两步还原钒渣过程中熔渣的黏度与结构特性

孙晓磊; 张灵犀; 陈敏

doi:10.3969/j.issn.1000-6532.2024.05.006

两步还原钒渣过程中熔渣的黏度与结构特性

东北大学　冶金学院，辽宁　沈阳　110819

基金项目: 国家自然科学基金项目（51774073，52174301）

详细信息

作者简介: 孙晓磊（1994-）男，硕士研究生，研究方向为钒渣的综合利用

通讯作者: 陈敏（1969-）男，教授，博士生导师，研究方向为冶金二次资源精细化利用。

中图分类号: TF646

收稿日期: 2022-11-18

刊出日期: 2024-10-25

Evolution of Viscosity and Structure Property during the Two-step Reduction of Vanadium Slags

School of Metallurgy, Northeastern University, Shenyang 110819, Liaoning, China

More Information

Corresponding author: CHEN Min, chenm@smm.neu.edu.cn

Received Date: 18 November 2022

Publish Date: 25 October 2024

摘要

摘要:
这是一篇冶金工程领域的论文。针对当前钒铁生产面临环境污染严重、流程冗长以及能耗较高等一系列问题，拟利用光伏硅片切割废料和铝灰分别作为预还原和终还原阶段的还原剂，对钒渣进行两步还原直接制备钒铁合金，研究了两步还原反应过程中对应渣系的黏度和熔体结构的演变规律。结果表明，1 873 K时，对应预还原过程的FeO-V₂O₃-Cr₂O₃-MnO-SiO₂-TiO₂-CaO渣系，随着渣中FeO组元含量的减少和SiO₂组元含量的增加，铁铬尖晶石逐渐分解，影响熔体结构的主要因素由渣中FeO含量的变化转变为SiO₂含量的变化，导致结构复杂度由0.176增至2.517，相应地，渣系黏度由0.092 Pa·s增至0.476 Pa·s；对应终还原过程的FeO-Cr₂O₃-MnO-V₂O₃-Al₂O₃-SiO₂-TiO₂-CaO渣系，随着渣中FeO、Cr₂O₃、MnO、V₂O₃组元含量的减少和Al₂O₃组元含量的增加，锰铬尖晶石逐渐分解，渣系由固液混合相转变为单一液相，影响熔体结构的主要因素为渣中Al₂O₃含量的变化，渣系由预还原阶段硅酸盐为主的熔体结构转变为终还原阶段铝硅酸盐为主的熔体结构，结构复杂度由0.252增至2.248，相应地，渣系黏度由0.091 Pa·s增至0.372 Pa·s。
- 冶金工程 /
- 两步还原 /
- 钒渣 /
- 黏度 /
- 熔体结构 /
- 结构复杂度
Abstract:
This is an article in the field of metallurgical engineering. At present, the cumbersome product routing of FeV alloy causes high energy consumption and hazardous leaching liquor waste. Therefore, a two-step direct reduction to produce FeV alloy from vanadium slags using photovoltaic silicon wafer cutting waste and aluminum ash as reductant, was investigated to solve the above problems. In the present work, the evolution of viscosity and the melt structure during the two-step reduction process of vanadium slags was investigated. The results showed that at 1 873 K, FeO-V₂O₃-Cr₂O₃-MnO-SiO₂-TiO₂-CaO slag system corresponding to the prereduction process, with the decrease of FeO content and the increase of SiO₂ content in the slags, the size of FeCr₂O₄ spinel decreased gradually. The transition of the main influencing factor of the melt structure from FeO to SiO₂ resulted in the increase of structure complexity, the structural complexity of the slag system increased from 0.176 to 2.517, the viscosity of the slag system increased from 0.092 Pa·s to 0.476 Pa·s. FeO-Cr₂O₃-MnO-V₂O₃-Al₂O₃-SiO₂-TiO₂-CaO slag system corresponding to the final reduction process, with the decrease of FeO, Cr₂O₃, MnO, V₂O₃ content and the increase of Al₂O₃ content in the slag, the size of MnCr₂O₄ spinel decreased gradually and the slag system comprised from a solid-liquid mixture to liquid, the transition of the main influencing factor from SiO₂ to Al₂O₃ resulted in the transformation of the main structure of the slag system from silicate to aluminosilicate, the structural complexity of the slag system increased from 0.252 to 2.248, and the viscosity of the slag system increased from 0.091 Pa·s to 0.372 Pa·s.
- Metallurgical engineering /
- Two-step reduction /
- Vanadium slags /
- Viscosity /
- Melt structure /
- Structural complexity

