气氛和化学组成对高铁煤灰熔融特性的影响机理

doi:10.11949/0438-1157.20220770

化工学报 ›› 2022, Vol. 73 ›› Issue (10): 4648-4658.DOI: 10.11949/0438-1157.20220770

气氛和化学组成对高铁煤灰熔融特性的影响机理

贺冲¹(), 白进², 郭晶³, 孔令学², 鲁浩², 李怀柱², 秦育红¹, 李文²

^1.太原理工大学环境科学与工程学院，山西晋中 030600
^2.中国科学院山西煤炭化学研究所煤转化国家重点实验室，山西太原 030001
^3.太原理工大学安全与应急管理工程学院，山西太原 030024

收稿日期:2022-06-01 修回日期:2022-07-22 出版日期:2022-10-05 发布日期:2022-11-02
通讯作者: 贺冲
作者简介:贺冲（1989—），男，博士，讲师，hechong@tyut.edu.cn
基金资助:
国家自然科学基金项目(22108190)

Effects of atmosphere and chemical composition on fusion characteristics of high-iron coal ash

Chong HE¹(), Jin BAI², Jing GUO³, Lingxue KONG², Hao LU², Huaizhu LI², Yuhong QIN¹, Wen LI²

^1.College of Environmental Science and Engineering, Taiyuan University of Technology, Jinzhong 030600, Shanxi, China
^2.State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^3.College of Safety and Emergency Management Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2022-06-01 Revised:2022-07-22 Online:2022-10-05 Published:2022-11-02
Contact: Chong HE

摘要/Abstract

摘要：

采用灰熔点仪、XRD和热力学模拟，研究气氛和化学组成对高铁煤灰熔融特性的影响机理。研究结果表明，灰熔融温度随铁含量、钙含量或硅铝比增加而降低。弱还原气氛下低钙或低硅铝比煤灰熔融存在明显的初始熔融阶段，熔融过程遵循“软化-熔融”机理，而空气气氛下高钙或高硅铝比煤灰熔融过程属于“熔融-溶解”机理。弱还原气氛下铁含量增加显著促进石英和钙长石熔融，空气气氛下钙含量增加促进刚玉和石英熔融或转化为钙基硅铝盐。弱还原气氛下液相含量随硅铝比或铁含量增加而增加，液相黏度随钙含量或铁含量增加而降低，促进熔融传质；空气气氛下低钙或低硅铝比煤灰中铁存在于含铁固溶体，导致液相黏度高或液相含量低，熔融传质受阻。

关键词: 煤灰, 气化, 熔融特性, 结晶, 相变, 化学组成, 气氛

Abstract:

Using ash melting point apparatus, XRD and thermodynamic simulation, the influence mechanism of atmosphere and chemical composition on the melting characteristics of high-speed iron coal ash was studied. The results indicate that the fusion temperature of high-iron coal ash decreases with the increasing iron content, or calcium content, or S/A (the mass ratio of SiO₂ to Al₂O₃). Further, the fusion behavior of high calcium or high S/A and high-iron ash under mild reducing atmosphere (MR) follows the “melting-dissolution” mechanism due to the existence of the initial melting stage, while the fusion of low calcium or low S/A and high-iron ash under air belongs to the “softening-melting” mechanism. The iron accelerates the melting of quartz and anorthite under MR, and the calcium promotes the melting of quartz and corundum or transformations of these minerals to the calcium-based aluminosilicates. Under MR, the liquid content increases with the iron content or S/A, and the liquid viscosity decreases with the increasing calcium content or iron content, improving the mass transfer. In contrast, the crystallization of iron-containing solid solutions which were found in the low-calcium or low S/A and high iron ash leads to a higher liquid viscosity or lower liquid content under air, inhibiting the mass transfer of ash melting.

Key words: coal ash, gasification, fusion characteristic, crystallization, phase change, chemical composition, atmosphere

中图分类号:

TQ 54

贺冲, 白进, 郭晶, 孔令学, 鲁浩, 李怀柱, 秦育红, 李文. 气氛和化学组成对高铁煤灰熔融特性的影响机理[J]. 化工学报, 2022, 73(10): 4648-4658.

