凝胶球负载零价铁活化过硫酸盐降解偶氮染料废水

doi:10.16085/j.issn.1000-6613.2017.06.050

摘要/Abstract

摘要： 铁活化过硫酸盐高级氧化技术中，由于反应速度快引起的铁流失是主要问题之一。本文制备了负载零价铁的海藻酸钠凝胶球催化剂（Fe-montmorillonite-sodium alginate balls，Fe-MABs），电子显微镜图表明海藻酸钠凝胶球和铁结合良好，并考察了过硫酸钠（sodium peroxydisulfate，PDS）用量、催化剂用量等因素对偶氮染料活性黑5（Reactive Black 5，RBK5）染料废水降解的影响，比较了Fe-MABs/PDS、Fe+C/PDS、Fe+C、PDS、Fe五种体系对RBK5的降解能力。结果表明，Fe-MABs/PDS体系能有效地降解RBK5，在RBK5初始浓度40mg/L条件下，PDS投加量为2mmol/L、Fe-MABs投加量40g/L、初始pH为7.0、温度为298K，在反应时间为30min和60min时，对RBK5降解率分别达到95.42%和99.90%；与Fe+C/PDS、Fe+C、Fe体系相比，Fe-MABs/PDS体系Fe的流失率减少可达90%以上。此外，通过采用甲醇和叔丁醇作为自由基淬灭剂发现Fe-MABs/PDS体系中产生的活性中间体硫酸根自由基SO₄^－·对降解过程起主要作用，并初步探索了Fe-MABs催化过硫酸盐体系对RBK5的降解动力学。

关键词: 海藻酸钠凝胶球, 非均相过硫酸盐催化体系, 活性黑5, 硫酸根自由基

Abstract: Persulfate can be effectively activited by iron. However,iron will leaching in the solution because of the rapid speed of the reaction. The montmorillonite-sodium alginate balls(MABs)with zero-valent iron loading(Fe-MABs)was prepared and characterized by the electron microscope. The results showed the well dispersion of iron on the sodium alginate gelatin ball. In addition,the effects of dosages of sodium peroxydisulfate(PDS)and catalyst to the degradation of Reactive Black 5(RBK5) were examined in batch experiments. The degradation ability to RBK5 follows this order:Fe+C/PDS> Fe-MABs/PDS> Fe+C> PDS> Fe. The results demonstrated that RBK5 could be degraded by Fe-MABs/PDS system effectively. Under the condition with initial RBK5 concentration 40mg/L,PDS dosage 2.0mmol/L,Fe-MABs dosage 40g/L,pH 7,temperature 298K,the degradation rate of RBK5 in aqueous solution could reach 95.42% and 99.90% within 30min and 60min,respectively. Comparing with Fe+C/PDS,Fe leaching ratio will reduce 90% in Fe-MABs/PDS system within 60min. By using methanol and chloroform as free radical quenchers,the active intermediate SO₄^-· play a leading role to the degradation process,which generated from the PDS activation. Finally,the dynamics was also calculated in the Fe-MABs catalyzing system.

Key words: montmorillonite-sodium alginate balls, persulfate catalytic heterogeneous systems, Reactive Black 5(RBK5), sulfate radical

中图分类号:

X703

吴丽颖, 王炳煌, 张圆春, 张倩, 王滴, 洪俊明. 凝胶球负载零价铁活化过硫酸盐降解偶氮染料废水[J]. 化工进展, 2017, 36(06): 2318-2324.

WU Liying, WANG Binghuang, ZHANG Yuanchun, ZHANG Qian, WANG Di, HONG Junming. Degradation of Reactive Black 5(RBK5)by gelatin balls loading iron activating sodium persulfate[J]. Chemical Industry and Engineering Progress, 2017, 36(06): 2318-2324.

