炉渣成分对冶炼白云鄂博矿高炉渣脱硫和排碱能力的影响

张国成; 王雅军; 罗果萍

doi:10.13374/j.issn2095-9389.2020.11.19.001

炉渣成分对冶炼白云鄂博矿高炉渣脱硫和排碱能力的影响

doi: 10.13374/j.issn2095-9389.2020.11.19.001

张国成^{1, 2, ,},
王雅军³,
罗果萍^2, ,

1.
包头师范学院化学学院, 包头 014030
2.
内蒙古科技大学材料与冶金学院, 包头 014010
3.
内蒙古包钢钢联股份有限公司技术中心, 包头 014010

基金项目: 国家自然科学基金资助项目（51664045）

详细信息

通讯作者:
张国成，E-mail: 644942242@qq.com

罗果萍，E-mail: luoguoping3@126.com

中图分类号: TF046
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- 被引次数: 0
出版历程
- 收稿日期: 2020-11-19
- 网络出版日期: 2021-06-18
- 刊出日期: 2022-07-25

Effect of slag composition on desulfurization and alkali removal ability of blast furnace slag for Bayan Obo iron ore

ZHANG Guo-cheng^{1, 2
, ,},
WANG Ya-jun³,
LUO Guo-ping^{2
, ,}

1.
Department of Chemistry, Baotou Teachers’ College, Baotou 014030, China
2.
School of Materials and Metallurgy, Inner Mongolia University of Science and Technology, Baotou 014010, China
3.
Technical Center, Steel Union Corp. of Baotou Steel in Inner Mongolia, Baotou 014010, China

More Information

Corresponding author: ZHANG Guo-cheng, E-mail: 644942242@qq.com; LUO Guo-ping, E-mail: luoguoping3@126.com

摘要

摘要: 为了探明炉渣成分对冶炼白云鄂博矿高炉渣脱硫和排碱能力的影响，在实际高炉渣成分的基础上，通过正交试验和Factsage 7.1热力学模拟软件绘制不同组分高炉渣渣系五元伪三元相图，探究了自由碱度（R_o）、w(MgO)和w(Al₂O₃)对高炉渣脱硫、排碱能力的影响规律，并结合生产实际给出了适宜的炉渣自由碱度（R_o）、w(MgO)和w(Al₂O₃)的控制范围。研究表明： R_o是影响炉渣脱硫、排碱能力的最显著因素，R_o增加，渣中O²⁻浓度升高，促使硅氧复合阴离子Si−O解体，炉渣黏度减小，炉渣与金属液体之间的传质过程得到促进，使得S²⁻更容易向渣中迁移，炉渣脱硫的热力学和动力学条件改善，脱硫能力提高，适宜的R_o应控制在1.05～1.15；w(MgO)是影响炉渣脱硫能力的次要因素，w(MgO)增加，炉渣的流动性和稳定性提高，有利于改善炉渣脱硫的动力学条件，且可降低炉渣中(K₂O+Na₂O)的活度，提高排碱能力，适宜w(MgO)应控制在15%左右；w(Al₂O₃)是影响炉渣排碱能力的次要因素，w(Al₂O₃)增加，易生成镁铝尖晶石(MgAl₂O₄)等高熔点物质，使炉渣中的自由氧离子消耗量增多，不利于脱硫反应动力学条件的改善，虽然增加w(Al₂O₃)有益于排碱，但高w(Al₂O₃)不利于脱硫，且会导致炉渣黏度上升，适宜w(Al₂O₃)应控制在12%左右。
- 高炉渣 /
- 白云鄂博矿 /
- 炉渣成分 /
- 脱硫 /
- 排碱
Abstract: To investigate the effect of slag composition on desulfurization and alkali removal ability of blast furnace slag for smelting Bayan Obo ore, based on the actual composition of blast furnace slag, the effect of free basicity (R_o), w(MgO), and w(Al₂O₃) on the desulfurization and alkali removal ability of blast furnace slag was investigated by performing orthogonal experiments and on the basis of five-element pseudoternary phase diagrams of various components of a blast furnace slag system calculated and drawn using Factsage 7.1 thermodynamic simulation software, and the appropriate control range of R_o, w(MgO) and w(Al₂O₃) in the slag were given in combination with the production practice. The results show that: R_o is the most significant factor affecting slag desulfurization and alkali removal ability. With the increase in R_o, the O²⁻ concentration in slag increases, resulting in Si−O disintegration, and slag viscosity decreases. In addition, the mass transfer between slag and metal liquid is accelerated, which makes S²⁻ easier to migrate into slag, the thermodynamic and kinetic conditions of slag desulfurization are improved, thus improving the desulfurization ability. The appropriate R_o should be controlled within the range of 1.05–1.15. w(MgO) is a secondary factor affecting the slag desulfurization ability. With the increase in w(MgO), the fluidity and stability of the slag are improved, which are beneficial for improving the kinetic conditions of slag desulfurization and reducing the activity of (K₂O+Na₂O) in the slag, thus improving the alkali removal ability. Appropriate w(MgO) should be controlled at approximately 15%. w(Al₂O₃) is a secondary factor affecting the alkali removal ability of blast furnace slag. With the increase in w(Al₂O₃), high melting point materials such as MgAl₂O₄ are easily formed, thereby increasing the consumption of free oxygen ions in the slag. This increase is not conducive to the improvement of desulfurization reaction kinetic conditions. Although increasing w(Al₂O₃) is beneficial for removing alkali, high w(Al₂O₃) is not conducive to desulfurization and leads to an increase in slag viscosity. Appropriate w(Al₂O₃) should be controlled at approximately 12%.
- blast furnace slag /
- Bayan Obo iron ore /
- slag composition /
- desulfurization /
- alkali removal

