耦燃烧下硫释放的影响[J]. 化工进展, 2022, 41(S1): 595-605.

DONG Kun, ZHAO Xu, YANG Fuxin, TAN Houzhang, LEI Yanzhou, CHEN Zhanjun. Effects of calcium-based additives on sulfur release during decoupling combustion of different coals[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 595-605.

图/表 10

图1 一段式卧式炉实验系统示意图

图2 两段式卧式炉实验系统示意图

表1 不同煤种的工业分析和元素分析（质量分数）

煤种	工业分析/%				元素分析/%
煤种	A_ad	V_ad	FC_ad	M_ad	C_d	H_d	N_d	S_d	O_d
烟煤	12.64	28.91	52.18	6.28	67.61	3.42	0.40	1.81	13.27
无烟煤	14.33	9.60	75.12	0.94	74.99	2.73	0.52	1.16	6.14
褐煤	15.95	31.30	43.01	9.72	60.54	3.66	0.42	1.04	16.67
高氯煤	4.26	30.00	48.02	17.72	64.37	3.92	0.33	0.14	26.06

表2 不同煤种的各形态硫分布（质量分数）

煤种	空气干燥基全硫S_t，ad/%	硫酸盐硫 S_s，ad/%	硫化铁硫 S_p，ad/%	有机硫 S_o.ad/%
烟煤	1.81	0.61	0.68	0.52
无烟煤	1.16	0.10	0.40	0.66
褐煤	1.04	0.02	0.32	0.70
高氯煤	0.14	0.02	0.04	0.08

