Characterization of Fe5(AsO3)3Cl2(OH)4·5H2O, a new ferric arsenite hydroxychloride precipitated from FeCl3–As2O3–HCl solutions relevant to arsenic immobilization

Tooeleite(Fe6(As03)4 SO4(OH)4·4 H_2 O) is widely precipitated for direct As(III) removal from sulfate-rich industrial effluents.However,whether or not Fe(III)-As(III)-Cl(-I) precipitate is produced in chloridizing leaching media for As immobilization is almost unknown.This work founded the existence of ferric arsenite(hydroxy)chloride as a new mineral for As(III)removal.Its chemical composition and solid characterization were subsequently studied by using scanning electron microscope with an energy dispersive spectrometer(SEM-EDS),X-ray diffraction(XRD),infrared(FT-IR),Raman spectroscopy and thermogravimetric(TG)curve.The results showed the formation of a yellow precipitate after 3-days reaction of Fe(III)/As(III) with molar ratio≈1.7 in chloride solution at pH 2.3 neutralized with NaOH.Compared with tooeleite,chemical analysis and solid characterization indicated that Cl(-I)replaces S04(-II) producing ferric arsenite hydroxychloride with formula Fe5(As03)_3-Cl_2(OH)4·5 H_2 O.This new plate shaped solid showed better crytallinity than tooeleite,although it has similar morphology and characteristic bands to tooeleite.The FT-IR bands at 628,964 cm-1 and the Raman bands at 448,610,961 cm-1 were assigned to Fe-O or As(Ⅲ)-O-Fe or As(Ⅲ)-O bending/stretching vibration,indicating that both arsenite and chloride substituted for the position of sulfate for ferric arsenite hydro xychloride produced due to the lack of the SO_4~(2-) vibrations.Cl-(I) also contributed to increase As removal efficiency in aqueous sulfate media under acidic pH conditions via the probable formation of sulfatechloride ferric arsenite.     

N,N’-二(2-羟丙基)哌嗪-H2SO4水溶液吸收SO2动力学

在鼓泡式反应器中,以N,N’-二(2-羟丙基)哌嗪(HPP)-硫酸水溶液为吸收剂,利用初始速率法探讨了SO2吸收反应动力学.结果表明:HPP-H2SO4水溶液吸收SO2为快速反应;吸收速率NA随着SO2进口体积浓度yA和吸收剂浓度CN的增大而增大,随着吸收温度T的升高而降低;吸收速率对CN是0.5级反应,对yA为0.85级反应.同时,建立了HPP-H2 SO4水溶液吸收SO2的吸收速率NA与CN、yA及T之间的经验关系式,发现该经验关系式的预测值与实验值符合较好,可用于工程设计计算.     

Simultaneous oxidation of Mn(II) and As(III) on cupric oxide (CuO) promotes As(III) removal at circumneutral pH

Oxidation of Mn(II) or As(III) by molecular oxygen is slow at pH < 9, while they can be catalytically oxidized in the presence of oxide minerals and then removed from contaminated water. However, the reaction mechanisms on simultaneous oxidation of Mn(II) and As(III) on oxide mineral surface and their accompanied removal efficiency remain unclear. This study compared Mn(II) oxidation on four common metal oxides (γ-Al₂O₃, CuO, α-Fe₂O₃ and ZnO) and investigated the simultaneous oxidation and removal of Mn(II) and As(III) through batch experiments and spectroscopic analyses. Among the tested oxides, CuO and α-Fe₂O₃ possess greater catalytic activity toward Mn(II) oxidation. Oxidation and removal kinetics of Mn(II) and As(III) on CuO indicate that O₂ is the terminal electron acceptor for Mn(II) and As(III) oxidation on CuO, and Mn(II) acts as an electron shuttle to promote As(III) oxidation and removal. The main oxidized product of Mn(II) on CuO is high-valent MnO_x species. This newly formed Mn(III) or Mn(IV) phases promote As(III) oxidation on CuO at circumneutral pH 8 and is reduced to Mn(II), which may be then released into solution. This study provides new insights into metal oxide-catalyzed oxidation of pollutants Mn(II) and As(III) and suggests that CuO should be considered as an efficient material to remediate Mn(II) and As(III) contamination.     

Removal of Ni(II) from strongly acidic wastewater by chelating precipitation and recovery of NiO from the precipitates

Strongly acidic wastewater produced in nonferrous metal smelting industries often contains high concentrations of Ni(II), which is a valuable metal. In this study, the precipitation of Ni(II) from strongly acidic wastewater using sodium dimethyldithiocarbamate (DDTC) as the precipitant was evaluated. The effects of various factors on precipitation were investigated, and the precipitation mechanism was also identified. Finally, the nickel in the precipitates was recovered following a pyrometallurgical method. The results show that, under optimised conditions (DDTC:Ni(II) molar ratio = 4:1; temperature = 25 °C), the Ni(II) removal efficiency reached 99.3% after 10 min. In strongly acidic wastewater, the dithiocarbamate group of DDTC can react with Ni(II) to form DDTCNi precipitates. Further recovery experiments revealed that high-purity NiO can be obtained by the calcination of DDTCNi precipitates, with the nickel recovery efficiency reaching 98.2%. The gas released during the calcination process was composed of NO₂, CS₂, H₂O, CO₂, and SO₂. These results provide a basis for an effective Ni(II) recovery method from strongly acidic wastewater.