参考文献

[1] 陈晓旸,薛智勇,吴丹,等. 基于硫酸自由基的高级氧化技术及其在水处理中的应用[J]. 水处理技术,2009,35(5):16-20. CHEN X Y,XUE Z Y,WU D,et al. Based on the sulfate radical advanced oxidation technology and its application in water treatment[J]. Technology of Water Treatment,2009,35(5):16-20.
[2] YANG S Y,YANG X,SHAO X T,et al. Activated carbon catalyzed persulfate oxidation of azo dye acid orange 7 at ambient temperature[J]. Journal of Hazardous Materials,2011,186(1):659-666.
[3] 江传春,肖蓉蓉,杨平. 高级氧化技术在水处理中的研究进展[J]. 水处理技术,2011,37(7):12-16. JIANG C C,XIAO R R,YANG P. Research process of advanced oxidation processes in wastewater treatment[J]. Technology of Water Treatment,2011,37(7):12-16.
[4] 卢徐节,刘琼玉,刘延湘,等. 高级氧化技术在印染废水处理中的应用[J]. 印染助剂,2011,28(5):7-11. LU X J,LIU Q Y,LIU Y X,et al. Application of advanced oxidation technologies in printing and dyeing wastewater treatment[J]. Textile Auxiliaries,2011,28(5):7-11.
[5] LIU C S,SHIH K,SUN C X,et al. Oxidative degradation of propachlor by ferrous and copper ion activated persulfate[J]. Science of the Total Environment,2012,416(2):507-512.
[6] XU X R,LI X Z. Degradation of azo dye Orange G in aqueoussolutions by persulfate with ferrous ion[J]. Separation & Purification Technology,2010,72(1):105-111.
[7] 王继鹏,胡林潮,杨彦,等. Fe²⁺活化过硫酸钠降解1,2-二氯苯[J]. 环境工程学报,2014,8(9):3767-3772. WANG J P,HU L C,YANG Y,et al. Sodium persulfate activation by Fe²⁺ for degradation of 1,2-dichlorobenzene[J]. Chinese Journal of Environmental Engineering,2014,8(9):3767-3772.
[8] 张金凤,杨曦,郑伟,等. 水体系中 Fe(Ⅱ)/S₂O₈²^－-S₂O₃²^－降解敌草隆的研究[J]. 中国环境科学,2008,28(7): 620-623. ZHANG J F,YANG X,ZHENG W,et al. Studies on Fe(Ⅱ)/S₂O₈^2--S₂O₃^2-degrading diuron in aqueous system[J]. China Environmental Science,2008,28(7):620-623.
[9] 蔡涛,张璐吉,胡六江,等. 零价铁活化过二硫酸盐氧化降解阿特拉津[J]. 应用化学,2013,30(1):114-119. CAI T,ZHANG L J,HU L J,et al. Degradation of atrazine by peroxydisulfate activatedwith zero-valent iron[J]. Applied Chemistry,2013,30(1):114-119.
[10] 杨世迎,马楠,王静,等. 零价铁-过二硫酸盐连续运行体系去除水中硝基苯[J]. 环境科学学报,2014,34(4):920-924. YANG S Y,MA N,WANG J. Degradation of nitrobenzene in aqueous solution by zero-valent iron/persulfate continuous operation system[J]. Acta Scientiae Circumstantiae,2014,34(4):920-924.
[11] LIANG C J,LAI M C. Trichloroethylene degradation by zero valent iron activated persulfate oxidation[J]. Environmental Engineering Science,2008,25(7):1071- 1077.
[12] USMAN M,FAURE P,RUBY C,et al. Application of magnetite-activated persulfate oxidation for the degradation of PAHs in contaminated soils[J]. Chemosphere,2012,87(3):234-240.
[13] OH S Y,KANG S G,KIM D W,et al. Degradation of 2,4-dinitrotoluene by persulfate activated with iron sulfides [J]. Chemical Engineering Journal,2011,172(2/3):641-646.
[14] 黄晓东,涂佳. 活性炭负载铁催化过硫酸盐降解酸性大红3R[J]. 环境科学学报,2014,34(6):1449-1454. HUANG X D,TU J. Degradation of Acid Red 3R by persulfate with Fe-loaded activated carbon as catalyst[J]. Acta Scientiae Circumstantiae,2014,34(6):1449-1454.
[15] ANISHA G S,PREMA P. Cell immobilization technique for the enhanced production of alpha-galactosidase by Streptomyces griseoloalbus[J]. Bioresource Technology,2008,99(9):3325-3330.
[16] KIM,HONG H,JUNG J,et al. Degradation of trichloroethylene(TCE) by nanoscale zero-valent iron(nZVI)immobilized in alginate bead[J]. Journal of Hazardous Materials,2010,176(1/2/3):1038-1043.
[17] HAMMOUDA S B,ADHOUM N,MONSER L. Chemical oxidation of a malodorous compound,indole,using iron entrapped in calcium alginate beads[J]. Journal of Hazardous Materials,2016,301:350-361.
[18] YANG S,WANG P,YANG X,et al. Degradation efficiencies of azo dye Acid Orange 7 by the interaction ofheat,UV and anions with common oxidants:persulfate,peroxymonosulfate and hydrogen peroxide[J]. Journal of Hazardous Materials,2010,179(1):552-558.
