煤矸石/粉煤灰对赤泥钠化还原焙烧反应的影响机制

doi:10.11949/0438-1157.20211588

化工学报 ›› 2022, Vol. 73 ›› Issue (5): 2194-2205.DOI: 10.11949/0438-1157.20211588

煤矸石/粉煤灰对赤泥钠化还原焙烧反应的影响机制

郭志强¹(),燕可洲¹(),张吉元²,柳丹丹²,高阳艳³,郭彦霞¹

^1.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重点实验室，山西太原 030006
^2.太原科技大学环境科学与工程学院，山西太原 030024
^3.山西大学环境与资源学院，山西太原 030006

收稿日期:2021-11-09 修回日期:2022-01-27 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 燕可洲
作者简介:郭志强(1996—)，男，硕士研究生，Gzqczz7@163.com
基金资助:
国家自然科学基金青年基金项目(22008144);山西省重点研发计划项目(201903D311006)

Influence mechanism of coal gangue / coal fly ash on the sodium reduction roasting reaction of red mud

Zhiqiang GUO¹(),Kezhou YAN¹(),Jiyuan ZHANG²,Dandan LIU²,Yangyan GAO³,Yanxia GUO¹

^1.Institute of Resources and Environmental Engineering, State Key Laboratory of Environmental Protection and Efficient Utilization of Coal Wastes, Shanxi University, Taiyuan 030006, Shanxi, China
^2.School of Environmental Science and Engineering, Taiyuan University of Science and Technology, Taiyuan 030024, Shanxi, China
^3.School of Environment and Resources, Shanxi University, Taiyuan 030006, Shanxi, China

Received:2021-11-09 Revised:2022-01-27 Online:2022-05-05 Published:2022-05-24
Contact: Kezhou YAN

摘要/Abstract

摘要：

煤矸石或粉煤灰与赤泥协同钠化还原焙烧均可实现其所含铁、铝、硅等元素的形态转化，使其易于分离回收；但对于它们分别与赤泥协同钠化还原焙烧反应差异性及机制的研究目前尚未见报道。采用X射线衍射分析方法，分别考察了煤矸石-赤泥、粉煤灰-赤泥体系钠化还原焙烧过程中，气氛类型、钠助剂添加量、焙烧温度、焙烧时间对还原焙烧产物物相组成的影响规律，并对两个反应体系中铁磁化效果及铝硅活化效果的差异性进行分析。结果表明：在钠化还原焙烧过程中，煤矸石-赤泥、粉煤灰-赤泥体系均可同步实现含铁物相的磁化和铝硅物相的活化，且随着钠助剂添加量、焙烧温度、焙烧时间的变化，含铁物相和铝硅物相呈现规律性变化；在相同铁磁化和铝硅活化效果前提下，煤矸石-赤泥体系所需钠助剂添加量、焙烧温度和焙烧时间均略低于粉煤灰-赤泥体系，这主要与煤矸石、粉煤灰中所含还原性物质和铝硅矿物的赋存形态、含量及微观结构有关。研究将为煤矸石、粉煤灰等煤基固废与赤泥协同钠化还原焙烧回收有价元素的原料筛选提供理论指导。

关键词: 烧结, 活化, 还原, 废物处理

Abstract:

Coal gangue or fly ash and red mud synergistic sodium reduction roasting can realize the form transformation of iron, aluminum, silicon and other elements contained in it, making it easy to separate and recycle. However, a research on the difference of sodium reduction roasting reaction between coal gangue - red mud system and coal fly ash-red mud system has not been reported. In this paper, the influence of atmosphere type, sodium additive amount, roasting temperature and roasting time on the phase composition of the reductive roasted product from coal gangue-red mud and coal fly ash-red mud system was investigated by X-ray diffraction analysis method. In addition, the difference of iron magnetization and aluminum-silicon activation between coal gangue-red mud and coal fly ash-red mud system was analyzed. The results showed that coal gangue-red mud and coal fly ash-red mud systems can simultaneously realize the magnetization of iron-containing phase and the activation of aluminum-silicon phase during the sodium reduction roasting process. The iron-containing phase and the aluminum-silicon phase showed regular changes with the change of sodium additive amount, roasting temperature and roasting time. The sodium additive amount, roasting temperature and roasting time for the coal gangue-red mud system were slightly lower than those for the coal fly ash-red mud system with the same degree of iron magnetization and aluminum-silicon activation. It is mainly related to the occurrence, content and microstructure of reducing substances and aluminosilicate minerals in coal gangue or coal fly ash. This study will provide a theoretical guidance for the feed selecting during the recovery of valuable elements by sodium reduction roasting of coal-based solid wastes (such as coal gangue, coal fly ash) and red mud.

