未燃煤粉及其还原产物在高钛型高炉渣中的行为研究

谢洪恩; 郑魁; 胡鹏; 唐文博; 令新科

doi:10.7513/j.issn.1004-7638.2024.06.016

未燃煤粉及其还原产物在高钛型高炉渣中的行为研究

doi: 10.7513/j.issn.1004-7638.2024.06.016

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

详细信息

作者简介:
谢洪恩，1977年出生，男，四川内江人，正高级工程师，主要研究方向：钒钛矿高炉冶炼，E-mail：pzhxiehongen@163.com

中图分类号: TF533
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- 被引次数: 0
出版历程
- 收稿日期: 2023-08-24
- 网络出版日期: 2024-12-30
- 刊出日期: 2024-12-30

Study on the behavior of unburnt pulverized coal and reduction productions of TiO₂ in high-titanium blast furnace slag

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

摘要

摘要: 采用旋转柱体法对配加未燃煤粉的高钛型高炉渣的黏度进行了测量，结合试验样品的宏观形貌和不同部位微观结构的表征，对未燃煤粉及其还原产物在高钛型高炉渣中的行为进行了分析。结果表明，未燃煤粉不可避免地会与渣中TiO₂反应，残余的未燃煤粉及其还原产物,如Ti(C,N)或TiC_xO_y等高熔点物相不均匀分布于渣中。随着初始未燃煤粉含量从0增加至5.51%，渣中TiC和TiN含量之和从0.456%升高至2.515%，反应生成的高熔点物质向下沉降聚集，残余的未燃煤粉则向上运动，与上部炉渣中的TiO₂继续反应生成高熔点物质或形成泡沫渣，并导致炉渣黏度显著升高，波动显著加剧，炉渣中部则几乎没有残余未燃煤粉和高熔点还原产物。
- 高钛型高炉渣 /
- 未燃煤粉 /
- 还原行为 /
- 黏度 /
- 碳氮化钛
Abstract: In this study, the viscosity of high-titanium blast furnace slags uniformly mixed with unburnt pulverized coal (UPC) was measured by using the method of rotating cylinder firstly. Then the distribution and behavior of the residual UPC and the reduction products were analyzed according to the macro morphology of these samples and their microscopic morphology of different parts. It was found that TiO₂ would inevitably be reduced by UPC, the high melting point reduction products such as Ti(C,N), TiC_xO_y and unburnt UPC distributed nonuniformly in the slag. As the initial UPC content increased from 0% to 5.51%, the total content of TiC and TiN increased from 0.456% to 2.515%. The high melting point reduction products deposited downwards and aggregated, while the unburnt UPC floated upwards and continued to react with TiO₂ to form foam slag, resulting in a significant increase in both viscosity and its fluctuation. However, there were negligible residual unburnt UPC and high melting point reduction products in the middle of the slag.
- high-titanium blast furnace slag /
- unburnt pulverized coal /
- reduction behavior /
- viscosity /
- titanium carbonitride

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图 1 制备未燃煤粉竖炉示意

Figure 1. Schematic diagram of the shaft furnace

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图 2 残余未燃煤粉照片

Figure 2. Photos of residual UPC

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图 3 未燃煤粉和残余未燃煤粉的光学显微照片

Figure 3. Optical micrographs of UPC and residual UPC

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图 4 不同炉渣的黏度－温度曲线

Figure 4. Viscosities varying with temperatures of different slags

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图 5 测量结束后试验样品的俯视照片

Figure 5. Top views of the samples after viscosity measurements

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图 6 测量结束后试验样品的纵向剖面照片

Figure 6. Cross-section photos of the samples after viscosity measurements

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图 7 样品M4底部沉积物的扫描电镜(SEM)照片及元素含量

Figure 7. SEM image and element contents of depositions at the bottom of sample M4

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图 8 样品M4顶部泡沫渣、中部和底部的光学显微照片

Figure 8. Optical micrograph of foam slag at the top, middle part and bottom of sample M4

