DESIGN AND DEVELOPMENT OF A STABILIZER FOR ARSENIC-CONTAINING RESIDUE BASED ON SIMPLEX-CENTROID DESIGN METHOD
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摘要: 以FeSO4·H2O、零价铁(ZVI)和二氧化锰(MnO2)为原料,采用单纯形重心设计法(SCMD)对混合料配比进行建模和优化,设计开发出一种新型复合铁基稳定剂,并应用于含砷废渣的稳定。结果表明:以质量分数为65.05% FeSO4·H2O、10.00% ZVI和24.95% MnO2混料制备的复合铁基稳定剂可实现最低成本的As长效稳定化。利用25%新型复合铁基稳定剂处理砷钙渣(ACR),可使As浸出浓度从162 mg/L降至0.645 mg/L,低于GB 18598—2019《污染废物填埋控制标准》规定的上限(1.2 mg/L)。采用SEM-EDS、FTIR和XPS方法研究了ACR中As的稳定机理,即有效态As通过Fe/Mn(氢化物)氧化物和Fe(Ⅲ)的吸附、络合和沉淀,形成稳定的非晶态Fe/Mn-As,复合铁基稳定剂结合H2SO4通过"释放-氧化-稳定"的过程获得优异的As稳定性能。该研究结果可为多组分复合稳定剂的设计和实现含砷固体废物的有效稳定提供理论依据。Abstract: In this study, the simplex-centroid design method (SCMD) was used to model and optimize the mixing ratio of FeSO4·H2O zero-valent iron (ZVI) and manganese dioxide (MnO2) as the raw materials, and a new composite Fe-based stabilizer was designed and developed, and then applied to the stabilization of arsenic-containing residue. The results showed that the optimum combination for high As stabilization performance and low cost of stabilizer was the mixture of 65.05, 10.00 and 24.95 % FeSO4·H2O, ZVI and MnO2. The leaching concentration of As decreased from 162 mg/L to 0.645 mg/L, lower than the limit value(1.2 mg/L) prescribed in China. The stability mechanism of As in ACR was studied by SEM-EDS, FTIR and XPS, while the available As was stabilized by adsorption, complexation and precipitation of Fe/Mn (hydride) oxide and Fe(Ⅲ), forming stable amorphous Fe/Mn-As. The composite Fe-based stabilizer combined with H2SO4 obtained excellent stability of As through a process of release-oxidation-stabilization. This study provides an sound theoretical basis for design of multi-component composite stabilizers and effective stabilization of arsenic-containing residue.
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Key words:
- arsenic-containing residue /
- mixture design /
- stabilizer /
- long-term stability
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[1] LOWENSTAM H A. Minerals formed by organisms[J]. Science, 1981, 211(4487): 1126-1131. [2] RIVEROS P A, DUTRIZAC J E, SPENCER P. Arsenic disposal practices in the metallurgical industry[J]. Canadian Metallurgical Quarterly, 2001, 40(4): 395-420. [3] ZHANG D N, WANG S F, WANG Y, et al. The long-term stability of calcium arsenates: implications for phase transformation and arsenic mobilization[J]. Journal of Environmental Sciences, 2019, 84(10): 29-41. [4] MARTINEZ-VILLEGAS N, BRIONES-GALLARDO R, RAMOS-LEAL J A, et al. Arsenic mobility controlled by solid calcium arsenates: a case study in Mexico showcasing a potentially widespread environmental problem[J]. Environmental Pollution, 2013, 176(5): 114-122. [5] YOON I H, MOON D H, KIM K W, et al. Mechanism for the stabilization/solidification of arsenic-contaminated soils with Portland cement and cement kiln dust[J]. Journal of Environmental Management, 2010, 91(11): 2322-2328. [6] 张淑媛, 童宏祥, 徐诗琦, 等. 次氯酸钙/氧化钙对高砷污泥的氧化稳定化处理[J]. 环境工程学报, 2018, 12(2): 625-629. [7] WANG X, ZHANG H, WANG L L, et al. Transformation of arsenic during realgar tailings stabilization using ferrous sulfate in a pilot-scale treatment[J]. The Science of the Total Environment, 2019, 668: 32-39. [8] CLANCY T M, SNYDER K V, REDDY R, et al. Evaluating the cement stabilization of arsenic-bearing iron wastes from drinking water treatment[J]. Journal of Hazardous Materials, 2015, 300: 522-529. [9] 罗中秋, 周新涛, 贾庆明, 等. 磷渣基地聚物材料固化砷钙渣的机理[J]. 硅酸盐学报, 2015, 43(5):699-704. [10] LI J S, WANG L, CUI J L, et al. Effects of low-alkalinity binders on stabilization/solidification of geogenic As-containing soils: spectroscopic investigation and leaching tests[J]. Science of the Total Environment, 2018, 631/632: 1486-1494. [11] LI Y, MIN X B, CHAI L Y, et al. Co-treatment of gypsum sludge and Pb/Zn smelting slag for the solidification of sludge containing arsenic and heavy metals[J]. Journal of Environmental Management, 2016, 181: 756-761. [12] LIU D G, MIN X B, KE Y, et al. Co-treatment of flotation waste, neutralization sludge, and arsenic-containing gypsum sludge from copper smelting: solidification/stabilization of arsenic and heavy metals with minimal cement clinker[J]. Environmental Science and Pollution Research, 2018, 25(8): 7600-7607. [13] 李辕成, 闵小波, 柴立元, 等. 冶炼废渣协同固化/稳定化含砷污泥[C]//第五届重金属污染防治及风险评价研讨会暨重金属污染防治专业委员会2015年学术年会,南宁, 2015: 261-267. [14] LI E P, YANG T, WANG Q, et al. Long-term stability of arsenic calcium residue (ACR) treated with FeSO4 and H2SO4: function of H+ and Fe(Ⅱ)[J]. Journal of Hazardous Materials, 2021, 420: 126549. [15] JING C Y, KORFIATIS G P, MENG X G. Immobilization mechanisms of arsenate in iron hydroxide sludge stabilized with cement[J]. Environmental Science & Technology, 2003, 37(21): 5050-5056. [16] JIA Y F, XU L Y, WANG X, et al. Infrared spectroscopic and X-ray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite[J]. Geochimica et Cosmochimica Acta, 2007, 71(7): 1643-1654. [17] SONG J, JIA S Y, YU B, et al. Formation of iron (hydr) oxides during the abiotic oxidation of Fe (Ⅱ) in the presence of arsenate[J]. Journal of Hazardous Materials, 2015, 294: 70-79. [18] WANG S F, ZHANG D N, LI X L, et al. Arsenic associated with gypsum produced from Fe (Ⅲ)-As (Ⅴ) coprecipitation: implications for the stability of industrial As-bearing waste[J]. Journal of Hazardous Materials, 2018, 360: 311-318.
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