预制铁酸钙技术对钒钛磁铁矿烧结行为的影响

谢皓; 李刚; 吕学伟; 孙小东; 何海熙

doi:10.7513/j.issn.1004-7638.2023.04.018

预制铁酸钙技术对钒钛磁铁矿烧结行为的影响

doi: 10.7513/j.issn.1004-7638.2023.04.018

谢皓^{1, 2,},
李刚¹,
吕学伟²,
孙小东¹,
何海熙¹

1.
中冶赛迪信息技术(重庆)有限公司, 重庆400041
2.
重庆大学材料科学与工程学院, 重庆400044

基金项目: 国家自然科学基金（51974048）。

详细信息

作者简介:
谢皓，1984年出生，男，甘肃礼县人，硕士研究生，主要从事炼铁工艺及智能化方面的研究，E-mail：Hao.Xie@cisdi.com.cn

中图分类号: TF046
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出版历程
- 收稿日期: 2022-12-23
- 刊出日期: 2023-08-30

Effect of preformed calcium ferrite addition on sintering behavior of vanadium titanomagnetite

Xie Hao^{1, 2
,},
Li Gang¹,
Lv Xuewei²,
Sun Xiaodong¹,
He Haixi¹

1.
CISDI-INFO Co., Ltd., Chongqing 400041, China
2.
College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China

摘要

摘要: 针对钒钛磁铁矿在烧结过程中的成品率低、强度差、能耗高等问题，提出了预制铁酸钙烧结新技术，并通过压块焙烧试验和热分析测试揭示该技术的可行性及理论依据。结果表明，随着预制铁酸钙替代生石灰比例增加，焙烧产物微观形貌由粒状结构向熔蚀结构转变，四元复合铁酸钙（SFCA）含量增加，钙钛矿含量降低，有利于焙烧过程的液相生成，烧结孔洞熔合程度增大，平均孔隙率从42.9%下降到36.2%，促进基体的致密化。升温过程中铁酸钙液相的生成可分为三个反应，根据生成温度由低到高依次为CF+CF₂→L的共熔反应，SFCA-I及SFCA的熔化分解反应；预制铁酸钙的加入可降低初始液相的产生温度，整体提高烧结液相量，提高比例约9%；预制铁酸钙技术可促进铁氧化物向初始液相中熔解，增加铁酸钙含量，促进固-液同化反应。
- 烧结 /
- 钒钛磁铁矿 /
- 预制铁酸钙 /
- 热分析(TG-DSC)
Abstract: In view of the problems of low yield, poor strength and high energy consumption in the sintering process of vanadium titanomagnetite, a new sintering technology of preformed calcium ferrite is proposed in this paper, and its feasibility and theoretical basis are revealed through the tablet sintering and thermal analysis test. The results show that with the increase of substitution ratio (preformed calcium ferrite to partially substitute CaO), the microstructure of roasted products changes from granular structure to melting corrosion structure, the content of SFCA increases, while perovskite content decreases. In addition, the quantity of melts increases, the coalesce of sintering bubbles is promoted, the average porosity decreases from 42.9% to 36.2%, and the densification of the matrix is promoted. The formation of calcium ferrite melts in the heating process can be divided into three reactions, according to the formation temperature from low to high, it is the eutectic reaction of CF+CF₂ → L, the melting of SFCA-I and SFCA, respectively; the addition of preformed calcium ferrite can reduce the generation temperature of initial melts, and increase the total sintering melts by about 9 %; promote the melting of iron oxides into the initial melts, increase the content of calcium ferrite, and promote solid-liquid assimilation reaction.
- sintering /
- vanadium titanomagnetite /
- preformed calcium ferrite /
- TG-DSC

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图 1 不同替代比例下烧结压块的光学显微照片

Figure 1. Optical micrographs of sintered tablets at various substitution ratios

(a)0; (b)20%; (c)50%

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图 2 不同替代比例烧结产品孔洞面积统计

Figure 2. Statistics of pore area of sintered products at various substitution ratios

(a)(a')0; (b)(b')50%

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图 3 不同替代比例下烧结样品的物相转变

Figure 3. Phase transformation of sinter blends with the addition of preformed CF