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图 1 S1～S6在1 873 K时急冷后的XRD

Figure 1.

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图 2 1 873 K时急冷渣样的SEM

Figure 2.

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图 3 不同渣样黏度随温度的变化曲线

Figure 3.

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图 4 急冷渣样的拉曼光谱Gaussian分峰拟合曲线

Figure 4.

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表 1 SCW、铝灰、钒渣的化学成分/%

Table 1. Chemical composition of SCW, aluminium ash and vanadium slags

名称	Al	Al₂O₃	SiO₂	SiC	Si	FeO	Cr₂O₃	MnO	V₂O₃	TiO₂
SCW	-	-	14.9	25.8	59.3	-	-	-	-	-
铝灰	39.3	48.8	11.9	-	-	-	-	-	-	-
钒渣	-	-	19.4	-	-	41.2	4.9	11.1	14.2	9.2

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表 2 实验渣样化学成分/%

Table 2. Chemical composition of test slags

名称	FeO	Cr₂O₃	MnO	V₂O₃	SiO₂	TiO₂	CaO	Al₂O₃
S1	36	5	11	13	18	9	8	-
S2	25	5	11	14	26	9	10	-
S3	11	5	11	16	37	9	11	-
S4	6	3	7	9	23	6	35	11
S5	-	-	7	9	24	6	37	17
S6	-	-	-	-	25	6	37	32

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表 3 渣样各结构单元拉曼特征峰位置

Table 3. Raman characteristic peak position of each structural unit of test slags

名称	S1	S2	S3	S4	S5	S6	结构单元
拉曼位移(cm^-1)	-	-	-	510	540	511	Al-O-Al弯曲振动^[12]
	580	580	575	579	602	567	Si-O-Si弯曲振动^[15]
	-	629	630	-	-	-	FeCr₂O₄中F_2g(3)振动^[16]
	-	-	-	665	-	-	MnCr₂O₄中A_1g振动^[17]
	675	-	-	-	-	-	FeCr₂O₄中A_1g振动^[17]
	710	710	709	710	690	-	V-O₃-V弯曲振动^[18]
	-	-	-	770	762	753	Al-O^-对称伸缩振动^[19]
	-	-	-	-	820	843	Al-O-Si伸缩振动^[20]
	872	851	849	853	861	-	[SiO₄]^4-中Si-O^-对称伸缩振动^[19-20]
	919	906	913	913	907	918	[Si₂O₇]^6-中Si-O^-对称伸缩振动^[19-20]
	951	995	978	1 000	959	991	[SiO₃]^2-中Si-O^-对称伸缩振动^[19-20]
	-	-	1 076	-	-	1 075	[Si₂O₅]^2-中Si-O^-对称伸缩振动^[19-20]

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表 4 渣中复杂结构和简单结构特征峰相对面积 /%

Table 4. Relative areas of characteristic peaks of complex structure and simple structure in test slag system

名称	Si-O-Si+Q²+Q³	Q⁰+Q¹	Al-O-Si	Al-O-Al	Al-O^-	SC
S1	14.94	85.06	-	-	-	0.176
S2	26.70	73.30	-	-	-	0.364
S3	71.57	28.43	-	-	-	2.517
S4	12.30	78.29	0	7.85	1.56	0.252
S5	26.33	35.42	22.21	4.01	12.03	1.108
S6	27.71	26.22	37.60	3.90	4.57	2.248

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