引用本文:
王艳, 杨硕, 张米雪, 李璨, 姚真真, 周璐璐. ZnFe/BC活化过硫酸盐降解金橙Ⅱ[J]. 环境化学, 2018, 37(12): 2630-2637
WANG Yan, YANG Shuo, ZHANG Mixue, LI Can, YAO Zhenzhen, ZHOU Lulu. Degradation of Orange II by ZnFe/BC catalyzed persulfate[J]. Environmental Chemistry, 2018, 37(12): 2630-2637

ZnFe/BC活化过硫酸盐降解金橙Ⅱ
王艳, 杨硕, 张米雪, 李璨, 姚真真, 周璐璐
安徽科技学院资源与环境院, 凤阳, 233100
摘要:
为了研究ZnFe/BC在常温下活化过硫酸盐(PS)产生硫酸根自由基(SO4·-)降解酸性偶氮染料金橙Ⅱ(AOⅡ)的效能,采用水热合成法制备了ZnFe/BC催化剂,并用X射线衍射(XRD)和扫描电子显微镜-能谱分析(SEM-EDS)对其形貌与负载成分进行了表征,结果显示生物炭上负载的球状颗粒物为ZnFe2O4和Fe3O4.考察了ZnFe/BC投加量、PS投加量、AOⅡ初始浓度以及初始pH对ZnFe/BC/PS体系降解AOⅡ效果的影响.结果显示,ZnFe/BC和PS投量的增加对AOⅡ的去除率均有提升效果,而随着AOⅡ初始浓度的增加,金橙Ⅱ的去除率逐渐降低,在初始pH值在3-10范围内,ZnFe/BC对PS均有较高的催化活性.ZnFe/BC催化剂投加量为0.5 g·L-1,PS投加量为5 mmol·L-1,溶液pH为初始值为6,反应90 min后,50 mg·L-1金橙Ⅱ的脱色率可达到93.7%,而且其降解速率符合拟一级反应动力学.延长反应时间至180 min,TOC去除率达到39.7%.通过对催化剂ZnFe/BC稳定性研究,发现经4次连续循环使用后,金橙Ⅱ脱色率仍然可保持在85%以上,说明该催化剂具有良好的循环使用性能.通过投加对苯醌、乙醇和叔丁醇等3种不同种类的猝灭剂,证实了ZnFe/BC/PS体系中具有SO4·-、·OH和O2·-活性物种.发芽实验证明,在反应时间为180 min内,金橙Ⅱ降解出水对小麦发芽的抑制率随反应时间的进行而先升高而逐渐降低,最后基本无抑制.
关键词:    过硫酸盐    金橙Ⅱ    自由基    催化氧化   
Degradation of Orange II by ZnFe/BC catalyzed persulfate
WANG Yan, YANG Shuo, ZHANG Mixue, LI Can, YAO Zhenzhen, ZHOU Lulu
College of Resource and Environment Anhui Science and Technology University, Fengyang, 233100, China
Abstract:
In order to study the effect of sulfate radical (SO4·-) on the degradation of acid azo dye orange Ⅱ (AOⅡ) by ZnFe/BC activated sulfate persulfate (PS) at room temperature, ZnFe/BC catalyst was prepared by hydrothermal synthesis method. The structure of ZnFe/BC was characterized by X ray diffraction (XRD) and scanning electron microscope-energy dispersive spectrometer (SEM-EDS). The results showed that spherical particle loaded on biochar (BC) was ZnFe2O4 and Fe3O4. The effect of ZnFe/BC dosage, PS concentration, initial AOⅡ concentration and initial pH on the degradation of AOⅡ in ZnFe/BC/PS system was investigated. The results showed that the removal rate of AOⅡ increased with the increase of ZnFe/BC dosage and PS concentration while it decreased when the initial AOⅡ concentration increased. When the initial pH was in range of 3-10, ZnFe/BC has high catalytic activity for PS. When ZnFe/BC addition was 0.5 g·L-1, PS concentration was 5 mmol·L-1, the initial pH was 6, and the initial AOⅡ concentration was 50 mg·L-1, the AOⅡ decolorization could reach 93.7% after reaction 90 min, and the degradation rate was accorded with the pseudo first order reaction kinetics. Extending the reaction time to 180min, the TOC removal rate reached 39.7%. The AOⅡ decolorization rate could still remain above 85% when ZnFe/BC was used for 4 continuous cycles in ZnFe/BC/PS system, which indicating that the catalyst had a good recycling performance. Three different kinds of quenching agents (p-benzoquinone, ethanol and tert-butyl alcohol) were added to the ZnFe/BC/PS system for AOⅡ degradation, respectively, and the result confirmed that active species SO4·-,·OH and O2·- consisted in ZnFe/BC/PS system. The germination experiment showed that among 180 min of the AOⅡ degradation reaction time, the inhibition rate of the effluent from AOⅡ degradation to wheat germination increased first, and then gradually decreased. Finally, the inhibition rate dropped down to near 0.
