钙法提钒尾渣的绿色资源化利用

何为; 王建; 戈文荪; 陈炼

doi:10.7513/j.issn.1004-7638.2022.06.015

钙法提钒尾渣的绿色资源化利用

doi: 10.7513/j.issn.1004-7638.2022.06.015

攀钢集团研究院有限公司, 钒钛资源综合利用国家重点实验室, 四川攀枝花 617000

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中图分类号: X757
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出版历程
- 收稿日期: 2022-03-01
- 刊出日期: 2023-01-13

Clean, high efficiency and green utilization of vanadium tailings extracted by calcium process

Pangang Group Research Institute Co., Ltd., State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, Panzhihua 617000, Sichuan, China

摘要

摘要: 以钙法提钒尾渣为研究对象，通过对尾渣成分、物相和主要元素赋存状态的分析,在结合前人研究的基础上,提出了钙法提钒尾渣通过物理法和火法冶金分离技术制取含钒铁合金及含钛炉渣的综合利用途径。研究表明：提钒尾渣经摇床脱硫处理后，分离出石膏渣和含钒富铁料，石膏渣供水泥厂使用，含钒富铁料配加一定比例的还原剂、粘接剂成球后，在矿热炉进行熔分还原冶炼，可获得钒含量3%左右的含钒铁合金及TiO₂含量36%左右的还原渣，含钒铁合金可用于含钒钢水合金化；还原渣可用于高钛渣冶炼。能实现钙法提钒尾渣中的有价元素铁、钒、钛等有效提取与回收以及减轻环保压力。
- 钙法提钒尾渣 /
- 摇床脱硫 /
- 矿热炉冶炼 /
- 含钒铁合金 /
- 还原渣 /
- 含钒钢水合金化
Abstract: Calcium extraction of vanadium tailings was taken as research object, the composition, phase and occurrence state of main elements of the tailings were analyzed. On the basis of combining previous studies, the comprehensive utilization of vanadium-bearing alloy and titanium-bearing furnace slag from calcium-based vanadium extraction tailings by physical method and pyrometallurgical separation technology is put forward. Studies have shown that after the removal of vanadium tailings by shaking desulfurization treatment, gypsum residue and iron-rich vanadium material were separated, gypsum residue is used in cement plants. V/Fe-rich material with a certain proportion of reducing agent and adhesive mixed press into pellets, smelting by ore-thermal furnace smelting reduction, ferroalloys with a vanadium content of about 3% and reduction slag containing about 36% TiO₂ were obtained, V-containing ferroalloys can be used for alloying V-containing molten steel, and reduced slag can be used for smelting high titanium slag. It can be exploited for effective extraction and recovery of valuable elements such as Fe, V and Ti from calcium-based extraction of vanadium tailings and can reduce the environmental pollution.
- calcium extraction of vanadium tailings /
- shaking desulfurization /
- ore-thermal furnace smelting /
- vanadium-containing ferroalloys /
- reduction slag /
- vanadium-containing molten steel alloying

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图 1 钙法提钒尾渣物相显微镜下识别

Figure 1. Identification of phase of vanadinmtailings extracted by calcium method under microscope

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图 2 含钒富铁料成球工艺流程

Figure 2. Process flow chart of vanadium-rich iron material balling

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图 3 (V₂O₅)、[V]与还原时间的关系

Figure 3. Relationship between (V₂O₅), [V] and reduction time

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图 4 提钒尾渣中氧化物的碳还原∆G⁰-T关系

Figure 4. Carbon reduction ∆G⁰-T of oxides in vanadium extraction tailings

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图 5 含钒铁合金温度截面

Figure 5. Ferroalloy temperature cross section

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图 6 1600 ℃时CaO-SiO₂-Al₂O₃-MgO-TiO₂渣系等温截面