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图 1 高温熔渣脱硫实验装置

Figure 1. High-temperature slag viscosity measuring device

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图 2 高温熔渣排碱实验装置

Figure 2. Experimental device for alkali removal of high-temperature slag

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图 3 高炉渣脱硫能力主观效应图

Figure 3. Subjective effect diagram of blast furnace slag desulfurization

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图 4 高炉渣排碱实验结果主观效应图

Figure 4. Subjective effect diagram of alkali removal from blast furnace slag

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5 不同R_o条件下的CaO−SiO₂−MgO−Al₂O₃−CaF₂五元渣伪三元相图.(a) R_o=0.95; (b) R_o=1.05; (c) R_o=1.15; (d) R_o=1.25

5. Pseudoternary phase diagram of CaO−SiO₂−MgO−Al₂O₃−CaF₂ five-component slag with different R_o: (a) R_o=0.95; (b) R_o=1.05; (c) R_o=1.15; (d) R_o=1.25

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图 6 不同MgO含量的CaO−SiO₂−MgO−Al₂O₃−CaF₂五元渣伪三元相图. (a) w(MgO)=10%; (b) w(MgO)=12%; (c) w(MgO)=14%; (d) w(MgO)=16%

Figure 6. Pseudoternary phase diagram of CaO−SiO₂−MgO−Al₂O₃−CaF₂ five-component slag with different MgO content: (a) w(MgO)=10%; (b) w(MgO)=12%; (c) w(MgO)=14%; (d) w(MgO)=16%

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图 7 不同Al₂O₃含量的 CaO−SiO₂−MgO−Al₂O₃−CaF₂ 五元渣伪三元相图. (a) w(Al₂O₃)=11%; (b) w(Al₂O₃)=13%; (c) w(Al₂O₃)=15%; (d) w(Al₂O₃)=17%

Figure 7. Pseudoternary phase diagram of CaO−SiO₂−MgO−Al₂O₃−CaF₂ five-component slag with different Al₂O₃ contents: (a) w(Al₂O₃)=11%; (b) w(Al₂O₃)=13%; (c) w(Al₂O₃)=15%; (d) w(Al₂O₃)=17%

