鐵酸鋅碳熱還原動力學及反應機理

李洋; 張建良; 袁驤; 劉征建; 李飛; 鄭安陽; 李占國

doi:10.13374/j.issn2095-9389.2021.08.05.003

鐵酸鋅碳熱還原動力學及反應機理

doi: 10.13374/j.issn2095-9389.2021.08.05.003

李洋^{1, 2},
張建良¹,
袁驤³,
劉征建^1, ,,
李飛⁴,
鄭安陽¹,
李占國¹

1.
北京科技大學冶金與生態工程學院，北京 100083
2.
北京首鋼股份有限公司煉鐵作業部，唐山 064404
3.
湖南華菱湘潭鋼鐵有限公司煉鐵廠，湘潭 411101
4.
山西建龍鋼鐵有限公司，運城 043800

基金項目: 中央高校基金科研業務費資助項目（06500170）；廣東省基礎與應用基礎研究基金聯合區域基金青年基金資助項目（2020A1515111008）

詳細信息

通訊作者:
E-mail: liuzhengjian@ustb.edu.cn

中圖分類號: TF01
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- 被引次數: 0
出版歷程
- 收稿日期: 2021-08-05
- 網絡出版日期: 2021-09-22
- 刊出日期: 2023-01-01

Kinetics and reduction mechanism of non-isothermal analysis carbothermal reduction of zinc ferrite

1.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.
Ironmaking Department of Beijing Shougang Co., Ltd., Tangshan 064404, China
3.
Ironmaking Department, Xiangtan Iron and Steel Co., Ltd of HuNan VaLin, Xiangtan 411101, China
4.
Shanxi Jianlong Industry Company, Ltd., Yuncheng 043800, China

More Information

Corresponding author: E-mail: liuzhengjian@ustb.edu.cn

摘要

摘要: 對鐵酸鋅非等溫碳熱還原反應動力學及其還原反應機理進行了研究。通過不同溫度條件下還原后的鐵酸鋅團塊物相分析(XRD)對其碳熱還原的物相轉變過程進行了解析，950 ℃時出現FeO_0.85·xZnO無定型物質，此時Fe³⁺被還原成Fe²⁺。探討了鐵酸鋅碳熱還原過程轉化率與轉化速率的關系，該還原過程可以劃分為三個階段，第二階段的轉化率變化最大(0.085～0.813)。最后，通過等轉化率法和主曲線擬合法對不同升溫速率條件下鐵酸鋅碳熱還原第二階段的動力學進行了分析，可以得出第二階段的平均活化能為362.16 kJ·mol^–1，且該階段活化能為331.01～490.04 kJ·mol^–1，變化較大，說明這一階段發生的反應較為復雜，且各反應之間的活化能差異明顯，二級化學反應是這一階段的主要控速環節，并確定了第二階段的主要控速方程。
- 含鋅粉塵 /
- 鐵酸鋅 /
- 碳熱還原 /
- 動力學 /
- 活化能
Abstract: The amount of zinc-containing EAF dust has increased due to the increased proportion of galvanized steel scrap used in the electric arc furnace (EAF) steelmaking process. If the zinc in the EAF dust is not recycled, it will not only lead to a waste of valuable metal resources but also results in environmental pollution. Zinc is mainly present in the EAF dust in the form of zinc ferrite (ZnFe₂O₄). Zinc ferrite is a kind of spinel mineral that exhibits a crystal lattice of greater stability, which increases the difficulty of recycling valuable elements such as zinc and iron from zinc-containing EAF dust. To further clarify the carbothermic reduction process of zinc ferrite, this paper studies the kinetics of the non-isothermal carbothermal reduction of zinc ferrite and its reduction reaction mechanism. The phase transition process of the zinc ferrite carbothermal reduction reaction was analyzed via the XRD results of the reduced zinc ferrite. FeO_0.85·xZnO was found at 950 °C when Fe³⁺ was reduced to Fe²⁺. The relationship between the conversion and conversion rate of the zinc ferrite carbothermal reduction process is discussed. The reduction process can be divided into three stages, and the conversion of the second stage changes greatly (0.085–0.813). Finally, the kinetics of the second stage of the carbothermic reduction of the zinc ferrite at different heating rates was evaluated through the isoconversional method and the master curve fitting method. The activation energy of the second stage is between 331.01–490.04 kJ·mol^?1, and the average activation energy is 362.16 kJ·mol^?1. The large change in the activation energy in the second stage indicates that the reactions in this stage are more complicated, and there are obvious differences in the activation energy between the reactions. The secondary chemical reaction is the main rate-controlling link in the second stage, and the kinetics equation of the second stage is determined.
- zinc-containing dust /
- zinc ferrite /
- carbothermal reduction /
- kinetics /
- activation energy

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圖 1 不同溫度條件下鐵酸鋅碳熱還原后的XRD結果

Figure 1. XRD analysis result of the products of zinc ferrite carbothermal reduction at different temperatures

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圖 2 無煙煤還原ZnFe₂O₄時轉化率變化曲線

Figure 2. Conversion ratio curve of ZnFe₂O₄ reduced by anthracite

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圖 3 不同升溫速率下鐵酸鋅還原轉化率與DTG（Derivative thermogravimetry）的關系

Figure 3. Relationship between conversion rate of the zinc ferrite and DTG at different heating rates

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圖 4 不同升溫速率下鐵酸鋅還原轉化率與DDTG關系

Figure 4. Relationship between conversion rate of the zinc ferrite and DDTG at different heating rates