Figure 6. Isothermal section of CaO-SiO₂-Al₂O₃-MgO-TiO₂slag system at 1600 ℃

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图 7 含钒富铁料球团矿热炉冶炼工艺流程

Figure 7. Smelting process of vanadium-rich iron pellet in arc furnace

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图 8 矿热炉熔炼过程中炉渣成分变化

Figure 8. Composition change of slag during the smelting process of ore-thermal electric furnace

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图 9 [C]含量对[V]含量的影响关系

Figure 9. Influence of [C] content on [V] content

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图 10 [C]含量对[Si]、[Ti]含量的影响关系

Figure 10. Influence of [C] content on [Si] and [Ti] content

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图 11 还原渣中FeO与含钒生铁[V]的关系

Figure 11. Relationship of reducing slag FeO and [V]

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图 12 还原渣中V₂O₅与FeO的关系

Figure 12. Relationship of reducing slag FeO and V₂O₅

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表 1 提钒尾渣主要化学成分

Table 1. Main chemical composition of vanadium extraction tailings %

TV	TFe	SiO₂	CaO	MnO	S	P	TiO₂	H₂O
0.8～1.4	20～35	10～15	4～10	3～7	1.0～2.5	0.04～0.06	7～11.0	20～35

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表 2 钙法提钒尾渣中主要元素的赋存状态

Table 2. Occurrence state of main elements in vanadium tailings extracted by calcium method %

矿物质	Al	Ca	Cr	Fe	K	Mg	Mn	Mo	Na	P	S	Si	Ti	V
铁（镁）氧化物	26.07	11.41	5.01	41.53	0.00	32.74	4.83	100.00	83.46	0.00	4.92	9.05	58.47	30.57
钛（铁）氧化物	0.15	0.03	0.00	0.10	0.00	0.24	0.00	0.00	0.00	0.00	0.00	0.03	0.56	0.07
铝（铁）氧化物	1.84	0.06	0.00	0.04	0.00	0.53	0.14	0.00	0.00	0.00	0.00	0.06	0.01	0.01
铁	0.00	0.00	0.00	0.86	0.00	0.00	0.44	0.00	0.00	0.00	0.00	0.00	0.06	0.12
硅酸钙（钒-镁）	11.65	31.66	0.00	1.61	3.21	22.27	18.91	0.00	0.00	70.38	12.21	16.70	4.45	36.06
铁（钛）硅酸盐	55.18	25.46	94.97	54.84	79.73	18.19	73.05	0.00	12.18	0.00	28.46	53.17	34.42	29.19
铝硅酸盐	3.83	0.72	0.02	0.21	7.05	1.35	0.41	0.00	0.87	0.00	0.00	1.91	0.07	0.20
镁硅酸盐	0.99	2.01	0.00	0.13	0.00	24.35	0.41	0.00	0.00	0.00	0.00	8.55	1.69	2.77
硫酸钙（铁）	0.00	27.48	0.00	0.58	10.02	0.00	1.42	0.00	3.49	0.00	54.31	0.51	0.20	0.00
钒酸铁	0.24	0.09	0.00	0.10	0.00	0.24	0.10	0.00	0.00	29.62	0.00	0.06	0.00	0.94
石英	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	0.00	9.92	0.00	0.00
氧化钙	0.05	1.08	0.00	0.00	0.00	0.10	0.29	0.00	0.00	0.00	0.09	0.02	0.07	0.07
总计	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00	100.00

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表 3 提钒尾渣粒度及硫含量分布

Table 3. Particle size and sulfur content distribution of tailings

粒级/mm	重量/g	产率/%	硫含量/%	分布率/%
≥0.3	40	0.75	0.323	0.21
−0.3～+0.15	570	10.71	0.234	2.15
−0.15～+0.074	945	17.75	0.082	1.25
−0.074～+0.052	350.4	6.58	0.145	0.82
−0.052～+0.037	654.5	12.30	0.088	0.93
−0.037～+0.019	1355.3	25.46	0.087	1.90
−0.019～+0.01	762.6	14.33	0.117	1.44
<0.01	645.3	12.12	8.78	91.31
合计	5323.1	100	1.17	100

