微波場下的釩渣氯化動力學

譚博; 王麗君; 閆柏軍; 周國治

doi:10.13374/j.issn2095-9389.2019.09.20.003

微波場下的釩渣氯化動力學

doi: 10.13374/j.issn2095-9389.2019.09.20.003

譚博¹,
王麗君^{1, 2, ,},
閆柏軍³,
周國治^{1, 2}

1.
北京科技大學鋼鐵共性技術協同創新中心，北京 100083
2.
北京科技大學鋼鐵冶金新技術國家重點實驗室，北京 100083
3.
北京科技大學冶金與生態工程學院，北京 100083

基金項目: 國家自然科學基金資助項目（51774027，51734002）

詳細信息

通訊作者:
E-mail：lijunwang@ustb.edu.cn

中圖分類號: TF19
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出版歷程
- 收稿日期: 2019-09-20
- 刊出日期: 2020-09-20

Kinetics of chlorination of vanadium slag by microwave heating

TAN Bo¹,
WANG Li-jun^{1, 2
, ,},
YAN Bai-jun³,
CHOU Kuo-chih^{1, 2}

1.
Collaborative Innovation Center of Steel Technology, University of Science and Technology Beijing, Beijing 100083, China
2.
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing, Beijing 100083, China
3.
School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

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

摘要

摘要: 研究了微波加熱條件下（500～800 ℃），AlCl₃氯化釩渣中有價金屬Fe、Mn、V和Cr變溫動力學。通過X射線衍射和掃描電鏡能譜表征了氯化產物隨時間的物相演變和形貌變化，考察了AlCl₃/釩渣的質量比和熔鹽配比對氯化提取率的影響。結果表明，AlCl₃/釩渣的質量比為1.5、(NaCl-KCl)/AlCl₃熔鹽質量比為1.66∶1時Fe、Mn、V和Cr的提取率最佳，分別為91.66%、92.96%、82.67%、75.82%和63.14%，微波加熱30 min，5種元素的提取率達到或者超過常規加熱方式6 h的氯化提取效果。通過熱力學和動力學分析，橄欖石相優先于尖晶石相發生氯化反應。而且V和Cr的氯化反應速度小于Fe和Mn。Fe和Mn氯化過程為擴散控制，其非等溫擴散活化能為17.02和17.10 kJ·mol^?1, V和Cr在氯化過程中的限制性環節為界面化學反應，其表觀活化能分別為40.00和50.92 kJ·mol^?1；微波與熔鹽耦合強化氯化反應的機理可以描述為擴散作用增強和局部化學反應增強。
- 釩渣 /
- 微波加熱 /
- 熔鹽 /
- 變溫動力學 /
- 強化擴散
Abstract: Microwave heating was used in this study to chlorinate the extraction of Fe, Mn, V, and Cr from vanadium slag using AlCl₃ molten salt at a temperature range from 500 to 800 °C. Microwave heating chlorination kinetics was studied in a non-isothermal mode. The effects of the AlCl₃/vanadium slag mass ratio and molten salt ratio on the extraction rate of chlorination peoducts were investigated. The structure and morphology evolution of microwave heating chlorination products were characterized by X-ray diffraction and scanning electron microscope with energy dispersive spectrometer. The results show that the highest extraction rate of the five elements (Fe, Mn, V, Cr, and Ti) can be achieved as 91.66%, 92.96%, 82.67%, 75.82% and 63.14%, when the mass ratios of AlCl₃/vanadium slag and NaCl–KCl/AlCl₃ are 1.5 and 1.66, respectively. These extraction rates in the microwave heating mode for 30 min are reached and exceeded by 6 h in the conventional heating method. Microwave heating will minimize the chlorination time and reduce the volatilization of AlCl₃. Based on the thermodynamics and kinetic analysis, the different phases of vanadium slag can be chlorinated using AlCl₃ in the range from 400 to 800 °C, and the olivine phase is superior to the spinel phase in chlorination. In addition, the chlorination rates of V and Cr are slower than those of Fe and Mn, and increasing the reaction time is advantageous for the chlorination of V and Cr. The chlorination of Fe and Mn is controlled by diffusion, and the non-isothermal diffusion activation energies of Fe and Mn are 17.02 and 17.10 kJ·mol^?1, respectively. In contrast, the chlorination of V and Cr is limited in the interfacial chemical reaction step, for whom the activation energies give 40.00 and 50.92 kJ·mol^?1, respectively. The combination effect of the microwave and molten salt on the chlorinating vanadium slag can be attributed to the enhancement of the diffusion and local chemical reaction.
- vanadium slag /
- microwave heating /
- molten salt /
- non-isothermal kinetics /
- enhanced diffusion