[19] HAMDAOUI O,NAFFRECHOUX E. Adsorption kinetics of 4-chlorophenol onto granular activated carbon in the presence of high frequency ultrasound[J]. Ultrasonics Sonochemistry,2009,16(1):15-22.
[20] LIANG C,SU H W. Identification of sulfate and hydroxyl radicals in thermally activated persulfate[J]. Industrial & Engineering Chemistry Research,2009,48(11):472-5.
[21] 赵进英,张耀斌,全燮,等. 加热和亚铁离子活化过硫酸钠氧化降解4-CP的研究[J]. 环境科学,2010,31(5):1233-1238. ZHAO J Y,ZHANG Y B,QUAN X,et al. Sodium peroxydisulfate activation by heat and Fe(Ⅱ) for the degradation of 4-CP[J]. Environmental Science,2010,31(5):1233-1238.
[22] LEE Y C,LO S L,CHIUEH P T,et al. Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation[J]. Water Research,2010,44(3):886-892.
[23] 杨世迎,杨鑫,王萍,等. 过硫酸盐高级氧化技术的活化方法研究进展[J]. 现代化工,2009,29(4):13-19. YANG S Y,YANG X,WANG P,et al. Advances in persulfate oxidation activation methods of persulfate oxidation[J]. Modern Chemical Industry,2009,29(4):13-19.
[24] FU F L,DIONYSIOU D D,LIU H. The use of zero-valent iron for groundwater remediation and wastewater treatment:a review [J]. Journal of Hazardous Materials,2014,267(3):194-205.
[25] 闫金霞,董韶峰,卜永强,等. 零价铁法处理染料废水脱色效果研究[J]. 染料与染色,2007,44(4):45-46. YAN Jinxia,DONG Shaofeng,BU Yongqiang,et al. A study on the decoloration of dye stuff wastewater by the ironscurf method[J]. Dyestuffs and Coloration,2007,44(4):45-46.
[26] 吴秋惠,吴皓,王令充,等. 海藻酸钠微球的制备及其在药物载体中的应用进展[J]. 中华中医药杂志,2011(8):791-794. WU Qiuhui,WU Hao,WANG Lingchong,et al. Review on preparation and application of alginate microspheres as drug carrier[J]. China Journal of Traditional Chinese Medicine and Pharmacy,2011(8):791-794.
[27] DING Dahu,LIU Chao,JI Yuefei,et al. Mechanism insight of degradation of norfloxacin by magnetite nanoparticles activated persulfate:identification of radicals and degradation pathway[J]. Chemical Engineering Journal,2016,308(1):330-339.
[28] 李德生,王宝山. 曝气铁炭微电解工艺预处理高浓有机化工废水[J]. 中国给水排水,2003,19(10):58-60. LI Desheng,WANG Baoshan. Pretreatment of high concentrated organic chemical wastewater by iron carbon micro-electrolysis process with aeration[J]. China Water & Wastewater,2003,19(10):58-60.
[29] BUXTON G V,GREENSTOCK C L,HELMAN W P,et al.Critical review of rate constants for reactions of hydrated electrons, hydrogen atoms and hydroxyl radicals(·OH/·O^-)in aqueous solution[J]. Journal of Physical & Chemical Reference Data,1988,17(2):513-531.
[30] EIBENBERGER H,STEENKEN S,O'Neill P,et al. Pulse radiolysis and electron spin resonance studies concerning the reaction of SO₄^-· with alcohols and ethers in aqueous solution[J]. The Journal of Physical Chemistry,1978,82(6):749-750.
[31] DIONYSIOU D,ANIPSITAKIS G P. Radical generation by the interaction of transition metals with common oxidants[J]. Environmental Science & Technology,2004,38(13):3705-3712.
[32] 张成. 基于硫酸根自由基的过硫酸钠高级氧化法氧化降解染料的研究[D]. 广州:华南理工大学,2012. ZHANG Cheng. The progress of oxidation-degradation of dye in advanced oxidation processes based on sulfate radical[D]. Guangzhou:South China University of Technology,2012.
[33] 叶张荣,马鲁铭. 铁屑内电解法对活性艳红X-3B脱色过程的机理研究[J]. 水处理技术,2005,31(8):65-67. YE Zhangrong,MA Luming. Mechanism of reactive brilliant Red X-3B decolorization by iron filings inner electrolysis process[J]. Technology of Water Treatment,2005,31(8):65-67.
[34] 李海燕,曾庆福. 铁屑还原及微波铁屑诱导氧化降解偶氮染料历程的研究[J]. 环境工程学报,2008,2(3):294-298. LI Haiyan,ZENG Qingfu. Study on degradation process of azo dye by iron internal electrolysis deoxidization and microwave induced oxidation[J].Chinese Journal of Environmental Engineering,2008,2(3):294-298.
[35] PADMAJA S,ALFASSI A B,NETA P,et al. Rate constants for reactions of SO₄^-radicals in acetonitrile[J]. International Journal of Chemical Kinetics,1993,25(3):193-198.