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圖 5 各階段相對轉化率與DTG關系.(a)第一階段；(b)第二階段；(c) 第三階段

Figure 5. Relationship between relative conversion rate and DTG in different reaction stages: (a) first stage; (b) second stage; (c) third stage

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圖 6 1/T與lnt之間的線性關系

Figure 6. Relationship between 1/T and lnt

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圖 7 不同轉化率時活化能與轉化率的關系

Figure 7. Relationship between activation energy and conversion rate

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圖 8 不同升溫速率時y(α)′與轉化率之間的關系曲線

Figure 8. Relationship between y(α)′ and conversion rate at different heating rates

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圖 9 鐵酸鋅碳熱還原反應各階段劃分及其化學反應示意圖

Figure 9. Schematic diagram of the stages and chemical reactions of the carbothermal reduction of zinc ferrite

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表 1 無煙煤還原鐵酸鋅反應階段劃分

Table 1. Reaction stages of zinc ferrite reduced by anthracite

Heating rate / (℃·min^–1)	First stage		Second stage		Third stage
Heating rate / (℃·min^–1)	α	Temperature / ℃	α	Temperature / ℃	α	Temperature / ℃
5	0–0.089	< 923.68	0.089–0.842	923.68–1100.54	0.842–1	> 1100.54
10	0–0.089	< 932.98	0.089–0.832	932.98–1132.26	0.832–1	> 1132.26
15	0–0.080	< 945.66	0.080–0.801	945.66–1135.51	0.801–1	> 1135.51
20	0–0.081	< 952.39	0.081–0.778	952.39–1138.36	0.778–1	> 1138.36
Average	0–0.085	< 938.68	0.085–0.813	938.68–1126.67	0.813–1	> 1126.67

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表 2 常見的還原反應機理函數^[22–24]

Table 2. Common mechanism functions in the reduction reaction^[22–24]

Mechanism		Code	Differential form, f(α)	Integral form, G(α)
Chemical reaction	n = 1	F1	(1?α)	?ln(1?α)
	n = 2	F2	(1?α)²	(1?α)^–1?1
	n = 3	F3	(1?α)³	[(1?α)^–1?1]/2
Diffusion	The two-dimensional diffusion control	D2	[?ln(1?α)]^–1	α+(1?α)ln(1?α)
	The three-dimensional diffusion control (Jander function)	D3	1.5(1?α)^2/3[1?(1?α)^1/3]^–1	[1?(1?α)^1/3]²
	The three-dimensional diffusion control (Ginstling–Brounshten function)	D4	1.5[(1?α)^1/3?1]^–1	(1?2α/3) ?(1?α)^2/3
Random nucleation and nuclei growth	Two dimension	A2	2(1?α)[?ln(1?α)]^1/2	[?ln(1?α)]^1/2
Random nucleation and nuclei growth	Three dimension	A3	3(1?$\alpha $)[?ln(1?$\alpha $)]^2/3	[?ln(1?$\alpha $)]^1/3
Exponential nucleation	Power series law, n = 3/2	P23	(2/3)α^?1/2	α^3/2
	Power series law, n = 1/2	P2	2α^1/2	α^1/2
	Power series law, n = 1/3	P3	3$\alpha $^2/3	α^1/3
	Power series law, n = 1/4	P4	4α^3/4	α^1/4
Phase boundary reaction	Cylindrical symmetry	R2	2(1?α)^1/2	1? (1?α)^1/2
Phase boundary reaction	Spherical symmetry	R3	3(1?α)^2/3	1?(1?α)^1/3

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表 3 不同升溫速率條件下各轉化率對應的溫度

Table 3. Reaction temperature corresponding to different conversion rates at different heating rates ℃

α	Heating rate / (℃·min^–1)
α	5	10	15	20
0.10	929.95	940.73	955.46	961.66
0.15	949.93	966.20	981.88	990.89
0.20	962.99	981.85	997.96	1007.57
0.25	973.01	993.59	1010.12	1020.07
0.30	981.44	1003.43	1020.07	1030.30
0.35	988.78	1011.77	1028.72	1039.35
0.40	995.45	1019.21	1036.92	1047.79
0.45	1001.87	1026.42	1044.75	1056.00
0.50	1008.79	1033.85	1052.55	1064.28
0.55	1016.65	1042.11	1061.12	1072.96
0.60	1026.25	1051.84	1071.16	1083.13
0.65	1037.79	1064.36	1083.55	1095.31
0.70	1051.73	1079.24	1098.20	1109.86
0.75	1069.33	1096.75	1114.68	1127.40
0.80	1090.04	1116.93	1135.03	1146.83

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表 4 不同轉化率時的活化能及第二階段平均活化能

Table 4. Activation energy at different conversion rates and average activation energy of the second stage

α	Activation energy / (kJ·mol^–1)	R2	Average activation energy / (kJ·mol^–1)
0.10	490.04	0.9668	362.16
0.15	405.92	0.9879
0.20	383.16	0.9935
0.25	369.52	0.9958
0.30	361.42	0.9974
0.35	353.63	0.9980
0.40	344.68	0.9978
0.45	336.49	0.9978
0.50	332.06	0.9978
0.55	331.01	0.9978
0.60	332.45	0.9975
0.65	334.62	0.9985
0.70	338.48	0.9992
0.75	350.61	0.9996
0.80	368.30	0.9995

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