RESEARCH ON WET DETOXIFICATION TECHNOLOGY OF CHROMITE ORE PROCESSING RESIDUE
-
摘要: 以治理铬渣中的Cr(Ⅵ)污染为目的,提出了硫酸浸出-硫酸亚铁还原的铬渣湿法解毒工艺,在对铬渣处理前后的表面形貌进行表征的基础上,探究了不同处理条件下铬渣中Cr(Ⅵ)的处理效果及其修复机理。结果表明:铬渣湿法球磨时间为20 min时,铬渣颗粒98.68%过200目筛,水溶性Cr(Ⅵ)的浸出率可达40.96%;铬渣硫酸添加量为60%,液固比为4∶1,酸溶时间为2.5 h时,Cr(Ⅵ)浸出趋于饱和,此时浸出终点pH为5.8,水溶性和酸溶性Cr(Ⅵ)总浸出率为95.38%;硫酸亚铁添加量为40%时,铬渣中Cr(Ⅵ)含量下降为1.38 mg/kg。铬渣中Cr(Ⅵ)的去除主要与硫酸对含Cr(Ⅵ)矿物的溶解、SO42-和CrO42-的离子交换以及Fe(Ⅱ)对溶液中Cr(Ⅵ)的还原作用有关。Abstract: Aiming at the treatment of Cr(Ⅵ) pollution in chromite ore processing residue (COPR), a wet detoxification process of COPR with sulfuric acid leaching and ferrous sulfate reduction was proposed in this paper. Based on the characterization of the surface morphologies of COPR before and after remediation, the treatment effect and remediation mechanism of Cr(Ⅵ) under different treatment conditions were investigated. The results showed that when the wet ball milling time of COPR was 20 min, 98.68% of the chromium slag particles passed through a 200 mesh sieve, and the leaching rate of water soluble Cr(Ⅵ) reached 40.96%. When the slag sulfuric acid was added at 60%, the liquid-solid ratio was 4∶1, and the acid dissolution time was 2.5 h, the leaching of Cr(Ⅵ) tended to be saturated. At this time, the pH of endpoint was 5.8, and the total leaching rate of Cr(Ⅵ) was 95.38%. When the ferrous sulfate was added at 40%, the content of Cr(Ⅵ) decreased to 1.38 mg/kg. The removal of Cr (Ⅵ) in COPR was mainly related to the dissolution of Cr(Ⅵ)-containing minerals by sulfuric acid, the ion exchange of SO42- and CrO42-, and the reduction of Cr(Ⅵ) in solution by Fe(Ⅱ).
-
Key words:
- chromite ore processing residue /
- acid solution /
- reduction /
- leaching rate /
- Cr(Ⅵ) treatment
-
LI Y Y, LIANG J L, YANG Z H, et al. Reduction and immobilization of hexavalent chromium in chromite ore processing residue using amorphous FeS2[J]. Science of the Total Environment, 2019, 658: 315-323. 陈滨宇. 解毒铬渣堆放场周围环境铬污染规律研究[J]. 环境科学与技术, 1989, 47(4): 8-10. WAZNE M, JAGUPILLA S C, MOON D H, et al. Assessment of calcium polysulfifide for the remediation of hexavalent chromium in chromite ore processing residue (COPR)[J]. Journal of Hazardous Materials, 2007, 143(3): 620-628. MOON D H, WAZNE M, DERMATAS D, et al. Long-term treatment issues with hromite ore processing residue (COPR): Cr6+ reduction and heave [J]. Journal of Hazardous Materials, 2007, 143(3): 629-635. 荣伟英, 周启星. 铬渣堆放场地土壤的污染过程、影响因素及植物修复[J]. 生态学杂志, 2010, 29(3): 598-604. DERMATAS D, CHRYSOCHOOU M, MOON D H, et al. Ettringite-induced heave in hromite ore processing residue (COPR) upon ferrous sulfate treatment[J]. Environmental Science & Echnology, 2006, 40(18): 5786-5792. 盛灿文, 柴立元, 王云燕,等. 铬渣的湿法解毒研究现状及发展前景[J]. 工业安全与环保, 2006, 32(2): 1-3. LI Y Y, CUNDY A B, FENG J X, et al. Remediation of hexavalent chromium contamination in chromite ore processing residue by sodium dithionite and sodium phosphate addition and its mechanism[J]. Journal of Environmental Management, 2017, 192: 100-106. JAGUPILLA S C, WAZNE M, MOON D H. Assessment of ferrous chloride and Portland cement for the remediation of chromite ore processing residue[J]. Chemosphere, 2015, 136: 95-101. GEELHOED J S, MEEUSSEN J C N, ROE M J, et al. Effect of iron(Ⅱ) sulfate addition on chromium(Ⅵ) leaching from columns of chromite ore processing residue[J]. Environmental Science & Technology, 2003, 37(14): 3206-3213. JAGUPILLA S C, MOONA D H, WAZNE M, et al. Effects of particle size and acid addition on the remediation of chromite ore processing residue using ferrous sulfate[J]. Journal of Hazardous Materials, 2009, 168: 121-128. 宋艳, 杨志平, 康绍辉,等. 铬渣中Cr(Ⅵ)的浸出及还原试验研究[J]. 湿法冶金, 2017, 36(5):380-383. 斯塔姆W, 摩尔根J. 水化学: 天然水体化学平衡导论[M]. 汤鸿霄,译. 