4.7 Article

Inhibition of Cr6+ by the formation of in-situ Cr3+ containing solid-solution in Al2O3-CaO-Cr2O3-SiO2 system

Journal

CERAMICS INTERNATIONAL
Volume 47, Issue 7, Pages 9578-9584

Publisher

ELSEVIER SCI LTD
DOI: 10.1016/j.ceramint.2020.12.092

Keywords

Al2O3-CaO-Cr2O3-SiO2 quaternary system; CaAl2Cr23+O7; Gehlenite; Anorthite; Cr(VI); Leaching kinetics(1)

Funding

  1. National Natural Science Foundation of China [51604203, 51950410587]
  2. China Postdoctoral Science Foundation [2019M652719]
  3. Hubei Natural Science Foundation [2018CFB759]

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The Al2O3-CaO-Cr2O3 system doped with SiO2 under heat treatment in an air atmosphere successfully inhibited the generation of toxic Cr6+ and transformed it into stable Cr3+, thus reducing harm. The investigation showed that the addition of SiO2 led to the disappearance of Cr6+ compound Ca4Al6Cr6+O16 and the formation of Cr3+ in a more stable phase, effectively preventing Cr6+ at elevated temperatures.
The pseudo-ternary Al2O3-CaO-Cr2O3 system is of great interest due to various pyrometallurgical applications. However, Cr3+ might be oxidized into toxic and carcinogenic Cr6+ during service, causing harm to humans and the environment. So, doping an adequate amount of SiO2 could suppress the generation of Cr6+. In this experiment, the Al2O3-CaO-Cr2O3 ternary system was doped with different amounts of SiO2 (0-47 wt%) and heat-treated at 1400 degrees C in the air atmosphere. The reaction mechanism and the phase evolution process were studied by implementing XRD, SEM-EDS, leaching tests, XPS, and associated software. In the Al2O3-CaO-Cr2O3 system under the air atmosphere, chromium primarily exists as a Cr3+ compound CaAl2Cr23+O7 and a Cr6+ compound Ca4Al6Cr6+O16 as a secondary phase. The Cr6+ leaching process was diffusion-controlled and more effective at elevated temperatures. However, Ca4Al6Cr6+O16 disappeared with the addition of SiO2. With the increase of SiO2 content, Cr2O3 tends to be in the Cr3+ form with gehlenite phase (Ca-2(Al, Cr)(2)SiO7) and anorthite phase (Ca(Al, Cr)(2)Si2O8), thereby inhibiting the Cr6+. Nevertheless, the investigated compositions in the quaternary systems do not exhibit Cr6+ in the air atmosphere at 1400 degrees C.

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