碱性氧化物对煤灰熔融特征行为的影响

doi:10.16085/j.issn.1000-6613.2019-0921

化工进展 ›› 2020, Vol. 39 ›› Issue (2): 496-505.DOI: 10.16085/j.issn.1000-6613.2019-0921

碱性氧化物对煤灰熔融特征行为的影响

郑烨¹(),李建波²,关彦军¹,杨凤玲³,张锴¹(),程芳琴³

^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.低品位能源利用技术及系统教育部重点实验室，重庆大学，重庆 400044
^3.山西大学资源与环境工程研究所，国家环境保护煤炭废弃物资源化高效利用技术重点实验室，山西太原 030006

收稿日期:2019-06-10 出版日期:2020-02-05 发布日期:2020-03-12
通讯作者: 张锴
作者简介:郑烨（1987—），男，博士研究生，研究方向为煤灰化学。E-mail：1142102039@ncepu.edu.cn。
基金资助:
国家自然科学基金委与陕西煤基低碳联合基金重点项目(U1610254);中央高校基本科研业务费专项(JB2017155)

Effects of basic oxides on ash fusion characteristic of coal ash

Ye ZHENG¹(),Jianbo LI²,Yanjun GUAN¹,Fengling YANG³,Kai ZHANG¹(),Fangqin CHENG³

^1.Beijing Key Laboratory of Emission Surveillance and Control for Thermal Power Generation, North China Electric Power University, Beijing 102206, China
^2.Key Laboratory of Low-grade Energy Utilization Technologies and Systems of the Ministry of Education of China, Chongqing University, Chongqing 400044, China
^3.Institute of Resources and Environment Engineering, School of Environmental & Resource Sciences, State Environmental Protection Key Laboratory of Efficient Utilization Technology of Coal Waste Resources, Shanxi University, Taiyuan 030006, Shanxi, China

Received:2019-06-10 Online:2020-02-05 Published:2020-03-12
Contact: Kai ZHANG

摘要/Abstract

摘要：

利用分析纯试剂制备了酸碱比为0.82，但Na₂O、CaO、MgO和Fe₂O₃含量不同的合成灰，并在815℃下在马弗炉中进行灼烧后，对其熔融温度进行测定。同时利用扫描电子显微镜-能谱仪（SEM-EDS）和X射线衍射仪（XRD）对样品微观形貌和矿物组成进行表征。结果表明：随着Na₂O质量分数从4%升高到12%，合成灰变形温度（DT）、软化温度（ST）、半球温度（HT）和流动温度（FT）分别从1225℃、1233℃、1255℃和1297℃下降为1162℃、1174℃、1181℃和1189℃，意味着Na₂O对合成灰具有较强的助熔效果；随着CaO和MgO含量在合成灰中分别增加，DT、ST和HT均单调上升，而FT则呈先下降后上升趋势，说明二者含量变化与合成灰熔融温度呈非线性关系；随着Fe₂O₃质量分数由5%增加至30%，FT由1215℃上升至1308℃，而其他3个熔融特征温度并无显著变化。通过SEM-EDS和XRD表征发现，合成灰中耐熔矿物（SiO₂和CaAl₂Si₂O₈等）和助熔矿物（CaMgSi₂O₆和NaAlSiO₄等）的比例变化和含钠矿物、含钙矿物之间低温共熔反应程度是影响其熔融温度的主要原因。综合对比所有合成煤灰熔融特征温度和化学组成发现，对于具有相同酸碱比的煤灰，DT主要与样品中Na₂O含量和碱土金属总量（CaO+MgO）密切相关影响，而FT主要受Na₂O和Fe₂O₃含量影响。

关键词: 煤灰, 碱性氧化物, 灰熔融温度, 矿物组成, 微观形貌

Abstract:

The fusion characteristics of twenty-three synthetic ashes with the same acidic to basic ratio (R_a/b) of 0.82 but with varying acidic oxides including Na₂O, CaO, MgO, and Fe₂O₃ were investigated. The synthetic ashes were prepared in accordance with the R_a/b of Zhundong coal ash, and then ashed in a muffle furnace at 815℃. These ashes were then subjected to ash fusion analyzer, SEM-EDS and XRD analysis for their fusion temperatures (AFTs), microstructures and mineralogical composition. The results showed that deformation temperature (DT), softening temperature (ST), hemispherical temperature (HT) and flow temperature (FT) of the synthetic ash decreased from 1225℃, 1233℃, 1255℃ and 1297℃, respectively, to 1162°C, 1174℃, 1181℃ and 1189℃ as Na₂O content increased from 4% to 12%, indicating that Na₂O played a significant role in decreasing AFTs. Likewise, as the CaO and MgO contents increased, DT, ST and HT were decreased, while FT was decreased first but increased afterwards, indicating that the effect of CaO and MgO addition on AFTs were non-linear. Furthermore, significant changes in AFTs were not observed as Fe₂O₃ mass fraction varied from 5% to 30%, with the exception that FT increased from 1215℃ to 1308℃. SEM-EDS and XRD analysis revealed that the variation in fusion characteristics of the synthetic ashes were mainly attributed to the proportion of refractory minerals mainly SiO₂ and CaAl₂Si₂O₈ and the fluxing minerals such as CaMgSi₂O₆ and NaAlSiO₄, as well as the degree of eutectic formation between Na- and Ca- bearing minerals. A comprehensive comparison between the measured AFTs and their corresponding basic oxide contents showed that DT was mainly affected by the overall amount of alkaline-earth metal (CaO and MgO) and Na₂O content, whereas FT was closely associated with Na₂O and Fe₂O contents in the synthetic ash.

Key words: coal ash, basic oxides, ash fusion temperature, mineral composition, micromorphology

中图分类号:

TQ536.4

郑烨,李建波,关彦军,杨凤玲,张锴,程芳琴. 碱性氧化物对煤灰熔融特征行为的影响[J]. 化工进展, 2020, 39(2): 496-505.

Ye ZHENG,Jianbo LI,Yanjun GUAN,Fengling YANG,Kai ZHANG,Fangqin CHENG. Effects of basic oxides on ash fusion characteristic of coal ash[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 496-505.

图/表 16

表1 准东煤灰化学组成和熔融特性分析

化学组分	质量分数/%	熔融特性	温度/℃
SiO₂	28.12	DT	1267
Al₂O₃	16.07	ST	1279
CaO	14.31	HT	1291
Fe₂O₃	22.07	FT	1414
MgO	9.67
Na₂O	8.01
TiO₂	0.69
K₂O	0.15
P₂O₅	0.64
MnO	0.27

表2 合成灰成分

样品	质量分数/%
样品	Na₂O	CaO	Fe₂O₃	MgO
Na₂O含量
Na₂O_4%	4.00	15.79	24.54	10.67
Na₂O_6%	6.00	15.17	23.58	10.25
Na₂O_8%	8.00	14.55	22.62	9.83
Na₂O_10%	10.00	13.93	21.66	9.41
Na₂O_12%	12.00	13.31	20.70	8.99
CaO含量
CaO_5%	10.05	5.00	27.82	12.13
CaO_10%	9.03	10.00	25.07	10.90
CaO_15%	8.02	15.00	22.29	9.69
CaO_20%	7.02	20.00	19.50	8.48
CaO_25%	6.02	25.00	16.71	7.27
CaO_30%	5.01	30.00	13.94	6.05
CaO_35%	4.03	35.00	11.10	4.87
MgO含量
MgO_5%	8.98	16.06	24.96	5.00
MgO_10%	8.09	14.45	22.46	10.00
MgO_15%	7.19	12.85	19.96	15.00
MgO_20%	6.29	11.24	17.47	20.00
MgO_25%	5.39	9.63	14.98	25.00
Fe₂O₃含量
Fe₂O₃_5%	12.48	22.30	5.00	15.22
Fe₂O₃_10%	11.21	20.03	10.00	13.76
Fe₂O₃_15%	9.96	17.81	15.00	12.23
Fe₂O₃_20%	8.72	15.58	20.00	10.7
Fe₂O₃_25%	7.47	13.35	25.00	9.18
Fe₂O_{3 30%}	6.23	11.13	30.00	7.64

