爐渣成分對冶煉白云鄂博礦高爐渣脫硫和排堿能力的影響

張國成; 王雅軍; 羅果萍

doi:10.13374/j.issn2095-9389.2020.11.19.001

爐渣成分對冶煉白云鄂博礦高爐渣脫硫和排堿能力的影響

doi: 10.13374/j.issn2095-9389.2020.11.19.001

張國成^{1, 2, ,},
王雅軍³,
羅果萍^2, ,

1.
包頭師范學院化學學院, 包頭 014030
2.
內蒙古科技大學材料與冶金學院, 包頭 014010
3.
內蒙古包鋼鋼聯股份有限公司技術中心, 包頭 014010

基金項目: 國家自然科學基金資助項目（51664045）

詳細信息

通訊作者:
張國成，E-mail: 644942242@qq.com

羅果萍，E-mail: luoguoping3@126.com

中圖分類號: TF046
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- HTML全文瀏覽量: 280
- PDF下載量: 44
- 被引次數: 0
出版歷程
- 收稿日期: 2020-11-19
- 網絡出版日期: 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: 為了探明爐渣成分對冶煉白云鄂博礦高爐渣脫硫和排堿能力的影響，在實際高爐渣成分的基礎上，通過正交試驗和Factsage 7.1熱力學模擬軟件繪制不同組分高爐渣渣系五元偽三元相圖，探究了自由堿度（R_o）、w(MgO)和w(Al₂O₃)對高爐渣脫硫、排堿能力的影響規律，并結合生產實際給出了適宜的爐渣自由堿度（R_o）、w(MgO)和w(Al₂O₃)的控制范圍。研究表明： R_o是影響爐渣脫硫、排堿能力的最顯著因素，R_o增加，渣中O^2?濃度升高，促使硅氧復合陰離子Si?O解體，爐渣黏度減小，爐渣與金屬液體之間的傳質過程得到促進，使得S^2?更容易向渣中遷移，爐渣脫硫的熱力學和動力學條件改善，脫硫能力提高，適宜的R_o應控制在1.05～1.15；w(MgO)是影響爐渣脫硫能力的次要因素，w(MgO)增加，爐渣的流動性和穩定性提高，有利于改善爐渣脫硫的動力學條件，且可降低爐渣中(K₂O+Na₂O)的活度，提高排堿能力，適宜w(MgO)應控制在15%左右；w(Al₂O₃)是影響爐渣排堿能力的次要因素，w(Al₂O₃)增加，易生成鎂鋁尖晶石(MgAl₂O₄)等高熔點物質，使爐渣中的自由氧離子消耗量增多，不利于脫硫反應動力學條件的改善，雖然增加w(Al₂O₃)有益于排堿，但高w(Al₂O₃)不利于脫硫，且會導致爐渣黏度上升，適宜w(Al₂O₃)應控制在12%左右。
- 高爐渣 /
- 白云鄂博礦 /
- 爐渣成分 /
- 脫硫 /
- 排堿
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 O^2? 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 S^2? 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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圖 1 高溫熔渣脫硫實驗裝置

Figure 1. High-temperature slag viscosity measuring device

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圖 2 高溫熔渣排堿實驗裝置

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

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圖 3 高爐渣脫硫能力主觀效應圖

Figure 3. Subjective effect diagram of blast furnace slag desulfurization

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圖 4 高爐渣排堿實驗結果主觀效應圖

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

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5 不同R_o條件下的CaO?SiO₂?MgO?Al₂O₃?CaF₂五元渣偽三元相圖.(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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圖 6 不同MgO含量的CaO?SiO₂?MgO?Al₂O₃?CaF₂五元渣偽三元相圖. (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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圖 7 不同Al₂O₃含量的 CaO?SiO₂?MgO?Al₂O₃?CaF₂ 五元渣偽三元相圖. (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 高爐渣實際化學成分

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 實驗設計方案

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 合成渣實際化學成分

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 高爐渣脫硫實驗結果極差分析

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 高爐渣脫硫實驗結果回歸方差分析

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 高爐渣排堿實驗結果

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 高爐渣排堿實驗結果回歸方差分析

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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