Key words: sintering, activation, reduction, waste treatment

中图分类号:

TQ 170.9

郭志强, 燕可洲, 张吉元, 柳丹丹, 高阳艳, 郭彦霞. 煤矸石/粉煤灰对赤泥钠化还原焙烧反应的影响机制[J]. 化工学报, 2022, 73(5): 2194-2205.

Zhiqiang GUO, Kezhou YAN, Jiyuan ZHANG, Dandan LIU, Yangyan GAO, Yanxia GUO. Influence mechanism of coal gangue / coal fly ash on the sodium reduction roasting reaction of red mud[J]. CIESC Journal, 2022, 73(5): 2194-2205.

图/表 20

表1 煤矸石、粉煤灰和赤泥主要化学组成

Table 1 Chemical compositions of coal gangue， coal fly ash and red mud

物质	Al₂O₃/%	SiO₂/%	CaO/%	Na₂O/%	Fe₂O₃/%	TiO₂/%	MgO/%	K₂O/%	LOI/%	Al/Si
煤矸石	21.06	41.36	0.95	0.43	2.52	0.77	0.50	2.00	23.4	0.61
粉煤灰	29.90	44.40	2.72	0.86	2.67	1.25	0.45	1.50	15.79	0.79
赤泥	27.40	22.40	19.40	9.89	7.81	3.95	0.92	0.81	7.42	1.43

图1 煤矸石、粉煤灰和赤泥的XRD谱图1—石英(SiO2); 2—高岭石(Al2[Si2O5](OH)4); 3—莫来石(Al6Si2O13); 4—方钠石(Na8Al6O12(OH)2(H2O)2); 5—水化石榴石(Ca3Al2(SiO4)(OH)8); 6—潘诺霞石((K,Na)AlSiO4); 7—钠霞石(NaAlSiO4); 8—赤铁矿(Fe2O3)

Fig.1 XRD patterns of coal gangue, coal fly ash and red mud

图2 不同气氛下CG-RM和CFA-RM体系钠化焙烧产物的XRD谱图(实验条件:Na∶Al∶Si=1.2∶1∶1,焙烧温度850℃,焙烧时间 120 min)△ 霞石(NaAlSiO4); ▲ 钠铝硅酸盐(Na6Al4Si4O17); □ 赤铁矿(Fe2O3); ■ 铁(Fe)

Fig.2 XRD patterns of the sodium roasting products of CG-RM and CFA-RM systems in different atmosphere

图3 不同钠助剂添加量下CG-RM和CFA-RM体系钠化还原焙烧产物的XRD谱图(实验条件:焙烧气氛 N2,焙烧温度 850°C,焙烧时间 120 min)△ 霞石(NaAlSiO4); ▲ 钠铝硅酸盐(Na6Al4Si4O17); ■ 铁(Fe)

Fig.3 XRD patterns of the sodium reduction roasting products of CG-RM and CFA-RM systems with different amount of sodium additive

图4 不同钠助剂添加量下CG-RM和CFA-RM体系钠化还原焙烧产物中活性相与磁性相的相对含量

Fig.4 Relative contents of active phase and magnetic phase in the sodium reduction roasting products of CG-RM and CFA-RM systems with different amount of sodium additives

图5 不同温度下CG-RM和CFA-RM体系钠化还原焙烧产物的XRD谱图(实验条件:焙烧气氛 N2,Na∶Al∶Si=1.2∶1∶1,焙烧时间 120 min)△ 霞石(NaAlSiO4); ▲ 钠铝硅酸盐(Na6Al4Si4O17); ■ 铁(Fe)