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表 1 高炉渣实际化学成分

Table 1. Actual chemical composition of blast furnace slag

w(CaO)/%	w(SiO₂)/%	w(MgO)/%	w(Al₂O₃)/%	w(F)/%	w(Na₂O)/%	w(K₂O)/%	w(S)/%	R_o
34.93	35.70	9.70	11.77	0.38	0.46	0.56	1.39	0.96

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表 2 实验设计方案

Table 2. Experimental design scheme

Experiment number	R_o	w(MgO)/%	w(Al₂O₃)/%
1#	C3(1.15)	A1(10)	B2(13)
2#	C1(0.95)	A3(14)	B4(17)
3#	C3(1.15)	A2(12)	B4(17)
4#	C1(0.95)	A4(16)	B2(13)
5#	C1(0.95)	A1(10)	B3(15)
6#	C3(1.15)	A3(14)	B1(11)
7#	C1(0.95)	A2(12)	B1(11)
8#	C3(1.15)	A4(16)	B3(15)
9#	C4(1.25)	A1(10)	B1(11)
10#	C2(1.05)	A3(14)	B3(15)
11#	C4(1.25)	A2(12)	B3(15)
12#	C2(1.05)	A4(16)	B1(11)
13#	C2(1.05)	A1(10)	B4(17)
14#	C4(1.25)	A3(14)	B2(13)
15#	C2(1.05)	A2(12)	B2(13)
16#	C4(1.25)	A4(16)	B4(17)
Note: R_o is the free basicity, and the calculation formula is as follows: $ {R}_{\mathrm{O}}=[w\left(\mathrm{C}\mathrm{a}\mathrm{O}\right)-1.473\times w\left(\mathrm{F}\right)]/w\left({\mathrm{S}\mathrm{i}\mathrm{O}}_{2}\right) $, which is the representation method of basicity of fluorine-containing blast furnace slag in Bayan Obo iron ore.

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表 3 合成渣实际化学成分

Table 3. Actual chemical composition of synthetic blast furnace slag

Experiment number	w(CaO)/%	w(SiO₂)/%	w(MgO)/%	w(Al₂O₃)/%	w(F)/%	w(Na₂O)/%	w(K₂O)/%	w(S)/%	R_o
1#	36.03	30.44	9.83	12.78	0.98	0.68	0.41	1.17	1.14
2#	31.07	31.05	13.21	16.21	0.73	0.59	0.32	1.01	0.96
3#	34.62	29.65	12.66	17.40	0.82	0.63	0.35	0.98	1.13
4#	32.56	32.16	14.73	13.14	0.82	0.58	0.41	1.06	0.97
5#	33.27	33.49	10.42	14.29	0.94	0.61	0.42	1.05	0.95
6#	35.93	30.22	13.63	11.66	0.91	0.63	0.45	1.16	1.14
7#	33.84	34.33	12.71	11.71	0.81	0.65	0.39	0.96	0.95
8#	32.75	27.98	16.38	15.27	0.72	0.58	0.35	0.87	1.13
9#	38.93	31.02	10.65	11.43	0.73	0.61	0.38	0.95	1.22
10#	32.52	30.25	14.52	15.54	0.79	0.67	0.37	0.96	1.04
11#	35.85	28.16	12.65	15.36	0.78	0.55	0.35	0.88	1.23
12#	33.16	31.11	15.92	11.13	0.82	0.66	0.38	0.97	1.03
13#	32.87	30.5	10.63	17.24	0.80	0.65	0.41	0.97	1.04
14#	36.22	28.71	14.68	13.57	0.73	0.56	0.35	0.86	1.22
15#	33.87	31.7	12.70	13.35	0.89	0.64	0.40	0.96	1.03
16#	32.84	26.59	16.31	17.72	0.65	0.55	0.32	0.82	1.20