北京:科学出版社, 1987, 129-134. JAGANYI D, WHEELER P J. Rooibos tea: equilibrium and extraction kinetics of aspalathin[J]. Food Chemistry, 2003, 83: 121-126. 刘帅霞. 两段式还原工艺解毒铬渣技术研究[D]. 上海:东华大学, 2013. MATERN K, KLETTI H, MANSFELDT T. Chemical and mineralogical characterization of chromite ore processing residue from two recent Indian disposal sites[J]. Chemosphere, 2016, 155: 188-195. YAO S, JING L, MIAO P, et al. Identification of Cr(Ⅵ) speciation in ferrous sulfate-reduced chromite ore processing residue (rCOPR) and impacts of environmental factors erosion on Cr(Ⅵ) leaching [J]. Journal of Hazardous Materials, 2019, 373: 389-396. CHRYSOCHOOU M, DERMATAS D. Application of the Rietveld method to assess chromium(Ⅵ) speciation in chromite ore processing residue[J]. Journal of Hazardous Materials, 2007, 141(2): 370-377. GUO B, SASAKI K, HIRAJIMA T, et al. Selenite and selenate uptaken in ettringite: immobilization mechanisms, coordination chemistry, and insights from structure[J]. Cement Concrete Research, 2017, 100: 166-175. PAPASSIOPI N, VAXEVANIDOU K, CHRISTOU C, et al. Synthesis, characterization and stability of Cr(Ⅲ) and Fe(Ⅲ) hydroxides[J]. Journal of Hazardous Materials, 2014, 264: 490-497. MILLS C T, BERN C R, WOLF R E, et al. Modifications to EPA method 3060A to improve extraction of Cr(Ⅵ) from chromium ore processing residue-contaminated soils[J]. Enviromental Science & Technology, 2017, 51(19): 11235-11243. KARAMALIDIS A K, VOUDRIAS E A. Anion leaching from refinery oily sludge and ash from incineration of oily sludge stabilized/solidified with cement[J]. Environmental Science & Technology, 2008, 42(16): 6124-6130. GLASSER F P. Fundamental aspects of cement solidification and stabilisation[J]. Journal of Hazardous Materials, 1997, 52(2/3): 151-170. HILLIER S, ROE M J, GEELHOED J S, et al. Role of quantitative mineralogical analysis in the investigation of sites contaminated by chromite ore processing residue[J]. Science of the Total Environment, 2003, 308(1/2/3): 195-210. WU J N, LI C L, YANG F. The disposition of chromite ore processing residue (COPR) incorporating industrial symbiosis[J]. Journal of Cleaner Production, 2015, 95: 156-162. TINJUM J M, BENSON C H, EDIL T B. Mobilization of Cr(Ⅵ) from chromite ore processing residue through acid treatment[J]. The Science of the Total Environment, 2008, 391(1): 13-25. VELASCO A, RAMÍREZ M, HERNÁNDEZ S, et al. Pilot scale treatment of chromite ore processing residue using sodium sulfide in single reduction and coupled reduction/stabilization processes[J]. Journal of Hazardous Materials, 2012, 207/208: 97-102. YANG H S, CHE Y J, LENG F G. Calcium leaching behavior of cementitious materials in hydrochloric acid solution[J]. Scientific Reports, 2018, UK 8. WAZNE M, JAGUPILLA S C, MOON D H, et al. Leaching mechanisms of Cr(Ⅵ) from chromite ore processing residue[J]. Journal of Environmental Quality, 2008, 37(6): 2125-2134. CHRYSOCHOOU M, FAKRA S C, MARCUS M A, et al. Microstructural analyses of Cr(Ⅵ) speciation in chromite ore processing residue (COPR)[J]. Environmental Science & Technology, 2009, 43(14): 5461-5466. MOON D H, WAZNE M, DERMATAS D, et al. Evaluation of ettringite-related swelling mechanisms for treated chromite ore processing residue[J]. Environmental Science and Pollution Research International, 2015, 22(1): 738-744. 徐文彬.铬渣解毒与氧化铬清洁制备工艺的研究[D].长沙:中南大学,2011. PALMER C D, WITTBRODT P R. Processes affecting the remediation of chromium-contaminated sites[J]. Environmental Health Perspectives, 1991, 92: 25-40. WANG X, ZHANG J D, WANG L L, et al. Long-term stability of FeSO4 and H2SO4 treated chromite ore processing residue (COPR): importance of H+ and SO42-[J]. Journal of Hazardous Materials, 2017, 321: 720-727.
点击查看大图
计量
- 文章访问数: 169
- HTML全文浏览量: 11
- PDF下载量: 0
- 被引次数: 0