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表 4 刻槽摇床脱硫效果

Table 4. Desulfurization effect of slotting and shaking table

编号	产率/ %	硫品位/ %	硫回收率/ %
给矿	100	1.17	100
刻槽-1	19.93	0.038	2.92
刻槽-2	23.53	0.045	3.43
刻槽-3	26.17	0.102	9.16
刻槽-4	20.02	1.054	47.16
刻槽-5	10.35	1.519	37.32

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表 5 含钒富铁料主要化学成分

Table 5. Main chemical compositions of vanadium-rich iron material %

	TV	TFe	SiO₂	CaO	MnO	Al₂O₃	TiO₂	S	P
范围	1.39～1.61	37～41.8	13.34～14.6	2.2～2.9	1.52～1.62	2.1～2.38	11.98～ 13.06	0.2～ 0.3	0.047～ 0.053
平均值	1.43	40.8	13.76	2.45	1.58	2.2	12.35	0.28	0.049

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表 6 含钒富铁料球团主要化学成分

Table 6. Main chemical composition of vanadium-rich iron pellet %

	TFe	MFe	V₂O₅	TiO₂	CaO	SiO₂	MnO	Al₂O₃	S	P
范围	32.36～ 38.65	<0.5	2.08～ 2.67	9.87～ 11.34	3.62～ 6.14	10.22～ 13.28	1.04～ 1.73	2.08～ 3.12	0.22～ 0.31	0.038～ 0.052
平均	35.62	<0.5	2.22	10.23	4.15	11.07	1.16	2.78	0.26	0.047

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表 7 含钒铁合金主要成分

Table 7. Main components of alloy %

	C	V	Si	Mn	Ti	S	P
范围	3.09～ 5.39	2.15～3.54	0.56～1.24	1.52～1.89	0.63～2.51	0.037～ 0.056	0.052～0.084
平均值	4.31	3.05	0.84	1.73	1.32	0.048	0.072

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表 8 高钛还原渣主要成分

Table 8. Main components of reducing slag %

组元	V₂O₅	CaO	FeO	MgO	MnO	TFe	SiO₂	TiO₂	Al₂O₃
范围	0.13～0.50	19.19～35.21	0.60～5.11	2.16～3.68	0.12～0.47	1.09～2.60	9.96～15.64	32.61～38.16	4.33～10.14
平均值	0.21	28.02	2.48	2.94	0.24	2.02	14.07	36.16	6.42

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表 9 HRB400E化学成分统计

Table 9. Main components of HRB400E

名称	w/%						统计炉数
名称	C	Si	Mn	P	S	V	统计炉数
试验	0.21～0.25	0.32～0.45	1.26～1.40	0.018～0.038	0.011～0.040	0.018～0.032	27
试验	0.235	0.38	1.32	0.029	0.028	0.025	27
原生产	0.21～0.25	0.30～0.47	1.22～1.37	0.012～0.037	0.007～0.035	0.021～0.035	34
原生产	0.227	0.38	1.31	0.021	0.025	0.027	34

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表 10 HRB400E力学性能统计

Table 10. Main mechanical properties of HRB400E

品种	规格组距/mm	R_eL/MPa	R_m /MPa	A /%	A_gt /%	强屈比	反弯	统计炉数
线材	Ø8、Ø10	(430～485)/460	(620～685)/658	(23.0～44.0)/35.0	(12.5～20.8)/16.2	(1.39～1.54)/1.47	合格	12
线材	Ø12	(440～500)/473	(625～695)/649	(28.0～41.0)/34.0	(11.3～20.5)/15.9	(1.40～1.56)/1.49	合格	15
标准要求		≥400	≥540	≥16	≥9.0	≥1.25	无裂纹

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