ELECTROCHEMICAL BEHAVIOR OF Ni2+ IN SiO2-CaO-MgO-Al2O3 MOLTEN SLAG AT 1673 K

doi:10.11900/0412.1961.2015.00065

Acta Metall Sin

2015, Vol. 51

Issue (8): 1001-1009 DOI: 10.11900/0412.1961.2015.00065

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ELECTROCHEMICAL BEHAVIOR OF Ni²⁺ IN SiO₂-CaO-MgO-Al₂O₃ MOLTEN SLAG AT 1673 K

Chuan HONG^1,²,Yunming GAO^1,²(

),Chuanghuang YANG²,Zhibo TONG²

1 The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081
2 Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education, Wuhan University of Science and Technology, Wuhan 430081

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Chuan HONG,Yunming GAO,Chuanghuang YANG,Zhibo TONG. ELECTROCHEMICAL BEHAVIOR OF Ni²⁺ IN SiO₂-CaO-MgO-Al₂O₃ MOLTEN SLAG AT 1673 K. Acta Metall Sin, 2015, 51(8): 1001-1009.

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Abstract

The modern iron and steel industry produces large emissions of CO₂ annually. Electrolytic reduction of molten slag containing iron oxide at high temperature using an inert oxygen evolving anode is an alternative process to reduce or eliminate the formation of CO₂. In order to establish reasonable process parameters of electrolytic method for steel containing Ni, it is necessary to master the electrochemical behavior of Ni²⁺ in molten slag. However, investigations on the electrochemical behavior of Ni²⁺ in molten slag at higher temperatures were very limited, which can probably be attributed to the experimental difficulties associated with the operation of high-temperature electrochemical cells. An electrolytic cell with a controlled oxygen flow and Pt, O₂(air)|ZrO₂ used as reference electrode was constructed integrally through a one-end-closed magnesia partially stabilized ZrO₂ solid electrolyte tube. Electrochemical behavior of Ni²⁺ on Ir electrode was investigated in SiO₂-CaO-MgO-Al₂O₃ molten slag at 1673 K by means of electrochemical techniques such as cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis. The results show that both diffusion in the molten slag and electromigration in the ZrO₂ solid electrolyte for the O²^- are not rate-determining steps of electrochemical reduction reaction process of electroactive ions. It is feasible to study electrochemical behavior of Ni²⁺ in the molten slag with the aid of the electrolytic cell with a controlled oxygen flow under the present experimental conditions. The reduction of Ni²⁺ on the Ir electrode in the molten slag is found to be a reversible reaction with a single step, and the rate of the process is diffusion controlled. Two diffusion coefficients of Ni²⁺ in the molten slag containing 3%NiO derived respectively from CV and CP are (3.50±0.18)×10^-⁶ and (2.80±0.22)×10^-⁶ cm²/s, which are consistent with records in the relevant literatures.

Key words: Ni²⁺ molten slag electrochemical behavior cathodic process electrolytic cell with controlled oxygen flow

Fund: Supported by National Natural Science Foundation of China (No.51174148)

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	Chuan HONG
	Yunming GAO
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	Zhibo TONG

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https://www.ams.org.cn/EN/10.11900/0412.1961.2015.00065 OR https://www.ams.org.cn/EN/Y2015/V51/I8/1001

Fig.1 Schematic of electrolytic cell

Fig.2 Open circuit potential (E)-time (t) curve response to dropping working electrode into molten slag containing 3%NiO and switching from Ar to air in the furnace tube

Fig.3 Cyclic voltammetric curves for molten slag with different NiO concentrations (w_NiO = 0, 1%, 3%, 5%) at scan rate of v = 0.2 V/s (E—potential, I—current)

Fig.4 Square wave voltammetric curves for the blank slag with frequency value of 30 Hz and for molten slag containing w_NiO=3% with different frequencies of 20, 30 and 40 Hz (Amplitude is 25 mV)

Fig.5 SEM images of the cross-section of Ir electrode for slag containing w_NiO=3% after potentiostatic electrolysis at -0.25 V (a), -0.70 V (b) and -1.30 V (c)

Fig.6 EDS analyses of spots 1 (a), 2 (b), 3 (c) and 4 (d) corresponding to Fig.5

Fig.7 SEM images of the MSZ-slag interface for slag containing w_NiO=3% after potentiostatic electrolysis at -0.70 V (a) and -1.30 V (b)

Fig.8 Cyclic voltammetric curves at scan rate of v=0.5 V/s with different scan cycles (w_NiO=3%)

Fig.9 Cyclic voltammetric curves for molten slag containing w_NiO=3% at different scan rates (v)

Fig.10 Reversal chronopotentiometry for molten slag containing w_NiO=3% with cathodic/anodic current of ±8 mA

Fig.11 Linear dependence of current of cathodic peak (I_pc) with v^1/2 corresponding to Fig.9

Table1 Collections for diffusion coefficient of Ni²⁺ in molten slag with similar composition and temperature

Fig.12 Chronopotentiograms for slag containing w_NiO=3% with different cathodic currents

Fig.13 Plot of cathodic currents (I) vs It^1/2 corresponding to Fig.12 (t—transition time)

Fig.14 Plots of E vs ln((t^1/2-t^1/2)/t^1/2) with different cathodic currents corresponding to Fig.12

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