不同异位修复工艺对高浓度铬渣污染土壤中Cr的去除特性

doi:10.11949/j.issn.0438-1157.20171354

摘要/Abstract

摘要：

以我国某铬盐厂的两种不同污染特性铬渣污染土壤（A土和B土）为研究对象，探讨了三种异位修复工艺（淋洗、稳定化、湿法解毒）去除铬渣污染土壤中总Cr和Cr（Ⅵ）的效果，并采用改进BCR顺序提取法分析了不同修复工艺对土壤中各形态Cr的去除效果。实验结果表明，三种异位修复工艺对铬污染土壤中Cr（Ⅵ）的去除效果为湿法解毒 > 稳定化 > 淋洗，湿法解毒工艺对A土、B土中Cr（Ⅵ）的去除率分别高达83.26%、92.94%；对铬污染土壤总铬去除效果最佳的是异位淋洗工艺，异位淋洗工艺对A土、B土总铬消减分别达54.87%、80.16%。异位淋洗工艺实现了对水溶态Cr（Ⅵ）、酸溶态Cr（Ⅵ）的泥水分离，是总铬消减的主要原因；稳定化工艺和湿法解毒工艺降低了土壤pH，促进了水溶态Cr、酸溶态Cr及可还原态Cr向可氧化态Cr的转化，因此土中总Cr并未发生显著消减。高浓度铬渣污染土壤经三种异位修复工艺处理后，A土Cr（Ⅵ）仍然残留736.6 mg·kg^-1，B土Cr（Ⅵ）仍然残留245.47 mg·kg^-1，酸溶态Cr的残留是导致三种工艺修复Cr（Ⅵ）效果受限的主要原因。

关键词: 铬渣, 污染土壤, 异位淋洗, 异位稳定化, 湿法解毒

Abstract:

Two different types of chromite ore processing residue(COPR) contaminated soil were selected from one of chromate plants in China as research objects. The removal efficiencies of total chromium and hexavalent chromium were investigated by using three ex-situ remediation technologies which were soil washing, ex-situ stabilization and wet-process detoxication. The removal mechanisms of various forms of chromium by three kinds of remediation technologies were studied using the modified BCR method. The results show that wet-process detoxication technology was favor in Cr(Ⅵ) reducing. Cr(Ⅵ) removal rate of the wet-process detoxication technology for soil A and soil B were up to 83.26%, 92.94%, respectively. The Cr(Ⅵ) removal rate of wet-process detoxication technology was higher than soil washing and ex-situ stabilization. For total chromium removal rate, soil washing was the best remediation technology. The total Cr removal rate of the soil washing technology for soil A and soil B were up to 54.87%, 80.16%, respectively. Separating soluble Cr(Ⅵ) and acid soluble Cr(Ⅵ) from soil were the main reasons for the reduction of total chromium. The total Cr remove was not significant for ex-situ stabilization and wet-process detoxication technology. Because, acid conditions which was reduced by these two remediation technologies, promote soluble Cr, acid soluble Cr and reducible Cr transformed into oxidizable Cr and the total amount Cr did not change. After remediation, the Cr(Ⅵ) residual of COPR contaminated soil still maintains a high level (the Cr(Ⅵ) residual content of soil A was 736.6 mg·kg^-1, the Cr(Ⅵ) residual content of soil B was 245.47 mg·kg^-1). The main reason was the acid soluble Cr residue.

Key words: chromite ore processing residue (COPR), contaminated soil, soil washing, ex-situ stabilization, wet-process detoxication technology

中图分类号:

朱文会, 李志涛, 王夏晖, 王兴润. 不同异位修复工艺对高浓度铬渣污染土壤中Cr的去除特性[J]. 化工学报, 2018, 69(6): 2730-2736.

ZHU Wenhui, LI Zhitao, WANG Xiahui, WANG Xingrun. Characteristics of chromium removing using different ex-situ remediations in soil seriously contaminated by chromite ore processing residue[J]. CIESC Journal, 2018, 69(6): 2730-2736.

