还原剂对偏高岭土基矿物聚合物解毒铬渣的影响
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摘要
目前常用的铬渣处理方法存在铬形态不稳定、残留的酸溶性Cr(Ⅵ)易淋出等问题,该研究以添加还原剂的偏高岭土基矿物聚合物来直接处理铬渣,探索铬渣的一步解毒/固化及无害化利用。实验中将铬渣和偏高岭土混合用于制备矿物聚合物,加入Na_2S、Na_2SO_3、FeSO_4和FeCl_2作还原剂,改变还原剂的添加比例,对比制备的偏高岭土/铬渣基矿物聚合物固化体的浸出性毒性实验中Cr的浓度,选择最佳还原剂种类及比例。并在最佳还原剂的基础上,探索铬渣的最大处理量。
At present, the commonly used chromium residue treatment method has the problems of unstable form of chromium, acid soluble Cr(Ⅵ). In this study, chromium residue was treated directly by adding a reducing agent, and a step of detoxification/solidification and harmless utilization of chromium residue was explored. In the experiment, chromium residue and metakaolin were mixed to prepare geopolymer. Adding Na_2S, Na_2SO_3, FeSO_4 and FeCl_2 as reducing agents, changing the proportion of reducing agents added, the concentration of Cr in the leachate toxicity experiments of the prepared metakaolin/chromium residue based geopolymer was compared, to select the best type and proportion of reducing agent. On the basis of the best reducing agent, the maximum treatment quantity of chromium residue is explored.
At present, the commonly used chromium residue treatment method has the problems of unstable form of chromium, acid soluble Cr(Ⅵ). In this study, chromium residue was treated directly by adding a reducing agent, and a step of detoxification/solidification and harmless utilization of chromium residue was explored. In the experiment, chromium residue and metakaolin were mixed to prepare geopolymer. Adding Na_2S, Na_2SO_3, FeSO_4 and FeCl_2 as reducing agents, changing the proportion of reducing agents added, the concentration of Cr in the leachate toxicity experiments of the prepared metakaolin/chromium residue based geopolymer was compared, to select the best type and proportion of reducing agent. On the basis of the best reducing agent, the maximum treatment quantity of chromium residue is explored.
引文
[1] Xu W, Li X, Zhou Q, et al. Remediation of chromite ore processing residue by hydrothermal process with starch[J]. Process Saf Environ, 2011,89:179-185.
[2] Hillier S, Roe MJ, Geelhoed JS, et al. Role of quantitative mineralogical analysis in the investigation of sites contaminated bychromite ore processing residue[J]. Sci Total Environ, 2003,308:195-210.
[3] Geelhoed JS, Meeussen JCL, Hillier S, et al. Identification and geochemical modeling of processes controlling leaching of Cr(Ⅵ)and other major elements from chromite ore processing residue[J]. Geochim Cosmochim Acta, 2002, 66:3927-3942.
[4] Chen H, Xiao Q, Xu H, et al. Countermeasures and suggestions for chromate industry pollution control[J]. Environ Prot Chem Ind, 2013,33:23-27.
[5] Palmer CD, Wittbrodt PR. Processes affecting the remediation of chromium-contaminated sites[J]. Environ Health Perspect, 1991,92:25-40.
[6] US EPA. In situ Treatment of Soil&Groundwater Contaminated with Chromium:Technical Resource Guide[R].EPA/625/R-00/005, Washington DC, 2000.
[7] Chrysochoou M, Johnston CP, Dahal G. A comparative evaluation of hexavalent chromium treatment in contaminated soil by calcium polysulfide and green-tea nanoscale zerovalent iron[J]. J Hazard Mater, 2012,201/202:33-42.
[8] Zayed A, Lytle CM, Qian JH, et al. Chromium accumulation, translocation and chemical speciation in vegetable crops[J]. Planta, 1998,206:293-299.
[9] Dermatas D, Chrysochoou M, Moon DH, et al. Christodoulatos, Ettringite-induced heave in chromite ore processing residue(COPR)upon ferrous sulfate treatment[J]. Environ Sci Technol, 2006,40:5786-5792.
[10] Du J, Lu J, Wu Q, et al. Reduction and immobilization of chromate in chromite ore processing residue with nanoscale zero-valent iron[J]. J Hazard Mater, 2012,215/216:152-158.