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圖 1 原釩渣的X射線衍射圖

Figure 1. X-ray diffraction pattern of the original vanadium slag

下載: 全尺寸圖片幻燈片

圖 2 Mobilelab-T系列微波工作站結構圖

Figure 2. Microwave workstation structure of the Mobilelab-T series

1—Type-K thermocouple; 2—Temperature controller; 3—Magenetron; 4—Quartz tube; 5—Insulation material; 6—Quartz crucible

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圖 3 方程（2）～（9）中標準吉布斯自由能隨溫度變化的曲線圖（1 mol AlCl₃標準化）

Figure 3. Plots of standard Gibbs free energy as a function of temperature in Equations (2)-(9) (normalized by 1 mol AlCl₃)

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圖 4 AlCl₃–KCl–NaCl三元相圖

Figure 4. AlCl₃–KCl–NaCl phase diagram

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圖 5 AlCl₃/釩渣質量比對有價金屬氯化的影響

Figure 5. Effect of mass ratio of AlCl₃/vanadium slag on chlorination of valuable metals

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圖 6 不同氯化時間下氯化產物的X射線衍射圖。（a） 350 s；（b） 500 s；（c） 650 s；（d）原釩渣

Figure 6. X-ray diffraction patterns of products with different chlorination time: (a) 350 s; (b) 500 s; (c) 650 s; (d) original vanadium slag

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圖 7 微波加熱不同時間氯化產物的掃描電鏡?能譜圖。（a） 350 s；（b） 500 s；（c） 650 s

Figure 7. SEM-EDS morphologies of products by microwave heating for differnet time: (a) 350 s; (b) 500 s; (c) 650 s

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圖 8 樣品升溫過程溫度/時間關系

Figure 8. T/t relationship of sample heating process

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圖 9 ${\rm{ln}}\dfrac{{1 - 3{{\left( {1 - x} \right)}^{{2 / 3}}} + 2\left( {1 - x} \right)}}{{{T^2}}}$（a）和 ${\rm{ln}}\dfrac{{1 - {{\left( {1 - x} \right)}^{{1 / 3}}}}}{{{T^{1.92}}}}$（b）與1/T的關系

Figure 9. Relationship between ${\rm{ln}}\dfrac{{1 - 3{{\left( {1 - x} \right)}^{{2 / 3}}} + 2\left( {1 - x} \right)}}{{{T^2}}}$ (a) and ${\rm{ln}}\dfrac{{1 - {{\left( {1 - x} \right)}^{{1 / 3}}}}}{{{T^{1.92}}}}$ (b) with 1/T

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表 1 釩渣的化學組成 (質量分數)

Table 1. Chemical composition of the V-slag %

V₂O₃	Cr₂O₃	MnO	FeO	TiO₂	SiO₂	Al₂O₃	MgO	CaO
9.17	1.78	5.20	37.69	10.40	21.23	7.46	3.47	3.60

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表 2 不同熔鹽配比的有價金屬提取率

Table 2. Valuable metal extraction rate of different molten salt ratios

Heating temperature/ ℃	Holding time/ min	Molten salt ratio	Valuable metal extraction rate /%
Heating temperature/ ℃	Holding time/ min	Molten salt ratio	V	Cr	Mn	Fe
600	30	A	3.7	12.1	64.7	59.0
		B	24.4	14.9	59.9	60.6
		C	30.6	24.7	64.0	59.1
900	30	A	74.2	68.1	88.1	89.5
		B	80.7	73.4	87.5	89.0
		C	88.5	78.7	97.7	96.3

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表 3 微波加熱不同時間氯化產物中有價金屬的提取率

Table 3. Chlorination rate of valuable metals in samples by microwave heating for various time

Reaction time /s	Reaction temperature/ ℃	Valuable metal extraction rate /%
Reaction time /s	Reaction temperature/ ℃	V	Cr	Mn	Fe
350	507.9	2.3	1.9	49.2	46.0
400	577.3	5.5	5.0	59.4	56.1
450	635.7	8.0	10.2	65.5	59.5
500	686.3	15.1	11.1	73.4	68.1
550	728.5	18.9	21.1	77.5	72.2
600	765.4	18.0	22.6	78.7	74.9

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表 4 動力學方程的相關系數

Table 4. Correlation coefficient of the kinetic equation

Kinetic equations	V	Cr	Mn	Fe
Eq.(12)	0.9126	0.9344	0.5684	0.6423
Eq.(13)	0.9360	0.9458	0.9024	0.9600
Eq.(14)	0.9462	0.9672	0.3587	0.6956

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