次氯酸钙/氧化钙对高砷污泥的氧化稳定化处理
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摘要
针对某硫酸厂废水处理后产生的高浓度含砷(As)污泥,开展氧化稳定化处理技术研究。以浸出毒性作为评价指标,探讨次氯酸钙和氧化钙联合使用对污泥中As的稳定化处理效果,结合XPS和XRD表征探讨了稳定化机制。结果表明:原始污泥中As主要以As(Ⅲ)形式存在,次氯酸钙能将As(Ⅲ)氧化成As(Ⅴ);加入氧化钙能同时提高Ca/As摩尔比和pH,Ca与As(Ⅴ)结合形成稳定的砷酸钙盐。依次加入质量比为5%的次氯酸钙和10%的氧化钙,使Ca/As摩尔比达到2.4以上,As的稳定化率达到99%以上,浸出浓度从181 mg·L~(-1)降低至1.5 mg·L~(-1),且浸出液pH小于12,达到《危险废物填埋污染控制标准》(GB 18598-2001)要求。
A strategy for oxidation and stabilization of sludge with high arsenic concentration,produced by a sulfuric plant was proposed.Calcium hypochlorite and calcium oxide were utilized and the stabilization effect was evaluated by toxicity characteristic leaching procedure(TCLP).The stabilization mechanism was discussed by Xray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD).As(Ⅲ) dominated in untreated sludge was oxidized into As(Ⅴ) by calcium oxide.The calcium oxide addition increased the Ca/As mole ratio and pH,then Ca reacted with As(Ⅴ) to produce calcium arsenate.With the addition of 5% calcium hypochlorite and10% calcium oxide(weight ratio),the stabilization ratio of As reached 99% with Ca/As molar ratio of 2.4,and the leaching concentration of As decreased from 181 mg·L~(-1) to 1.5 mg·L~(-1) at pH less than 12.The result meets the Standard for Pollution Control on the Security Landfill Site for Hazardous Wastes(GB 18598-2001).
A strategy for oxidation and stabilization of sludge with high arsenic concentration,produced by a sulfuric plant was proposed.Calcium hypochlorite and calcium oxide were utilized and the stabilization effect was evaluated by toxicity characteristic leaching procedure(TCLP).The stabilization mechanism was discussed by Xray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD).As(Ⅲ) dominated in untreated sludge was oxidized into As(Ⅴ) by calcium oxide.The calcium oxide addition increased the Ca/As mole ratio and pH,then Ca reacted with As(Ⅴ) to produce calcium arsenate.With the addition of 5% calcium hypochlorite and10% calcium oxide(weight ratio),the stabilization ratio of As reached 99% with Ca/As molar ratio of 2.4,and the leaching concentration of As decreased from 181 mg·L~(-1) to 1.5 mg·L~(-1) at pH less than 12.The result meets the Standard for Pollution Control on the Security Landfill Site for Hazardous Wastes(GB 18598-2001).
引文
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[3]陈萌,杨国录,余亮英.粉煤灰和Na OH固化稳定化受污淤泥试验研究[J].华中科技大学学报(自然科学版),2013,41(10):123-127
[4]尹贞,廖书林,马强,等.几种稳定化药剂修复铬污染土壤的研究[J].环境工程,2016,34(5):166-169
[5]CLANCY T M,HAYES K F,RASKIN L.Arsenic waste management:A critical review of testing and disposal of arsenic-bearing solid wastes generated during arsenic removal from drinking water[J].Environmental Science&Technology,2013,47(19):10799-10812
[6]KIM J Y,DAVIS A P,KIM K W.Stabilization of available arsenic in highly contaminated mine tailings using iron[J].Environmental Science&Technology,2003,37(1):189-195
[7]王浩,潘利祥,张翔宇,等.复合稳定剂对砷污染土壤的稳定研究[J].环境科学,2013,34(9):3587-3594
[8]程毅,黄剑明,周柏明,等.生石灰在污泥重金属钝化中的应用[J].环境工程,2012(S2):325-326
[9]NISHIMURA T,ROBINS R G.a re-evaluation of the solubility and stability regions of calcium arsenites and calcium arsenates in aqueous solution at 25℃[J].Mineral Processing&Extractive Metallurgy Review,1998,18(3/4):283-308
[10]朱义年,张华,梁延鹏,等.砷酸钙化合物的溶解度及其稳定性随p H值的变化[J].环境科学学报,2005,25(12):1652-1660
[11]UNGUREANU G,SANTOS S,RUI B,et al.Arsenic and antimony in water and wastewater:Overview of removal techniques with special reference to latest advances in adsorption[J].Journal of Environmental Management,2015,151:326-342
[12]YOKOYAMA Y,TANAKA K,TAKAHASHI Y.Differences in the immobilization of arsenite and arsenate by calcite[J].Geochimica Et Cosmochimica Acta,2012,91:202-219
[13]CHEN X,YANG L,ZHANG J,et al.Exploration of As(Ⅲ)/As(Ⅴ)uptake from aqueous solution by synthesized calcium sulfate whisker[J].Chinese Journal of Chemical Engineering,2014,22(11/12):1340-1346
[14]PANTSAR-KALLIO M,MANNINEN P K G.Speciation of mobile arsenic in soil samples as a function of p H[J].Science of the Total Environment,1997,204(2):193-200
[15]ZHANG G S,QU J H,LIU H J,et al.Removal mechanism of As(Ⅲ)by a novel Fe-Mn binary oxide adsorbent:Oxidation and sorption[J].Environmental Science&Technology,2007,41(13):4613-4619
[16]DING M,JONG B H W S,ROOSENDAAL S J,et al.XPS studies on the electronic structure of bonding between solid and solutes:Adsorption of arsenate,chromate,phosphate,Pb2+,and Zn2+ions on amorphous black ferric oxyhydroxide[J].Geochimica Et Cosmochimica Acta,2000,64(7):1209-1219
[17]熊正为,朱雷,杨博豪,等.水泥回转窑共处置含砷污泥[J].环境工程学报,2016,10(1):301-305
[18]AND J Y K,DAVIS A P,KIM K W.Stabilization of available arsenic in highly contaminated mine tailings using iron[J].Environmental Science&Technology,2003,37(1):189-195