高铬型钒钛铁精矿球团氧化焙烧-盐酸浸出提钒

吴恩辉; 李军; 徐众; 侯静; 黄平; 李宏

doi:10.7513/j.issn.1004-7638.2022.06.003

高铬型钒钛铁精矿球团氧化焙烧-盐酸浸出提钒

doi: 10.7513/j.issn.1004-7638.2022.06.003

吴恩辉^{1, 2, ,},
李军^{1, 2},
徐众^{1, 2},
侯静^{1, 2},
黄平^{1, 2},
李宏^{1, 2}

1.
攀枝花学院钒钛学院, 四川攀枝花 617000
2.
钒钛资源综合利用四川省重点实验室, 四川攀枝花 617000

基金项目: 四川省科技计划项目资助（2020YFH0195）；攀枝花市科技计划项目资助（2021CY-G-4）。

详细信息

作者简介:
吴恩辉，1984年出生，男，安徽泗县人，博士，副教授，通讯作者，研究方向为钒钛磁铁矿综合利用，E-mail：wuenhui1026@126.com

通讯作者:
吴恩辉，1984年出生，男，安徽泗县人，博士，副教授，通讯作者，研究方向为钒钛磁铁矿综合利用，E-mail：wuenhui1026@126.com

中图分类号: TF841.3
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出版历程
- 收稿日期: 2022-09-26
- 刊出日期: 2023-01-13

Extraction of vanadium from high-chromium vanadium-bearing titanomagnetite pellets by oxidation roasting-HCl leaching process

Wu Enhui^{1, 2
, ,},
Li Jun^{1, 2},
Xu Zhong^{1, 2},
Hou Jing^{1, 2},
Huang Ping^{1, 2},
Li Hong^{1, 2}

1.
College of Vanadium and Titanium, Panzhihua University, Panzhihua 617000, Sichuan, China
2.
Vanadium and Titanium Resources Comprehensive Utilization Key Laboratory of Sichuan Province, Panzhihua 617000, Sichuan, China

摘要

摘要: 以高铬型钒钛铁精矿为原料，研究其在氧化焙烧-盐酸浸出过程中球团强度与钒浸出行为之间的相互关系。热力学分析结果表明，在氧化钙存在的条件下，高铬型钒钛铁精矿中主要化合物的氧化反应顺序依次为：FeTiO₃>Fe₃O₄>Fe₂SiO₄>FeV₂O₄>FeCr₂O₄。氧化产物物相分析结果证实，钛铁矿比磁铁矿更易氧化，氧化产物的主要物相为Fe₂O₃和Fe₉TiO₁₅。氧化温度和盐酸浓度分别是氧化过程和浸出过程中影响钒浸出率和浸出后球团强度的关键因素；浸出后球团强度与V₂O₅浸出率呈现较为明显的负相关关系；返烧可以有效提升浸出后球团强度，在返烧温度1200 ℃，返烧时间90 min条件下，返烧后球团强度大于3 000 N/球。
- 提钒 /
- 高铬型钒钛铁精矿 /
- 球团 /
- 氧化焙烧 /
- 盐酸 /
- 浸出
Abstract: The relationship between crushing strength of pellets and leaching behaviors of vanadium in oxidation roasting-HCl leaching process from high-chromium vanadium-bearing titanomagnetite concentrates were investigated in this work. The results of the thermodynamic analysis of oxidizing roasting process show that the order of reaction of main compounds is: FeTiO₃>Fe₃O₄>Fe₂SiO₄>FeV₂O₄>FeCr₂O₄. The phase analysis results of oxidation roasting process show that the oxidation reaction of the ilmenite is easier to magnetite, and the main phases of oxidation pellets are Fe₂O₃ and Fe₉TiO₁₅. Experimental results indicate that the oxidation temperature and HCl concentration are the key factors affecting the leaching efficiency of vanadium and the crushing strength of leached pellets in the oxidation process and leaching process respectively. There is an obvious negative correlation between the leaching efficiency of vanadium and the crushing strength of leached pellets. The crushing strength of leached pellets can be effectively increased by return roasting process. The crushing strength of pellets after return roasting is greater than 3 000 N/pellet under the condition of roasting temperature of 1 200 ℃ for 90 min, which can be used as raw materials for blast furnace ironmaking.
- extraction vanadium /
- high-chromium vanadium-bearing titanomagnetite concentrates /
- pellet /
- oxidation roasting /
- hydrochloric acid /
- leaching

HTML全文

图 1 高铬型钒钛铁精矿的微观形貌

Figure 1. Microstructure of high-chromium vanadium-bearing titanomagnetite concentrates

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图 2 体系内反应自由能与温度的关系

Figure 2. Gibbs free energies of reactions in the system as functions of temperature

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图 3 氧化温度对焙烧产物物相组成的影响

Figure 3. XRD patterns of samples roasted at different oxidizing temperature

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图 4 氧化时间对产物物相组成的影响

Figure 4. XRD patterns of samples roasted with varying oxidizing time

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图 5 氧化球团中钒和铁的XPS图谱

Figure 5. XPS spectra of V and Fe for oxidized pellets

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图 6 氧化工艺参数对氧化球团强度的影响

Figure 6. Effect of oxidation process parameters on the strength of oxidized pellets