图3 一段式燃烧模式下不同种煤的硫动态析出曲线

图4 一段式燃烧模式下添加CaO后硫动态析出曲线

图5 不同煤种、不同工况下SO2释放量及脱除效率

图6 两段燃烧模式下不同种煤的硫动态析出曲线

图7 两段燃烧模式下添加CaO后硫动态析出曲线

图8 两段燃烧模式下不同煤种SO2释放量及脱硫效率

参考文献 31

1	卢晓燕. 碳中和背景下中国煤炭行业转型发展路径研究[J]. 煤炭经济研究, 2021, 41(8): 64-68.
	LU X Y. Research on the transformation and development path of China’s coal industry under the background of carbon neutrality[J]. Coal Economic Research, 2021, 41(8): 64-68.
2	ZHAO Y, WANG S, DUAN L, et al. Primary air pollutant emissions of coal-fired power plants in China: current status and future prediction[J]. Atmospheric Environment, 2008, 42(36): 8442-8452.
3	苗强. 燃煤脱硫技术研究现状及发展趋势[J]. 洁净煤技术, 2015, 21(2): 59-63.
	MIAO Q. Research status and progress of steam coal desulfurization technologies[J]. Clean Coal Technology, 2015, 21(2): 59-63.
4	赵永椿, 马斯鸣, 杨建平, 等. 燃煤电厂污染物超净排放的发展及现状[J]. 煤炭学报, 2015, 40(11): 2629-2640.
	ZHAO Y C, MA S M, YANG J P, et al. Status of ultra-low emission technology in coal-fired power plant [J]. Journal of China Coal Society, 2015, 40(11): 2629-2640.
5	史文峥, 杨萌萌, 张绪辉, 等. 燃煤电厂超低排放技术路线与协同脱除[J]. 中国电机工程学报, 2016, 36(16): 4308-4318, 4513.
	SHI W Z, YANG M M, ZHANG X H, et al. Ultra-low emission technical route of coal-fired power plants and the cooperative removal [J]. Proceedings of the CSEE, 2016, 36(16): 4308-4318, 4513.
6	冯鹏, 李正鸿, 刘鹤欣, 等. 超低排放燃煤电厂中SO₃的迁移及脱除特征[J]. 化工进展, 2020, 39(11): 4660-4667.
	FENG P, LI Z H, LIU H X, et al. Migration and removal characteristics of SO₃ in ultra-low emission coal-fired power plant [J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4660-4667.
7	孙林兵, 倪中海, 张丽芳, 等. 煤热解过程中氮、硫析出形态的研究进展[J]. 洁净煤技术, 2002(3): 47-50.
	SUN L B, NING Z H, ZHANG L F, et al. Research advancement of nitrogen and sulfur separate out form in coal pyrolysis process [J]. Clean Coal Technology, 2002(3): 47-50.
8	HU Y, NAITO S, KOBAYASHI N, et al. CO₂, NO _x and SO₂ emissions from the combustion of coal with high oxygen concentration gases[J]. Fuel, 2000, 79(15): 1925-1932.
9	王保文, 李贺宇, 王维, 等. 部分氧解耦煤化学链燃烧中硫的演化与分布[J]. 石油学报(石油加工), 2020, 36(6): 1129-1139.
	WANG B W, LI H Y, WANG W, et al. Evolution and distribution of sulfur in chemical looping combustion with partial oxygen uncoupling of coal[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2020, 36(6): 1129-1139.
10	吕娟, 黄利华, 滕德亮, 等. 相对湿度对钙基脱硫剂干法烟气脱硫效率的影响[J]. 环境工程学报, 2020, 14(6): 1563-1569.
	LU J, HUANG L H, TENG D L, et al. Effect of relative humidity on dry flue gas desulfurization by calcium-based desulfurizer [J]. Chinese Journal of Environmental Engineering, 2020, 14(6): 1563-1569.
11	秦跃强, 陈雪莉, 陈汉鼎, 等. 添加CaO对煤热解过程中砷和硫迁移转化的影响[J]. 燃料化学学报, 2017, 45(2): 147-156.
	QIN Y Q, CHEN X L, CHEN H D, et al. Effects of adding CaO on the release and transformation of arsenic and sulfur during coal pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2017, 45(2): 147-156.
12	尚校, 高士秋, 汪印, 等. 不同煤燃烧方式降低NO _x 排放比较及解耦燃烧应用[J]. 燃料化学学报, 2012, 40(6): 672-679.
	SHANG X, GAO S Q, WANG Y, et al. Comparison of NO_x reduction among different coal combustion methods and the application of decoupling combustion [J]. Journal of Fuel Chemistry and Technology, 2012, 40(6): 672-679.
13	许鑫玮, 谭厚章, 王学斌, 等. 煤粉工业锅炉预燃式低氮燃烧器试验研究与开发[J]. 洁净煤技术, 2020, 26(5): 36-41.
	XU X W, TAN H Z, WANG X B, et al. Experimental study and development on a pre-burning low-NO _x burner for pulverized coal industry boiler [J]. Clean Coal Technology, 2020, 26(5): 36-41.
14	陈隆, 王乃继. 解耦燃烧技术在煤粉工业锅炉高速燃烧器中的应用研究[J]. 煤质技术, 2021, 36(4): 1-7.
	CHEN L, WANG N J. Applied research of decoupling combustion in pulverized coal industrial boilers equipped with high-speed burner [J]. Goal Quality Technology, 2021, 36(4): 1-7.
15	WU X, FAN W, LIU S, et al. Effect of high temperature and separated combustion on SO₂ release characteristics during coal combustion under O₂/CO₂ atmosphere[J]. Journal of the Energy Institute, 2020, 93(6): 2388-2398.