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图 4 烧结混合料在升温过程中的TG-DSC曲线

Figure 4. TG-DSC curves of different sintering mixture samples during heating

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图 5 烧结混合料在降温过程中的TG-DSC曲线

Figure 5. TG-DSC curves of different sintering mixture samples during cooling

下载: 全尺寸图片幻灯片

表 1 钒钛磁铁矿烧结矿物相组成

Table 1. Phase compositions of VTM iron ore sinter %

作者	时间	R	TM	TH	P	SFCA	TP	AT	C2S	G
任允芙^[1]	1986		45.45	23.23	7.31	5.85	2.35			11.68
蒋大军^[6]	2017		46～49	12～15	1～3	20～23	1～3	1	3～5	8～11
胡鹏^[7]	2017	1.84	35～37	11～13	4～8	29～31		4～7		16～18
何木光^[8]	2015	2.13	20～22	32～34	6～8	20～22	17～19
李劲明^[9]	2008	2.4	26～28	22～25	1～1.5	23～28	16～18
甘勤^[10]	2000	1.7	28	38	2	3	23			6
何木光^[11]	2012	2.4	22～26	28～31	1.5～1.8	25～28	12～16.5			1～1.5
蒋大军^[12]	2012	2.2	32～34	27～29	3～4	18～20	1～2	2～4	3～5	12～14
何木光^[13]	2010		29～31.2	28～31	1.2～1.8	15～17.5	18～19.5		1～2	2.8～3
何木光^[14]	2013	2.9	20～23	21～24	4～5	30～33	1～3	6～8	1～3	7～10
Yu ^[15]	2015	2.0	38	35	7	4.5
何木光^[2]	2016		33～35	20～23	5～7	15～18	3～5	7～9	1～3	6～9
* R-二元碱度，TM-钛磁铁矿，TH-钛赤铁矿，P-钙钛矿，SFCA-铁酸钙，TP-钛辉石，AT-钛榴石，C2S-硅酸二钙，G-玻璃体

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表 2 烧结原料主要化学成分

Table 2. Chemical compositions of sintering raw materials %

原料	TFe	FeO	Al₂O₃	MgO	SiO₂	CaO	TiO₂	V₂O₅	S	P
VTM	55.62	30.72	3.41	3.28	3.3	0.587	10.3	0.68	0.517	0.006
铁矿A	61.12	28.3	0.131	1.96	1.12	4.19			1.4	0.137
铁矿 B	43.75	1.29	6.66	0.624	22.94	1.18	0.582		0.118	0
铁矿 C	61.31	9.33	0.702	0.427	9.23	0.716			0.04	0.074
石灰石	0.35		0.89	1.12	2.38	52.54			0.0115

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表 3 不同替代比例下的烧结物料配比

Table 3. Material ratio under different substitution ratios %

替代比例	VTM	铁矿A	铁矿C	铁矿B	石灰石	生石灰	铁酸钙	返矿
0	63.15	12.63	4.74	4.74	9.47	5.26	0	15
20	61.67	12.33	4.63	4.63	9.25	4.11	3.38	15
50	59.59	11.92	4.47	4.47	8.93	2.48	8.13	15

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表 4 烧结料在升温过程中的各阶段反应

Table 4. Reaction of sinter blend in each heating stage

替代比例/%	温度区间/ ℃	峰值/ ℃	曲线特征		DSC峰面积分/(J·g⁻¹)	物理化学变化
替代比例/%	温度区间/ ℃	峰值/ ℃	TG	DSC	DSC峰面积分/(J·g⁻¹)	物理化学变化
0	45～200		略有失重	“V”型		物理水蒸发
20
50
0	345～500	440	失重	小吸热峰		Ca(OH)₂分解
20
50
0	525～600	570	略有增重	小放热峰		磁铁矿氧化
20
50
0	691～827	785	大幅失重	吸热峰	65.3	石灰石分解
20	692～835	795			59.65
50	691～815	774			46.76
0	827～1160		略有增重	宽吸热段		二元铁酸钙生成及磁铁矿氧化
20	835～1154
50	815～1153
0	1160～1220	1186	略有失重	小吸热峰	0.59	CF+CF₂共熔
20	1154～1219	1190			4.32
50	1153～1211	1187			3.18
0	1220～1289	1277	略有失重	强吸热峰	39.38	SFCA-I熔化
20	1219～1292	1275			38.94
50	1211～1288	1271			39.11
0	1289～1320	1302	略有失重	小吸热峰	3.39	SFCA熔化
20	1292～1317	1303			2.32
50	1288～1317	1301			2.11
0	1320～1400	1361	略有失重	较强吸热峰	18.16	铁矿物熔化及赤铁矿分解
20	1317～1400	1362			21.66
50	1317～1400	1362			22.40

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表 5 升温过程中铁酸钙及铁矿物熔化所吸收热量

Table 5. Heat absorbed by the melting of SFCA and iron ore in heating

替代比例/%	CF+CF₂共熔 /(J·g⁻¹)	SFCA-I熔化 /(J·g⁻¹)	SFCA熔化 /(J·g⁻¹)	铁矿物熔化 /(J·g⁻¹)	总液相 /(J·g⁻¹)	提高百分比/%
0	0.59	39.38	3.39	18.16	61.52	0
20	4.32	38.94	2.32	21.66	67.24	9.3
50	3.18	39.11	2.11	22.40	66.8	8.58

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表 6 烧结料在降温过程中的各阶段反应

Table 6. Reaction of sinter blend in each stage of cooling

替代比例/%	温度区间/ ℃	峰值/ ℃	曲线特征		DSC峰面积分/(J·g⁻¹)	物理化学变化
替代比例/%	温度区间/ ℃	峰值/ ℃	TG	DSC	DSC峰面积分/(J·g⁻¹)	物理化学变化
0	1336～1281	1313	略有增重	放热峰	29.28	铁氧化物析出及磁铁矿氧化
20	1355～1288	1326			27.25
50	1360～1288	1327			28.54
0	1227～1195	1216	略有增重	放热峰	7.77	铁酸钙析出及磁铁矿氧化
20	1228～1196	1217			9.27
50	1226～1195	1217			11.62

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