图1 合成灰Na2O含量变化对熔融特征温度影响

图2 不同Na2O含量合成灰SEM图片和EDS分析

图3 1000℃合成灰中Na2O含量变化XRD图

1—SiO2；2—Fe2O3；3—CaSiO3；4—Ca2Fe2O5；5—CaO；6—CaAl2Si2O8；7—Ca3MgSi2O8；8—Ca2Al2SiO7

图4 合成灰CaO含量变化对熔融特征温度影响

图5 不同CaO含量合成灰SEM图片和EDS分析

图6 1000℃合成灰中CaO含量变化XRD图

1—SiO2；2—Fe2O3；3—CaMgSi2O6；4—CaSiO3；5—CaO

图7 合成灰MgO含量变化对熔融特征温度影响

图8 不同MgO含量合成灰SEM图片和EDS分析

图9 1000℃合成灰中MgO含量变化XRD图

1—SiO2；2—Fe2O3；3—CaSiO3；4—CaO；5—NaAlSiO4；6—Mg2SiO4；7—Ca3Fe2Si3O12；8—Ca2MgSi2O7；9—Ca2SiO4

图10 合成灰Fe2O3含量变化对熔融特征温度影响

图11 不同Fe2O3含量合成灰SEM照片和EDS分析

图12 1000℃合成灰中Fe2O3含量变化XRD图

1—SiO2；2—CaO；3—CaSiO3；4—Fe2O3；5—Ca3Fe2Si3O12

图13 碱性氧化物对变形温度影响

图14 碱性氧化物对流动温度影响

参考文献 21

1	ZHOU J B, ZHUANG X G, ALASTUEY A, et al. Geochemistry and mineralogy of coal in the recently explored Zhundong large coal field in the Junggar basin, Xinjiang province, China[J]. International Journal of Coal Geology, 2010, 82: 51-67.
2	张守玉, 陈川, 施大钟, 等. 高钠煤燃烧利用现状[J]. 中国电机工程学报, 2013, 33(5): 1-12.
	ZHANG Shouyu, CHEN Chuan, SHI Dazhong, et al. Situation of combustion utilization of high sodium coal[J]. Proceedings of the CSEE, 2013, 33(5): 1-12.
3	LI J B, ZHU M M, ZHANG Z Z, et al. The mineralogy, morphology and sintering characteristics of ash deposits on a probe at different temperatures during combustion of blends of Zhundong lignite and a bituminous coal in a drop tube furnace[J]. Fuel Processing Technology, 2016, 149: 176-186.
4	陈晓东, 孔令学, 白进, 等. 高温气化条件下Na₂O对煤灰中矿物质演化行为的影响[J]. 燃料化学学报, 2016, 44(3): 263-272.
	CHEN Xiaodong, KONG Lingxue, BAI Jin, et al. Effect of Na₂O on mineral transformation of coal ash under high temperature gasification condition[J]. Journal of Fuel Chemistry and Technology, 2016, 44(3): 263-272.
5	VASSILEV S V, KITANO K, TAKEDAB S, et al. Influence of mineral and chemical composition of coal ashes on their fusibility[J]. Fuel Processing Technology, 1995(45): 27-51.
6	WANG Y, XIANG Y, WANG D X, et al. Effect of sodium oxides in ash composition on ash fusibility[J]. Energy & Fuels, 2016, 30: 1437-1444.
7	ZHAO Y L, ZHANG Y M, BAO S X, et al. Effect of stone coal chemical composition on sintering behavior during roasting[J]. Industrial & Engineering Chemistry Research, 2014, 53: 157-163.
8	王东旭, 陈裕辉, 王洋, 等. MgO含量对高钠煤灰熔融特性的影响[J]. 化工进展, 2018, 37(4): 1392-1401.
	WANG Dongxu, CHEN Yuhui, WANG Yang, et al. Effect of MgO content on the ash fusibility of high sodium coal[J]. Chemical Industry and Engineering Progress, 2018, 37(4): 1392-1401.
9	段锦, 李寒旭, 郝华东, 等. 钙镁复合助熔剂对长平煤灰熔融特性影响研究[J]. 硅酸盐通报, 2016, 35(12): 3936-3941.
	DUAN Jin, LI Hanxu, HAO Huadong, et al. Effect of calcium and magnesium compound flux on Changping coal ash fusibility[J]. Bulletin of the Chinese Ceramic Society, 2016, 35(12): 3936-3941.