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图 9 R_O, R_TCN and R_C 随初始未燃煤粉含量的变化

Figure 9. The changes of R_O, R_TCN and R_C with the initial UPC contents in slags

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图 10 未燃煤粉及其还原产物在渣中的分布和行为

Figure 10. The distribution and behavior of reduction products and UPC in slags

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表 1 喷吹煤粉和未燃烧煤粉的化学成分

Table 1. Chemical compositions of PCI and UPC %

名称	C_ad	V_daf	A_d	S_t	灰分分析
名称	C_ad	V_daf	A_d	S_t	CaO	SiO₂	MgO	Al₂O₃	Fe₂O₃	TiO₂	K₂O	Na₂O
喷吹煤粉	80.60	9.78	11.74	0.78	1.88	49.51	0.44	38.13	3.90	1.18	0.722	1.32
未燃煤粉	88.70	0.17	11.97	0.48	2.10	50.54	0.54	37.65	3.36	1.38	0.66	1.13

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表 2 基准高炉渣化学成分

Table 2. Chemical composition of on-site blast furnace slag %

CaO	SiO₂	MgO	Al₂O₃	MnO	FeO	TiO₂	Ti₂O₃	TiO	TiC	TiN
26.46	25.52	8.40	13.70	0.63	1.03	21.20	0.897	0.504	0.100	0.356

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表 3 炉渣未燃煤粉配加方案

Table 3. Adding scheme of UPC to slag

编号	燃烧率/%	炉渣质量/g	未燃煤粉质量/g	未燃煤粉含量/%
M0	100	170.00	0	0
M1	90	168.04	1.96	1.15
M2	80	166.12	3.88	2.28
M3	70	164.25	5.75	3.38
M4	60	162.42	7.58	4.46
M5	50	160.63	9.37	5.51

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表 4 残余未燃煤粉的质量和C含量

Table 4. The mass and C contents of unconsumed UPC

编号	质量/g	C/%
M1	0.87	84.40
M2	2.77	84.80
M3	4.00	85.80
M4	6.82	86.00
M5	7.50	86.90

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表 5 不同样品的低价钛化合物含量

Table 5. Mass fractions of different titanium compounds of slags after viscosity measurements %

编号	TiO₂	Ti₂O₃	TiO	TiC	TiN
M0	21.20	0.897	0.504	0.100	0.356
M1	21.43	2.570	0.955	0.905	0.681
M2	21.64	2.570	1.050	1.110	0.727
M3	21.55	2.270	1.250	1.360	0.681
M4	21.19	0.247	1.910	1.730	0.526
M5	21.24	0.648	1.880	2.190	0.325

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表 6 R_O、R_C和R_TCN的计算结果

Table 6. The calculation results of R_O, R_C and R_TCN

编号	O_loss/g	${\mathrm{O}}_{{\mathrm{TiO}}_2} $/g	R_O/%	C_coms/g	C_UPC/g	R_C/%	Ti_TiCN/g	${\mathrm{Ti}}_{{\mathrm{TiO}}_2} $/g	R_TCN/%
M1	2.28	14.40	15.85	1.392	1.74	80.08	2.10	21.61	9.73
M2	2.52	14.38	17.51	1.633	3.44	47.44	2.41	21.57	11.17
M3	2.70	14.16	19.04	1.845	5.10	36.17	2.65	21.24	12.49
M4	2.76	13.77	20.05	2.008	6.72	29.86	2.91	20.65	14.09
M5	3.02	13.65	22.10	2.342	8.31	28.18	3.22	20.47	15.72

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表 7 R_O、R_C和R_TCN的拟合结果

Table 7. The calculation results of R_O, R_C and R_TCN

	equation	a	b	c	Adj. R²
R_O	y = a + bx	14.28	1.38		0.988
R_TCN	y = a + bx	8.05	1.37		0.996
R_C	y = aexp(-x/b) + c	136.27	1.23	26.70	0.999

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