[11] Kiser JR, Manning BA. Reduction and immobilization of chromium(Ⅵ)by iron(Ⅱ)-treated fauja site[J]. J Hazard Mater, 2010,174:167-174.
[12] Graham MC, Farmer JG, Anderson P, et al. Calcium polysulfide remediation of hexavalent chromium contamination from chromite ore processing residue[J]. Sci Total Environ,2006,364:32-44.
[13] Velasco A, Ram?'rez M, Herna'ndez S, et al. Pilot scale treatment of chromite ore processing residue using sodium sulfide in single reduction and coupled reduction/stabilization processes[J]. J Hazard Mater, 2012,207/208:97-102.
[14] Zhang D, He S, Dai L, et al. Treatment of chromite ore processing residue by pyrolysis with rice straw[J]. Chemosphere, 2009,77:1143-1145.
[15] Kindness A, Macias A, Glasser FP. Immobilization of chromium in cement matrices[J]. Waste Manage, 1994,14:3-11.
[16] Davidovits J. Geopolymers-inorganic polymeric new materials[J].J Therm Anal, 1991,37:1633-1656.
[17] Zhang J, Provis JL, Feng D, et al. Geopolymers for immobilization of Cr6+, Cd2+and Pb2+[J]. J Hazard Mater, 2008,157:587-598.
[18] Silva PD, Sagoe-Crenstil K, Sirivivatnanon V. Kinetics of geopolymerization:role of Al2O3and SiO2[J]. Cem Concr Res, 2007,37:512-518.
[19] Lu QY. Research of Preparation and Application of Geopolymer[R].Fuzhou:Fuzhou University, 2005.
[20] USEPA. Toxicity Characteristic Leaching Procedure Method 1311, 1992[R]. Washington, DC.
[21] GB/T 15555.4-1995,固体废物六价铬的测定二苯碳酰二肼分光光度法[S].GB/T 15555.4-1995, Solid Waste-Determination of Chromium(Ⅵ)-1, 5-Diphenylcarbohydrazide Spectrophotomatric Method[S].
[22] GB/5085.3-2007,危险废物鉴别标准浸出毒性鉴别[S].GB/5085.3-2007, Identification Standards for Hazardous Wastes-Identification for Extraction Toxicity[S].
[23] GB/T 17671-1999,水泥胶砂强度检验方法[S].GB/T 17671-1999, Method of Testing Cements-Determination of Strength[S].
[24] Dupont L, Guillon E. Removal of hexavalent chromium with a lignocellulosic substrate extracted from wheat bran[J]. Environmental Science and Technology, 2003, 37(18):4235-4241.
[25] Li X, Cao J, Zhang W. Stoichiometry of Cr(Ⅵ)immobilization using nanoscale zero valent iron(nZVI):a study with high-resolution X-ray photoelectron spectroscopy(HRXPS)[J]. Industrial&Engineering Chemistry Research,2008,47(7):2131-2139.
[26] Terlingen J G A, Feijen J, Hoffman A S. Immobilization of surface-active compounds on polymer supports using glowdischarge processes:1. sodium dodecyl-sulfate on poly(propylene)[J]. Journal of Colloid and Interface Science,1993,155(1):55-65.
[2] Hillier S, Roe MJ, Geelhoed JS, et al. Role of quantitative mineralogical analysis in the investigation of sites contaminated bychromite ore processing residue[J]. Sci Total Environ, 2003,308:195-210.
[3] Geelhoed JS, Meeussen JCL, Hillier S, et al. Identification and geochemical modeling of processes controlling leaching of Cr(Ⅵ)and other major elements from chromite ore processing residue[J]. Geochim Cosmochim Acta, 2002, 66:3927-3942.
[4] Chen H, Xiao Q, Xu H, et al. Countermeasures and suggestions for chromate industry pollution control[J]. Environ Prot Chem Ind, 2013,33:23-27.
[5] Palmer CD, Wittbrodt PR. Processes affecting the remediation of chromium-contaminated sites[J]. Environ Health Perspect, 1991,92:25-40.
