含钛高炉渣/绿矾协同焙烧富集金红石机理研究

刘维燥; 何民宇; 刘清才; 张强

doi:10.13779/j.cnki.issn1001-0076.2022.03.011

含钛高炉渣/绿矾协同焙烧富集金红石机理研究

1.
重庆大学材料科学与工程学院, 重庆 400044

2.
龙佰四川钛业有限公司, 四川德阳 6182093

基金项目:
国家自然科学基金青年科学基金项目(52104322)

详细信息

作者简介: 刘维燥, 男, 博士, 讲师, 研究方向为固体废物资源循环利用, E-mail: liuwz@cqu.edu.cn

通讯作者: 张强, E-mail: 491408119@qq.com

中图分类号: TD982;TF046.2;X758

收稿日期: 2022-03-29

刊出日期: 2022-06-25

Study on the Mechanism of Rutile Beneficiation by Roasting Titanium-bearing Blast Furnace Slag with Copperas

1.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China

2.
LB Sichuan Titanium Industry Co., Ltd., Deyang 618209, Sichuan, China

More Information

Corresponding author: ZHANG Qiang, 491408119@qq.com

Received Date: 29 March 2022

Publish Date: 25 June 2022

摘要

摘要:
含钛高炉渣和绿矾是以钒钛磁铁矿为原料经选矿后冶炼生铁和二氧化钛工艺中排出的两种主要固体废弃物, 上述两种固废的共同处置对钛铁工业的发展具有重要意义。采用含钛高炉渣和绿矾为原料, 提出了一种富集金红石的新工艺。含钛高炉渣和绿矾经过共焙烧, 其中绿矾热分解为二氧化硫和三氧化二铁, 进而二氧化硫和含钛高炉渣中的钙钛矿及含钛辉石发生硫酸化反应, 钙镁组分转化为硫酸盐, 而钛组分被富集为金红石。系统地研究了工艺参数对含钛高炉渣富集过程的影响。研究发现, 加入Na₂SO₄可以显著提高Ti的富集效率。在绿矾与含钛高炉渣质量比为2、硫酸钠添加量为10%、焙烧温度为650℃、保温时间4 h的最优条件下, 含钛高炉渣中钛的转化率达98%, 富集后金红石含量约为8.6%, 后续可通过浮选进一步富集。Na₂SO₄的加入促进了熔融Na₃Fe (SO₄)₃的形成, 熔融物能够渗透含钛高炉渣内部进行硫酸化反应, 气液固相反应加速了钛的富集过程。
- 含钛高炉渣 /
- 硫酸亚铁 /
- 金红石 /
- 工业固废 /
- 富集分离
Abstract:
Titanium-bearing blast furnace slag (TBFS) and copperas are two major solid wastes discharged from pig iron and titania production with vanadium-titanium magnetite ore as feedstock. Co-disposal of the above two wastes is of great importance for the development of ferrotitanium industry. In this study, a novel process for rutile beneficiation was proposed by using TBFS and copperas. TBFS and copperas were co-roasted, where copperas was thermally decomposed into sulfur dioxide and ferric oxide, and the sulfur dioxide continued to react with the CaTiO₃ and titanium-bearing diopside in TBFS. During the sulfation reaction of TBFS, the calcium and magnesium was converted into corresponding sulfates, while titanium was beneficiated to rutile. The effects of process parameters on beneficiation were studied systematically. It was found that addition of Na₂SO₄ significantly enhanced the conversion efficiency of Ti. Under the optimal conditions, i.e. a mass ratio of copperas to TBFS of 2, Na₂SO₄ dosage of 10%, roasting temperature of 650℃, roasting time of 4 h, the conversion efficiency of Ti reached 98%. The content of rutile reached 8.6%, which can be further beneficiated by flotation. The addition of Na₂SO₄ promoted the formation of molten Na₃Fe(SO₄)₃, which was able to penetrate inside the TBFS and proceed sulfation reaction with inner TBFS. And gas-liquid-solid phase reactions facilitated the beneficiation of titanium.
- titanium-bearing blast furnace slag /
- ferrous sulfate /
- rutile /
- industrial solid waste /
- beneficiation and separation

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图 1 含钛高炉渣XRD谱图

Figure 1.

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图 2 CaTiO₃与FeSO₄反应的(a)标准吉布斯自由能变化及(b)平衡组成

Figure 2.

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图 3 焙烧温度(a)、物料比(b)、保温时间(c)和添加剂(d)对钙钛矿转化率和绿矾分解率的影响

Figure 3.

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图 4 不同焙烧温度和物料比影响下焙烧渣的XRD谱图

Figure 4.

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图 5 (a) 不同的硫酸钠添加量对含钛高炉渣、钙钛矿转化率和绿矾分解率的影响和(b)不同焙烧条件下焙烧渣的XRD谱图

Figure 5.

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图 6 未添加(a)和添加10% Na₂SO₄ (b)时焙烧样品SEM图像

Figure 6.

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图 7 加入10% Na₂SO₄焙烧渣的EDS元素分布图

Figure 7.

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表 1 含钛高炉渣及绿矾化学成分 /%

Table 1. Chemical composition of the titanium-bearing blast furnace slag and copperas

物质	CaO	SiO₂	TiO₂	Al₂O₃	MgO	SO₃	Fe₂O₃	SO₃	其他
含钛高炉渣	30.38	26.11	18.36	11.00	7.14	2.69	1.86	/	2.47
绿矾	/	/	1.43	/	2.00	/	48.70	47.28	0.59

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表 2 CaTiO₃与FeSO₄共焙烧可能发生的反应

Table 2. Possible reactions when roasting ferrous sulfate with CaTiO₃

Reaction equations
CaTiO₃+2FeSO₄→CaSO₄+TiO₂+Fe₂O₃+SO₂(g)	(1)
Ca(Ti, Mg, Al)(Si, Al)₂O₆+FeSO₄ →Ca/MgSO₄+ Fe₂O₃+Al₂O₃+SiO₂+TiO₂	(2)
2FeSO₄→ Fe₂O₃+2SO₂(g)+1/2O₂(g)	(3)
CaTiO₃+SO₂(g)+1/2O₂(g) →CaSO₄+TiO₂	(4)
Ca(Ti, Mg, Al)(Si, Al)₂O₆+SO₂+O₂→Ca/MgSO₄+Al₂O₃+SiO₂+TiO₂	(5)

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