16	安冬冬, 谢召祥, 张本强, 等. 煤热解过程中硫元素释放进展研究[J]. 能源与节能, 2021(10): 44-46.
	AN D D, XIE Z X, ZHANG B Q, et al. Study on development of sulfur release in process of coal pyrolysis [J]. Energy and Conservation, 2021(10): 44-46.
17	谢新媛. 煤燃烧过程固硫剂的研究进展[J]. 化工进展, 2004, 23(10): 1062-1066.
	XIE X Y. Studying progress of desulfurizer during coal combustion [J]. Chemical Industry and Engineering Progress, 2004, 23(10): 1062-1066.
18	冯盛丹, 樊建江, 李平, 等. 马莲台煤热解过程中硫元素的迁移规律研究[J]. 煤炭工程, 2018, 50(7): 133-136.
	FENG S D, FAN J J, LI P, et al. Investigation of sulfur migration law during pyrolysis of maliantai coal [J]. Coal Engineering, 2018, 50(7): 133-136.
19	程军. 炉内高温燃烧两段脱硫的机理研究[D]. 杭州: 浙江大学, 2002.
	CHENG J. Mechanisms of two-stage desulfurization technology at high temperature during coal combustion in furnaces [D]. Hangzhou: Zhejiang University, 2002.
20	曹欣玉, 卜成, 葛林甫, 等. 煤燃烧过程中硫的析出规律及脱硫的研究[J]. 环境污染与防治, 1989(6): 2-6, 15,41.
	CAO X Y, PU C, GE L F, et al. Study on precipitation law of sulfur and desulfurization during coal combustion [J]. Environmental Pollution & Control, 1989(6): 2-6, 15, 41.
21	刘诗薇, 邹冲, 赵俊学, 等. 不同焦煤中硫的赋存形态及热解气体逸出分析[J]. 煤炭转化, 2018, 41(2): 24-30.
	LIU S W, ZHOU C, ZHAO J X, et al. Speciation of sulfur and regularity of pyrolysis gas evolution in different coking coals [J]. Coal Conversion, 2018, 41(2): 24-30.
22	苏银皎, 滕阳, 张锴, 等. 煤热解过程中汞和硫的释放特性[J].动力工程学报, 2022, 42(1): 19-26.
	SU Y J, TENG Y, ZHANG K, et al. Release characteristics of mercury and sulfur during coal pyrolysis[J]. Journal of Chinese Society of Power Engineering, 2022, 42(1): 19-26.
23	刘少林, 孔娇, 申岩峰, 等. 高有机硫炼焦煤分选组分中硫的赋存形态及其热变迁行为研究[J]. 燃料化学学报, 2019, 47(8): 915-924.
	LIU S L, KONG J, SHEN Y F, et al. Sulfur occurrence and transformation during pyrolysis of the flotation fraction from coking coals with high organic sulfur[J]. Journal of Fuel Chemistry and Technology, 2019, 47(8): 915-924.
24	刘轩, 赵元财, 滕阳, 等. 煤中砷与硫洗选过程迁移和燃烧过程释放特性[J]. 燃料化学学报, 2022, 50(7): 21-31.
	LIU X, ZHAO Y C, TENG Y, et al. Migration behaviors of arsenic and sulfur from coal during washing process and theirrelease characteristics during combustion process [J]. Journal of Fuel Chemistry and Technology, 2022, 50(7): 21-31.
25	刘志红, 涂威, 韩正伟. 煤中硫在氩气气氛下迁移规律试验研究[J]. 煤炭技术, 2018, 37(2): 310-312.
	LIU Z H, TU W, HAN Z W. Experimental study on migration patterns of sulfur in coal under argon atmosphere[J]. Coal Technology, 2018, 37(2): 310-312.
26	孙丽娜, 李凯, 汤立红, 等. 常见金属氧化物烟气脱硫研究进展[J]. 化工进展, 2017, 36(1): 181-188.
	SUN L N, LI K, TANG L H, et al. Research progress of common metal oxides for flue gas desulfurization [J]. Chemical Industry and Engineering Progress, 2017, 36(1): 181-188.
27	王小明. 干法及半干法脱硫技术[J]. 电力科技与环保, 2018, 34(1): 45-48.
	WANG X M. Technology about dry desulfurization and semi -dry desulfurization [J]. Electric Power Environmental Protection, 2018, 34(1): 45-48.
28	谢建军, 杨学民, 吕雪松, 等. 煤热解过程中硫氮分配及迁移规律研究进展[J]. 化工进展, 2004, 23(11): 1214-1218.
	XIE J J, YANG X M, LYU X S, et al. Progress on transformation behavior of sulfur and nitrogen during coal pyrolysis [J]. Chemical Industry and Engineering Progress, 2004, 23(11): 1214-1218.
29	郑瑛, 史学锋, 周英彪, 等. 煤燃烧过程中硫分析出规律的研究进展[J]. 煤炭转化, 1998(1): 36-40.
	ZHENG Y, SHI X F, ZHOU Y B, et al. Research progress on the law of sulfur analysis during coal combustion[J]. Coal Conversion, 1998(1): 36-40.
30	汪波, 郝晓路, 李永华. 煤热解过程中硫的释放与转化研究[J]. 电力科学与工程, 2016, 32(10): 73-78.
	WANG B, HE X L, LI Y H. Emission and conversion of sulfur in coal under pyrolysis conditions [J]. Electric Power Science and Engineering, 2016, 32(10): 73-78.
31	IBARRA J V, BONET A J, MOLINER R. Release of volatile sulfur-compounds during low-temperature pyrolysis of coal [J]. Fuel, 1994, 73(6): 933-939.