Fig.5 XRD patterns of the sodium reduction roasting products of CG-RM and CFA-RM systems in different temperature

图6 不同温度下CG-RM和CFA-RM体系钠化还原焙烧产物中活性相与磁性相的相对含量

Fig.6 Relative contents of active phase and magnetic phase in the sodium reduction roasting products of CG-RM and CFA-RM systems in different temperature

图7 不同时间下CG-RM和CFA-RM体系钠化还原焙烧产物的XRD谱图(实验条件:焙烧气氛 N2,Na∶Al∶Si=1.2∶1∶1,焙烧温度850°C)△ 霞石(NaAlSiO4);▲ 钠铝硅酸盐(Na6Al4Si4O17); ■ 铁(Fe)

Fig.7 XRD patterns of the sodium reduction roasting products of CG-RM and CFA-RM systems at different time

图8 不同时间下CG-RM和CFA-RM体系钠化还原焙烧产物中活性相与磁性相的相对含量

Fig.8 Relative contents of active phase and magnetic phase in the sodium reduction roasting products of CG-RM and CFA-RM systems at different time

表2 煤矸石-赤泥和粉煤灰-赤泥体系钠化还原焙烧优化实验条件差异

Table 2 Difference of optimum experimental conditions for sodium reduction roasting of coal gangue-red mud and coal fly ash-red mud systems

体系	钠铝硅比(mol)	温度/℃	时间/min
煤矸石-赤泥-碳酸钠	1.2∶1∶1	800	90
粉煤灰-赤泥-碳酸钠	1.5∶1∶1	850	150

表3 煤矸石和粉煤灰工业成分测试

Table 3 Industrial composition test of coal gangue and coal fly ash

物质	水分/%	灰分/%	挥发分/%	固定碳/%
煤矸石	0.53	75.46	9.07	14.94
粉煤灰	0.17	88.81	1.66	9.36

图9 煤矸石（a）和粉煤灰（b）的拉曼光谱图

Fig.9 Raman spectra of coal gangue (a) and coal fly ash (b)

图10 煤矸石（a）和粉煤灰（b）热重图

Fig.10 Thermogravimetric diagram of coal gangue (a) and coal fly ash (b)

图11 高岭石（a）和莫来石（b）晶体结构

Fig.11 Crystal structure of kaolinite（a）and mullite（b）

表4 高岭石和莫来石晶体结构基本参数

Table 4 Basic crystal structure parameters of kaolinite and mullite

a : 5.148 ?

b : 8.920 ?

c : 14.535 ?

α : 90.000°

β : 100.200°

γ : 90.000°

a : 7.430 ?

b : 7.580 ?

c : 5.740 ?

α : 90.000°

β : 90.000°

γ : 90.000°

图12 煤矸石、粉煤灰的实测XRD谱图与高岭石、莫来石的模拟XRD谱图

Fig.12 Measured XRD patterns of coal gangue and fly ash and simulated XRD patterns of kaolinite and mullite

图13 高岭石和莫来石能带结构

Fig.13 Energy band structure of kaolinite and mullite

图14 高岭石（a）和莫来石（b）的总态密度

Fig.14 Density of state of kaolinite (a) and mullite (b)

图15 高岭石和莫来石中Al、Si、O原子的分态密度

Fig.15 Density of states of Al, Si and O atoms in kaolinite and mullite

表5 高岭石和莫来石的平均键长和重叠布局数

Table 5 Average bond length and overlap number of kaolinite and mullite

矿物	键类型	键长/nm	重叠布局数
高岭石	Si—O	1.628	0.535
高岭石	Al—O	2.420	0.0287
莫来石	Si—O	1.624	0.588
莫来石	Al—O	1.837	0.368

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煤矸石/粉煤灰对赤泥钠化还原焙烧反应的影响机制

Influence mechanism of coal gangue / coal fly ash on the sodium reduction roasting reaction of red mud

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