参考文献 31

[1]	纪柱. 中国铬盐近五十年发展概况[J]. 无机盐工业, 2010, 42(12):1-6. JI Z. Development status of China's chromium salts in recent 50 years[J]. Inorganic Chemicals Industry, 2010, 42(12):1-6.
[2]	刘玉强, 李丽, 王琪, 等. 典型铬渣污染场地的污染状况与综合整治对策[J]. 环境科学研究, 2009, 22(2):249-253. LIU Y Q, LI L, WANG Q, et al. Study on pollution situation at typical chrome residue contaminated sites and corresponding integrated remediation plan[J]. Research of Environmental Sciences, 2009, 22(2):249-253.
[3]	王兴润, 张艳霞, 王琪, 等. 铬污染建筑废物不同清洗剂的作用效果比较[J]. 化工学报, 2012, 63(10):3255-3261. WANG X R, ZHANG Y X, WANG Q, et al. Comparison of different washing agents for disposal of chromium-contaminated construction waste[J]. CIESC Journal, 2012, 63(10):3255-3261.
[4]	朱文会, 王兴润, 董良飞, 等. 海藻酸钠包覆型Fe-Cu双金属PRB填料的除Cr(Ⅵ)特性[J]. 化工学报, 2013, 64(9):3373-3380. ZHU W H, WANG X R, DONG L F, et al. Characteristics of removing Cr(Ⅵ) of Fe-Cu bimetal PRB coated by sodium alginate[J]. CIESC Journal, 2013, 64(9):3373-3380.
[5]	罗建峰, 曲东. 青海海北化工厂铬渣堆积场土壤铬污染状况研究[J]. 西北农业学报, 2006, 15(6):244-247. LUO J F, QU D. Study on the soil Cr pollution in residue piling yard in Qinghai province[J]. Acta Agriculturae Boreali-occidentalis Sinica, 2006, 15(6):244-247.
[6]	曹泉, 王兴润. 铬渣污染场地污染状况研究与修复技术分析[J]. 环境工程学报, 2009, 3(8):1493-1497. CAO Q, WANG X R. Study on pollution characteristics of contaminated sites with chrome and discussion on common remediation technologies[J]. Chinese Journal of Environmental Engineering, 2009, 3(8):1493-1497.
[7]	KHAN F I, HUSAIN T, HEJAZI R. An overview and analysis of site remediation technologies[J]. Journal of Environmental Management, 2004, 71(2):95-122.
[8]	SON A J, SHIN K H, LEE J U, et al. Chemical and eco-toxicity assessment of PAH-contaminated soils remediated by enhanced soil flushing[J]. Environmental Engineering Science, 2003, 20(3):197-206.
[9]	JUHASZ A L, SMITH E, SMITH J, et al. In situ remediation of DDT-contaminated soil using a two-phase cosolvent flushing-fungal biosorption process[J]. Water, Air & Soil Pollution, 2003, 147(1):263-274.
[10]	ALTER S R, BRUSSEAU M L, PIATT J J, et al. Use of tracer tests to evaluate the impact of enhanced-solubilization flushing on in-situ biodegradation[J]. Journal of Contaminant Hydrology, 2003, 64(3/4):191-202.
[11]	JEYASINGH J, PHILIP L. Bioremediation of chromium contaminated soil:optimization of operating parameters under laboratory conditions[J]. Journal of Hazardous Materials, 2005, 118(1/2/3):113-120.
[12]	DESJARDIN V, BAYARD R, HUCK N, et al. Effect of microbial activity on the mobility of chromium in soils[J]. Waste Management, 2002, 22(2):195-200.
[13]	LI G, GUO S H, LI S C, et al. Comparison of approaching and fixed anodes for avoiding the ‘focusing’ effect during electrokinetic remediation of chromium-contaminated soil[J]. Chemical Engineering Journal, 2012, 203(1):231-238.
[14]	王璇, 熊惠磊, 马俊, 等. 废弃铬盐厂土壤中铬的赋存特征及异位淋洗修复可行性研究[J]. 环境工程学报, 2016, 10(11):6746-6752. WANG X, XIONG H L, MA J, et al. Research on occurrence characteristics of chromium in soils and feasibility study of ex-situ soil washing for an abandoned chrome chemicals manufacturing facility[J]. Chinese Journal of Environmental Engineering, 2016, 10(11):6746-6752.
[15]	张辉, 付融冰, 郭小品, 等. 铬污染土壤的还原稳定化修复[J]. 环境工程学报, 2017, 11(11):6163-6168. ZHANG H, FU R B, GUO X P, et al. Experimental research on stabilization remediation of chromium contaminated soil[J]. Chinese Journal of Environmental Engineering, 2017, 11(11):6163-6168.
[16]	王兴润, 李丽, 刘雪, 等. 铬渣治理技术的应用进展及特点分析[J]. 中国给水排水, 2009, 25(4):10-14. WANG X R, LI L, LIU X, et al. Application developments and characteristics analysis of treatment technologies of chromium residues[J]. China Water & Wastewater, 2009, 25(4):10-14.