Key words:    persulfate    orange II    free radical    catalytic oxidation   
收稿日期: 2018-04-25
基金项目: 安徽省自然科学基金(1808085MB49),安徽省教育厅重点项目(KJ2016A178),安徽省高校优秀中青年骨干人才国内外访学研修(gxfxZD2016179),安徽科技学院优秀中青年骨干教师和国家级大学生创新创业训练计划(201710879023)资助.
王艳,E-mail:wangyanht@163.com
相关功能
PDF(KB) Free
打印本文
加入收藏夹
把本文推荐给朋友
作者相关文章
王艳  在本刊中的所有文章
杨硕  在本刊中的所有文章
张米雪  在本刊中的所有文章
李璨  在本刊中的所有文章
姚真真  在本刊中的所有文章
周璐璐  在本刊中的所有文章

参考文献:
[1] KURTAN U, AMIR M, BAYKAL A, et al. Magnetically recyclable Fe3O4@His@Cu nanocatalyst for degradation of Azo dyes[J]. Journal of Nanoscience and Nanotechnology, 2016, 16(3):2548-2556.
[2] MATZEK L W, CARTER K E. Activated persulfate for organic chemical degradation:A review[J]. Chemosphere, 2016, 151:178-188.
[3] 朱维晃, 杨瑞, 王宏伟. 蒽醌活化过硫酸盐降解罗丹明B[J]. 环境化学, 2015, 34(10):1948-1954. ZHU W H, YANG R, WANG H W. Degradation of rhodamine B by quinone-activated persulfate process[J]. Environmental Chemistry, 2015, 34(10):1948-1954(in Chineses).
[4] 吴昊, 孙丽娜, 王辉, 等. 活化过硫酸钠原位修复石油类污染土壤研究进展[J]. 环境化学, 2015, 34(11):2085-2095. WU H, SUN L N, WANG H, et al. Persulfate in-situ remediation of petroleum hydrocarbon contaminated soil[J]. Environmental Chemistry, 2015, 34(11):2085-2095(in Chineses).
[5] LI D, CHEN D, YAO Y, et al. Strong enhancement of dye removal through addition of sulfite to persulfate activated by a supported ferric citrate catalyst[J]. Chemical Engineering Journal, 2016, 288:806-812.
[6] DIVYA D S, KURIAN M. Catalytic peroxide oxidation of persistent chlorinated organics over nickel-zinc ferrite nanocomposites[J]. Journal of Water Process Engineering, 2017, 16:69-80.
[7] CAI C, LIU J, ZHANG Z Y, et al. Visible light enhanced heterogeneous photo-degradation of Orange Ⅱ by zinc ferrite (ZnFe2O4) catalyst with the assistance of persulfate[J]. Separation and Purification Technology, 2016, 165:42-52.
[8] BOCZKAJ G, FERNANDES A. Wastewater treatment by means of advanced oxidation processes at basic pH conditions:A review[J]. Chemical Engineering Journal,2017, 320:608-633.
[9] ZHANG X L, FENG M B, QU R J, et al. Catalytic degradation of diethyl phthalate in aqueous solution by persulfate activated with nano-scaled magnetic CuFe2O4/MWCNTs[J]. Chemical Engineering Journal, 2016, 301:1-11.
[10] LIANG C J, HUANG C F, MOHANTY N, et al. A rapid spectrophotometric determination of persulfate anion in ISCO[J], Chemosphere, 2008, 73:1540-1543.