Chong HE, Jin BAI, Jing GUO, Lingxue KONG, Hao LU, Huaizhu LI, Yuhong QIN, Wen LI. Effects of atmosphere and chemical composition on fusion characteristics of high-iron coal ash[J]. CIESC Journal, 2022, 73(10): 4648-4658.

图/表 8

表1 兖州煤灰的化学组成

Table 1 Chemical composition of YZ coal ash

组成	含量/%
SiO₂	35.17
Al₂O₃	19.16
Fe₂O₃	16.31
CaO	18.04
MgO	1.83
Na₂O	0.51
K₂O	0.31
SO₃	8.05
TiO₂	0.61

表2 高铁模拟灰的化学组成

Table 2 Chemical composition of high-iron synthetic ash

样品	含量/%
样品	SiO₂	Al₂O₃	Fe₂O₃	CaO
YZ	39.61	21.64	18.39	20.36
不同铁含量的煤灰
F5	46.11	25.19	5.00	23.70
F10	43.68	23.86	10.00	22.45
F15	41.26	22.54	15.00	21.21
F20	38.83	21.21	20.00	19.96
F25	36.40	19.89	25.00	18.71
不同钙含量的高铁煤灰
Ca5	49.54	27.07	18.39	5.00
Ca15	43.08	23.53	18.39	15.00
Ca25	36.61	20.00	18.39	25.00
Ca35	30.14	16.47	18.39	35.00
不同硅铝比的高铁煤灰
SA1	30.63	30.63	18.39	20.36
SA2	40.83	20.42	18.39	20.36
SA3	45.94	15.31	18.39	20.36
SA4	49.00	12.25	18.39	20.36

图1 气氛和化学组成对煤灰熔融温度的影响

Fig.1 Effects of atmosphere and chemical composition on the flow temperature of coal ash

图2 不同气氛下高铁煤灰的熔融过程

Fig.2 Fusion process of high-iron coal ash under different atmospheres

图3 灰样在1200℃的XRD谱图1—刚玉(Al2O3); 2—钙长石(CaAl2Si2O8); 3—赤铁矿(Fe2O3); 4—方石英(SiO2); 5—石英(SiO2); 6—硅灰石(CaSiO3); 7—假硅灰石(Ca3Si3O9);8—黄长石(Ca2Al2SiO7); 9—硅酸二钙(Ca2SiO4); 10—橄榄石(Fe2SiO4); 11—斜硅钙石(Ca2SiO4); 12—硅酸铁(Fe2SiO4)

Fig.3 XRD patterns of ash at 1200℃1—corundum (Al2O3);2—anorthite (CaAl2Si2O8);3—hematite (Fe2O3); 4—cristobalite (SiO2); 5—quartz (SiO2); 6—wollastonite (CaSiO3); 7—pseudowollastonite (Ca3Si3O9); 8—gehlenite (Ca2Al2SiO7); 9—calcium silicate (Ca2SiO4); 10—fayalite (Fe2SiO4); 11—larnite (Ca2SiO4);12—iron silicate (Fe2SiO4)

图4 1350℃铁含量对高温灰渣物相组成、铁分布及液相黏度的影响

Fig.4 Effect of Fe2O3 content on phase composition [(a) MR; (b) air], iron distribution (c), and slag viscosity (d) at 1350℃

图5 1350℃钙含量对高温灰渣物相组成、铁分布及液相黏度的影响

Fig.5 Effect of CaO content on phase composition [(a) MR; (b) air], iron distribution (c), and slag viscosity (d) at 1350℃

图6 1350℃硅铝比对高温灰渣物相组成、铁分布及液相黏度的影响

Fig.6 Effect of S/A on phase composition [(a) MR; (b) air], iron distribution (c), and slag viscosity (d) at 1350℃

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气氛和化学组成对高铁煤灰熔融特性的影响机理

Effects of atmosphere and chemical composition on fusion characteristics of high-iron coal ash

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