[17]	SUN B, ZHAO F J, LOMBI E, et al. Leaching of heavy metals from contaminated soils using EDTA[J]. Environmental Pollution, 2001, 113(2):111-120.
[18]	PICHTEL J, PICHTEL T M. Comparison of solvents for ex-situ removal of chromium and lead from contaminated soil[J]. Environmental Engineering Science, 1997, 14(2):97-104.
[19]	王兴润, 刘雪, 颜湘华, 等. 铬渣污染土壤清洗剂筛选研究[J]. 环境科学研究, 2010, 23(11):1405-1409. WANG X R, LIU X, YAN X H, et al. Selection of washing agents for remediation of chromium slag-contaminated soil[J]. Research of Environmental Sciences, 2010, 23(11):1405-1409.
[20]	PONDER S M, DARAB J G, MALLOUK T E, et al. Remediation of Cr(Ⅵ) and Pb(Ⅱ) aqueous solutions using supported nanoscale zero-valent iron[J]. Environment Science &Technology, 2000,34(12):2564-2569.
[21]	朱文会, 董良飞, 王兴润, 等. Cr(Ⅵ)污染地下水修复的PRB填料实验研究[J]. 环境科学, 2013, 34(7):215-221. ZHU W H, DONG L F, WANG X R, et al. Experimental study on the remediation of chromium contaminated groundwater with PRB media[J]. Environmental Science, 2013, 34(7):215-221.
[22]	胡月, 赵勇胜, 沈勇, 等. 不同因素对多硫化钙处理地下水中Cr(Ⅵ)效果影响[J]. 生态环境学报, 2015, 24(2):294-299. HU Y, ZHAO Y S, SHEN Y, et al. Effects of different factors on the Cr(Ⅵ)-contaminated ground water by calcium polysulfide[J]. Ecology and Environmental Sciences, 2015, 24(2):294-299.
[23]	CHRYSOCHOOU M, FERREIRA D R, JOHNSTON C P. Calcium polysulfide treatment of Cr(Ⅵ)-contaminated soil[J]. Journal of Hazardous Materials, 2010, 179(1/2/3):650-657.
[24]	DERMATAS D, CHRYSOCHOOU M, MOON D H, et al. Ettringite-induced heave in chromite ore processing residue(COPR) upon ferrous sulfate treatment[J]. Environmental Science & Technology, 2006, 40(18):5786-5792.
[25]	王旌, 付融冰, 罗启仕, 等. 亚铁盐对城市污泥中重金属的稳定化作用研究[J]. 环境科学, 2010, 31(4):1036-1040. WANG J, FU R B, LUO Q S, et al. Stabilization of heavy metal in sewage sludge by using a ferrous iron[J]. Environmental Science, 2010, 31(4):1036-1040.
[26]	中华人民共和国环境保护部. 固体废物六价铬的测定碱消解/火焰原子吸收分光光度法:HJ 687-2014[S]. 北京:中国环境科学出版社,2014. Ministry of Environmental Protection of the People's Republic of China. Solid waste-Determination of hexavalent chromium-By alkaline digestion/flame atomic absorption spectrophotometic:HJ 687-2014[S]. Beijing:China Environmental Science Press, 2014.
[27]	中华人民共和国环境保护部. 土壤总铬的测定火焰原子吸收分光光度法:HJ 491-2009[S]. 北京:中国环境科学出版社,2009. Ministry of Environmental Protection of the People's Republic of China. Solid quality-Determination of total chromium-Flame atomic absorption spectrometry:HJ 491-2009[S]. Beijing:China Environmental Science Press, 2009.
[28]	QUEVAUVILLER P, RAURET G, MUNTAU H. Evaluation of a sequential extraction procedure for the determination of extractable trace metal contents sediments[J]. Fresenius's Journal of Analytical Chemistry, 1994, 349(12):808-814.
[29]	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会. 土壤和沉积物13个微量元素形态顺序提取程序:GB/T 25282-2010[S]. 北京:中国标准出版社, 2011. General Administration of Quality Supervision, Inspection and Quarantine of the People's Republic of China, Standardization Administration of the People's Republic of China. Soil and sediment-Sequential extraction procedure of speciation of 13 trace elements:GB/T 25282-2010[S]. Beijing:Standards Press of China, 2011.
[30]	DHAL B, THATOI H N, DAS N N, et al. Chemical and microbial remediation of hexavalent chromium from contaminated soil and mining/metallurgical solid waste:a review[J]. Journal of Hazardous Materials, 2013, 250/251(30):272-291.
[31]	刘雪, 王兴润, 张增强. pH和有机质对铬渣污染土壤中Cr赋存形态的影响[J]. 环境工程学报, 2010, 4(6):1436-1440. LIU X, WANG X R, ZHANG Z Q. Potential influences of pH and organic matter on the occurrence forms of chromium-contaminated soils[J]. Chinese Journal of Environmental Engineering, 2010, 4(6):1436-1440.