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表 4 高炉渣脱硫实验结果极差分析

Table 4. Range analysis of experimental results of blast furnace slag desulfurization

Experiment number	R_o	w(MgO)	w(Al₂O₃)	w[S]	w(S)	L_s
1#	C3	A1	B2	0.017	1.260	74.120
2#	C1	A3	B4	0.018	1.010	56.110
3#	C3	A2	B4	0.019	1.044	76.550
4#	C1	A4	B2	0.013	1.030	79.230
5#	C1	A1	B3	0.022	1.040	47.270
6#	C3	A3	B1	0.012	1.240	103.330
7#	C1	A2	B1	0.020	1.010	50.500
8#	C3	A4	B3	0.010	0.991	99.100
9#	C4	A1	B1	0.013	1.070	82.310
10#	C2	A3	B3	0.015	0.978	65.200
11#	C4	A2	B3	0.008	0.941	117.630
12#	C2	A4	B1	0.014	1.040	74.290
13#	C2	A1	B4	0.020	1.010	50.500
14#	C4	A3	B2	0.008	0.979	122.380
15#	C2	A2	B2	0.021	1.070	50.950
16#	C4	A4	B4	0.010	0.867	86.700
Factor level mean, K₁	58.28	63.55	77.61	—	—	—
Factor level mean, K₂	60.24	73.91	81.67	—	—	—
Factor level mean, K₃	88.28	86.76	82.30	—	—	—
Factor level mean, K₄	102.26	84.83	67.47	—	—	—
Range, R	43.98	23.21	14.84	—	—	—

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表 5 高炉渣脱硫实验结果回归方差分析

Table 5. Variance analysis of experimental results of blast furnace slag desulfurization

Parameter		D_f	SS	MS	F value	Significance F
w(S)	Regression analysis	3	0.000262	8.74×10⁻⁵	15.49949	0.000198
	Residual	12	6.77×10⁻⁵	5.64×10⁻⁶	—	—
	Sum	15	0.00033	—	—	—
L_s	Regression analysis	3	6573.193	2191.064	12.04054	0.000847
	Residual	11	2001.713	181.9739	—	—
	Sum	14	8574.906	—	—	—
Note: D_f represents degree of freedom; SS represents regression sum of squares; MS represents mean square; F value represents analysis of variance test statistics.

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表 6 高炉渣排碱实验结果

Table 6. Experimental results of alkali removal from blast furnace slag

Experiment number	R_o	w(MgO)	w(Al₂O₃)	w(K₂O+Na₂O)/%
1#	C3	A1	B2	0.608
2#	C1	A3	B4	0.680
3#	C3	A2	B4	0.295
4#	C1	A4	B2	0.881
5#	C1	A1	B3	0.826
6#	C3	A3	B1	0.650
7#	C1	A2	B1	0.638
8#	C3	A4	B3	0.158
9#	C4	A1	B1	0.212
10#	C2	A3	B3	0.203
11#	C4	A2	B3	0.097
12#	C2	A4	B1	0.971
13#	C2	A1	B4	0.42
14#	C4	A3	B2	0.346
15#	C2	A2	B2	0.580
16#	C4	A4	B4	0.129
Factor level mean, K₁	0.756	0.517	0.618	—
Factor level mean, K₂	0.544	0.403	0.604	—
Factor level mean, K₃	0.428	0.470	0.321	—
Factor level mean, K₄	0.196	0.535	0.381	—
Range, R	0.560	0.132	0.297	—

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表 7 高炉渣排碱实验结果回归方差分析

Table 7. Variance analysis of experimental results of alkali removal from blast furnace slag

Parameter	D_f	SS	MS	F value	Significance F
Regression analysis	3	0.843671	0.281224	8.973547	0.00216
Residual	12	0.37607	0.031339	—	—
Sum	15	1.219742	—	—	—

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