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图 7 氧化工艺参数对钒浸出率和浸出后球团强度的影响

Figure 7. Effect of oxidation process parameters on the leaching efficiency of vanadium and crushing strength of leached pellets

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图 8 浸出工艺参数对钒浸出率和浸出后球团强度的影响

Figure 8. Effect of leaching process parameters on the leaching efficiency of vanadium and crushing strength of leached pellets

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图 9 浸出时间对钒浸出率和浸出后球团强度的影响

Figure 9. Effect of leaching time on the leaching efficiency of vanadium and crushing strength of leached pellets

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图 10 盐酸浓度对钒浸出率和浸出后球团强度的影响

Figure 10. Effect of hydrochloric acid concentration on the leaching efficiency of vanadium and crushing strength of leached pellets

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图 11 返烧温度对球团强度的影响

Figure 11. Effect of return roasting temperature on the crushing strength of pellets

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图 12 钒浸出率与浸出后球团强度的相关性

Figure 12. Relationship between the leaching efficiency of vanadium and crushing strength of leached pellets

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图 13 反应过程示意

Figure 13. The diagrammatic drawing of reaction process

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表 1 高铬型钒钛铁精矿的主要化学成分

Table 1. Main chemical composition of high chromium-bearing vanadium titanomagnetite concentrates %

Fe₃O₄	FeO	TiO₂	V₂O₅	Cr₂O₃	MgO	Al₂O₃	SiO₂	CaO	SO₃	MnO
58.61	9.93	11.03	0.69	0.67	7.57	3.79	5.46	0.69	1.02	0.25

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表 2 高铬型钒钛铁精矿的粒度组成

Table 2. Size distribution of high chromium-bearing vanadium titanomagnetite concentrates

粒度/μm	占比/%
<45	14.9
45～75	53.8
75～125	23.2
>125	8.1

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表 3 氧化焙烧条件对氧化球团强度、浸出球团强度和钒浸出的影响正交试验

Table 3. Orthogonal test on effect of oxidizing roasting conditions on CS of oxidized pellets, CS of leached pellets and leaching efficiency of V₂O₅

	序号	氧化温度/ ℃	氧化时间/ h	Ca(OH)₂添加量/ %	膨润土添加量/ %	氧化球团抗压强度/(N.球⁻¹)	浸出球团抗压强度/(N.球⁻¹)	V₂O₅浸出率/%
	1	1200	1	1	1.5	3707.7	3084.1	17.13
	2	1200	2	1.5	0.75	2772.8	3477.0	12.19
	3	1200	3	2	0	2720.5	677.2	36.17
	4	1100	1	1.5	0	555.8	225.6	37.15
	5	1100	2	2	1.5	1404.7	431.1	44.24
	6	1100	3	1	0.75	1140.2	305.3	43.12
	7	1000	1	2	0.75	325.6	127.2	34.00
	8	1000	2	1	0	300.4	195.8	48.00
	9	1000	3	1.5	1.5	322.8	183.0	34.26
氧化球团抗压强度	K1	3067.0	1529.7	1716.1	1811.7
	K2	1033.6	1492.6	1217.1	1412.9
	K3	316.3	1394.5	1483.6	1192.2
	极差 R	2750.7	135.2	499.0	619.5
浸出球团抗压强度	K1	2412.8	1145.6	1195.1	1232.7
	K2	320.7	1368.0	1295.2	1303.2
	K3	168.7	388.5	411.8	366.2
	极差 R	2244.1	979.5	883.4	937.0
V₂O₅浸出率	K1	21.83	29.43	36.09	31.88
	K2	41.50	34.81	27.87	29.77
	K3	38.75	37.85	38.14	40.44
	极差 R	19.67	8.42	10.27	10.67

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表 4 浸出条件对浸出球团强度和钒浸出的影响正交试验

Table 4. Orthogonal test on effect of leaching conditions on CS of leached pellets and leaching efficiency of V₂O₅

	序号	浸出温度/ ℃	浸出时间/ d	液固比	盐酸浓度 /(mol·L⁻¹)	浸出球团抗压强度/ (N·球⁻¹)	V₂O₅ 浸出率/%
	1	30	21	9	0.1	2466.1	19.85
	2	30	14	6	0.5	828.8	46.73
	3	30	7	3	0.9	966.2	19.97
	4	50	21	6	0.9	815.3	48.75
	5	50	14	3	0.1	2500.0	0.81
	6	50	7	9	0.5	614.6	27.06
	7	70	21	3	0.5	966.3	23.73
	8	70	14	9	0.9	912.6	33.45
	9	70	7	6	0.1	1975.7	7.78
浸出球团抗压强度	K1	1420.4	1185.5	1331.1	2313.9
	K2	1310.0	1413.8	1206.6	803.2
	K3	1284.9	1415.9	1477.5	898.0
	极差 R	135.5	230.4	270.9	1510.7
V₂O₅ 浸出率	K1	28.85	30.78	26.78	9.48
	K2	25.54	26.99	34.42	32.50
	K3	21.65	18.27	14.84	34.06
	极差 R	7.20	12.51	19.58	24.58

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