[6] US EPA. In situ Treatment of Soil&Groundwater Contaminated with Chromium:Technical Resource Guide[R].EPA/625/R-00/005, Washington DC, 2000.
[7] Chrysochoou M, Johnston CP, Dahal G. A comparative evaluation of hexavalent chromium treatment in contaminated soil by calcium polysulfide and green-tea nanoscale zerovalent iron[J]. J Hazard Mater, 2012,201/202:33-42.
[8] Zayed A, Lytle CM, Qian JH, et al. Chromium accumulation, translocation and chemical speciation in vegetable crops[J]. Planta, 1998,206:293-299.
[9] Dermatas D, Chrysochoou M, Moon DH, et al. Christodoulatos, Ettringite-induced heave in chromite ore processing residue(COPR)upon ferrous sulfate treatment[J]. Environ Sci Technol, 2006,40:5786-5792.
[10] Du J, Lu J, Wu Q, et al. Reduction and immobilization of chromate in chromite ore processing residue with nanoscale zero-valent iron[J]. J Hazard Mater, 2012,215/216:152-158.
[11] Kiser JR, Manning BA. Reduction and immobilization of chromium(Ⅵ)by iron(Ⅱ)-treated fauja site[J]. J Hazard Mater, 2010,174:167-174.
[12] Graham MC, Farmer JG, Anderson P, et al. Calcium polysulfide remediation of hexavalent chromium contamination from chromite ore processing residue[J]. Sci Total Environ,2006,364:32-44.
[13] Velasco A, Ram?'rez M, Herna'ndez S, et al. Pilot scale treatment of chromite ore processing residue using sodium sulfide in single reduction and coupled reduction/stabilization processes[J]. J Hazard Mater, 2012,207/208:97-102.
[14] Zhang D, He S, Dai L, et al. Treatment of chromite ore processing residue by pyrolysis with rice straw[J]. Chemosphere, 2009,77:1143-1145.
[15] Kindness A, Macias A, Glasser FP. Immobilization of chromium in cement matrices[J]. Waste Manage, 1994,14:3-11.
[16] Davidovits J. Geopolymers-inorganic polymeric new materials[J].J Therm Anal, 1991,37:1633-1656.
[17] Zhang J, Provis JL, Feng D, et al. Geopolymers for immobilization of Cr6+, Cd2+and Pb2+[J]. J Hazard Mater, 2008,157:587-598.
[18] Silva PD, Sagoe-Crenstil K, Sirivivatnanon V. Kinetics of geopolymerization:role of Al2O3and SiO2[J]. Cem Concr Res, 2007,37:512-518.
[19] Lu QY. Research of Preparation and Application of Geopolymer[R].Fuzhou:Fuzhou University, 2005.
[20] USEPA. Toxicity Characteristic Leaching Procedure Method 1311, 1992[R]. Washington, DC.
[21] GB/T 15555.4-1995,固体废物六价铬的测定二苯碳酰二肼分光光度法[S].GB/T 15555.4-1995, Solid Waste-Determination of Chromium(Ⅵ)-1, 5-Diphenylcarbohydrazide Spectrophotomatric Method[S].
[22] GB/5085.3-2007,危险废物鉴别标准浸出毒性鉴别[S].GB/5085.3-2007, Identification Standards for Hazardous Wastes-Identification for Extraction Toxicity[S].
[23] GB/T 17671-1999,水泥胶砂强度检验方法[S].GB/T 17671-1999, Method of Testing Cements-Determination of Strength[S].
[24] Dupont L, Guillon E. Removal of hexavalent chromium with a lignocellulosic substrate extracted from wheat bran[J]. Environmental Science and Technology, 2003, 37(18):4235-4241.
[25] Li X, Cao J, Zhang W. Stoichiometry of Cr(Ⅵ)immobilization using nanoscale zero valent iron(nZVI):a study with high-resolution X-ray photoelectron spectroscopy(HRXPS)[J]. Industrial&Engineering Chemistry Research,2008,47(7):2131-2139.
[26] Terlingen J G A, Feijen J, Hoffman A S. Immobilization of surface-active compounds on polymer supports using glowdischarge processes:1. sodium dodecyl-sulfate on poly(propylene)[J]. Journal of Colloid and Interface Science,1993,155(1):55-65.