10	马志斌, 白宗庆, 白进, 等. 高温弱还原气氛下高硅铝比煤灰变化行为的研究[J]. 燃料化学学报, 2012, 40(3): 279-285.
	MA Zhibin, BAI Zongqing, BAI Jin, et al. Evolution of coal ash with high Si/Al ratio under reducing atmosphere at high temperature[J]. Journal of Fuel Chemistry and Technology, 2012, 40(3): 279-285.
11	RAASK E. Mineral impurities in coal combustion: behavior, problems, and remedial measures[M]. Bristol: Hemisphere Pulishing, 1985: 160-166.
12	XU J, LIU X, ZHAO F, et al. Study on fusibility and flow behavior of high-calcium coal ash[J]. Journal of Chemical Engineering of Japan, 2014, 47(9): 711-716.
13	SONG W J, TANG L H, ZHU X D, et al. Prediction of Chinese coal ash fusion temperatures in Ar and H₂ atmospheres[J]. Energy & Fuels, 2009, 23: 1990-1997.
14	PRONOBIS M. Evaluation of the influence of biomass co-combustion on boiler furnace slagging by means of fusibility correlations[J]. Biomass & Bioenergy, 2005, 28(4): 375-383.
15	郑烨, 马志斌, 关彦军, 等. 煤矸石灰添加对准东煤灰熔融特性影响[J]. 化工进展, 2019, 38(4): 1714-1720.
	ZHENG Ye, MA Zhibin, GUAN Yanjun, et al. Effect of coal gangue ash addition on the fusibility of Zhundong coal ashes[J]. Chemical Industry and Engineering Progress, 2019, 38(4): 1714-1720.
16	王勤辉, 景妮洁, 骆仲泱, 等. 灰成分影响煤灰烧结温度的实验研究[J]. 煤炭学报, 2010, 35(6): 1015-1020.
	WANG Qinhui, JING Nijie, LUO Zhongyang, et al. Experiments on the effect of chemical components of coal ash on the sintering temperature[J]. Journal of China Coal Society, 2010, 35(6): 1015-1020.
17	范建勇，周永刚，李培, 等. 准东煤灰熔融温度表征结渣特性的试验研究[J]. 煤炭学报, 2013, 38(s2): 478-482.
	FAN Jianyong, ZHOU Yonggang, LI Pei, et al. Research on Zhundong coal’s ash melting temperature characterizing its slagging characteristics[J]. Journal of China Coal Society, 2013, 38(s2): 478-482.
18	付子文, 王长安, 车得福, 等. 成灰温度对准东煤灰理化特性影响的实验研究[J]. 工程热物理学报, 2014, 35(3): 609-613.
	FU Ziwen, WANG Changan, CHE Defu, et al. Experimental study on the effect of ashing temperature on physicochemical properties of Zhundong coal ashes[J]. Journal of Engineering Thermophysics, 2014, 35(3): 609-613.
19	王东旭, 祁超, 王洋. 等. CaO含量对高钠煤灰熔融特性的影响[J]. 燃料化学学报, 2017, 45(9): 1025-1034.
	WANG Dongxu, QI Chao, WANG Yang, et al. Effect of CaO content on the ash fusibility of high sodium coal[J]. Journal of Fuel Chemistry and Technology, 2017, 45(9): 1025-1034.
20	LI W D, LI M, LI W F, et al. Study on the ash fusion temperatures of coal and sewage sludge mixtures[J]. Fuel, 2010, 89: 1566-1572.
21	YAN T G, KONG L X, BAI J, et al. Thermo mechanical analysis of coal ash fusion behavior[J]. Chemical Engineering Science, 2016, 147: 74-82.

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碱性氧化物对煤灰熔融特征行为的影响

Effects of basic oxides on ash fusion characteristic of coal ash

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