[1]	李东泽, 张祥, 田键, 胡攀, 姚杰, 朱林, 卜昌盛, 王昕晔. 基于水泥窑脱硝的碳基还原NO _x 研究进展[J]. 化工进展, 2023, 42(9): 4882-4893.
[2]	郑成强, 李小龙, 李军状, 段玖祥, 杨林军. 燃煤电厂逃逸氨迁移转化特性研究进展[J]. 化工进展, 2022, 41(2): 964-973.
[3]	高天, 张伊黎, 熊卓, 赵永椿, 张军营. 改性氧化钛光催化氧化单质汞性能及其影响因素研究进展[J]. 化工进展, 2022, 41(2): 690-700.
[4]	李亚林, 刘蕾, 关明玥, 孙猛, 李柳婷, 毛瑞月, 何海洋. 纳米CaO₂激发餐厨垃圾碳组分合成水凝胶及溶胀性能分析[J]. 化工进展, 2022, 41(11): 6120-6129.
[5]	王小虎, 吴葵霞, 吴德华, 张其龙, 董勇. 电石渣在燃煤电厂脱硫工艺中的应用研究进展[J]. 化工进展, 2021, 40(S2): 140-148.
[6]	李兵, 张其龙, 王猛, 李济琛, 席雯, 周灿. 碱性吸收剂脱除燃煤烟气中HCl的研究进展[J]. 化工进展, 2021, 40(S1): 404-410.
[7]	于洋, 周欣, 程俊峰, 董长青, 王玉山, 刘英华. 燃煤电厂可凝结颗粒物检测方法、排放特征及脱除技术研究进展[J]. 化工进展, 2021, 40(8): 4515-4524.
[8]	赵瑞, 张翼, 余学海, 史晓宏, 刘毅, 王鹏, 韩涛. 中试平台SCR低温催化剂测试与氨逃逸分布特征[J]. 化工进展, 2021, 40(8): 4610-4615.
[9]	李亚林, 刘蕾, 李坤鹏, 林康, 窦雪, 毕雅洁. 球状纳米CaO₂的制备及其协同电渗透污泥深度脱水[J]. 化工进展, 2021, 40(7): 4047-4054.
[10]	马双忱, 林宸雨, 周权, 吴忠胜, 刘琦, 陈文通, 樊帅军, 要亚坤, 马采妮. 基于深度神经网络的脱硫系统预测模型及应用[J]. 化工进展, 2021, 40(3): 1689-1698.
[11]	于英利, 付旭晨, 戴莹莹, 荣俊, 高正平, 蔡斌, 胡俊虎. 燃煤电站锅炉水冷壁壁面高温腐蚀问题分析与对策[J]. 化工进展, 2020, 39(S1): 90-96.
[12]	赵红涛, 王树民. 燃煤烟气胺法脱碳MVR再生系统关键参数及能耗分析[J]. 化工进展, 2020, 39(S1): 256-262.
[13]	于伟静, 马超, 谭闻濒, 崔磊, 陈玉彬, 李昌浩. 燃煤电厂白色烟羽控制研究进展[J]. 化工进展, 2020, 39(S1): 232-241.
[14]	涂弢, 郭浩, 程华金, 邱建民, 王学重, 刘庆生. 锂辉石-氧化钙烧结法提锂的物相重构与动力学[J]. 化工进展, 2020, 39(9): 3478-3486.
[15]	张瑞翔,王鹏,伍婷婷,刘建忠,周俊虎. 声波与喷雾对于飞灰颗粒团聚的影响[J]. 化工进展, 2020, 39(3): 858-863.