[11] 马瑞进, 余正祥, 王啸宇, 等. PDS脱硫液中硫代硫酸钠、亚硫酸钠含量测定方法[J]. 化工技术与开发, 2012, 41(11):56-57. MA R J, YU Z X, WANG X Y, et al. Determination method of sodium thiosulphate and sodium sulfite in PDS desulfurization solutions[J]. Technology & Development of Chemical Industry, 2012, 41(11):56-57(in Chineses).
[12] 中华人民共和国国家标准GB/T 5009.1-2003食品卫生检验方法理化部分总则[S].北京:中国标准出版社,2004. National standard of People's Republic of China GB/T 5009.1-2003 methods of food hygienic analysis -physical and chemical section-general principles[S]. Beijing:China Standard Press, 2004(in Chineses).
[13] PARSHETTI G K, TELKE A A, KALYANI D C, et al. Decolorization and detoxification of sulfonated azo dye methyl orange by Kocuria rosea MTCC 1532[J]. Journal of Hazardous Materials, 2010, 176(1-3):503-509.
[14] LAMHAMDI M, BAKRIM A, AARAB A, et al. Lead phytotoxicity on wheat (Triticum aestivum L.) seed germination and seedlings growth[J], Comptes Rendus-Biologies, 2011, 334(2):118-126.
[15] CHEN Z P, FANG W Q, ZHANG B, et al. High-yield synthesis and magnetic properties of ZnFe2O4 single crystal nanocubes in aqueous solution[J]. Journal of Alloys and Compounds, 2013, 550:348-352.
[16] HAN L J, ZHOU X, WAN L N, et al. Synthesis of ZnFe2O4 nanoplates by succinic acid-assisted hydrothermal route and their photocatalytic degradation of rhodamine B under visible light[J]. Journal of Environmental Chemical Engineering, 2014, 2:123-130.
[17] KAKAVANDI B. Heterogeneous Fenton-like catalytic oxidation of tetracycline by AC@Fe3O4, as a heterogeneous persulfate activator:Adsorption and degradation studies[J]. Journal of Industrial & Engineering Chemistry, 2017, 45:323-333.
[18] ZULFIKAR M A, AFRITA S, WAHYUNINGRUM D, et al. Preparation of Fe3O4-chitosan hybrid nano-particles used for humic acid adsorption[J]. Environmental Nanotechnology Monitoring & Management, 2016, 6:64-75.
[19] HUSSAIN I, LI M, ZHANG Y, et al. Insights into the mechanism of persulfate activation with nZVI/BC nanocomposite for the degradation of nonylphenol[J]. Chemical Engineering Journal, 2017, 311:163-172.
[20] PENG H J, XU L Y, ZHANG W, et al. Different kinds of persulfate activation with base for the oxidation and mechanism of BDE209 in a spiked soil system[J]. Science of the Total Environment, 2017, 574:307-313.
[21] WU Y L, PRLHO R, BRIGANTE M, et al. Activation of persulfate by Fe(Ⅲ) species:Implications for 4-tert-butylphenol degradation[J]. Journal of Hazardous Materials, 2017, 322:380-386.
[22] DENG J, FENG S F, MA X Y, et al. Heterogeneous degradation of Orange Ⅱ with peroxymonosulfate activated by ordered mesoporous MnFe2O4[J]. Separation and Purification Technology, 2016, 167:181-189.
[23] CHENG X, GUO H G, ZHANG Y L, et al. Oxidation of 2,4-dichlorophenol by non-radical mechanism using persulfate activated by Fe/S modified carbon nanotubes[J]. Journal of Colloid and Interface Science, 2016, 469:277-286.
[24] MONTEAGUDO J M, DURÁN A, GONZÁLEZ R, et al. In situ chemical oxidation of carbamazepine solutions using persulfate simultaneously activated by heat energy, UV light, Fe2+ ions, and H2O2[J]. Applied Catalysis B, 2015, 176-177:120-129.
[25] RANI S K, EASWARAMOOTHY D, BILAL I M, et al. Studies on Mn(Ⅱ)-catalyzed oxidation of alpha-amino acids by peroxomonosulphate in alkaline mediumdeamination and decarboxylation:a kinetic approach[J]. Applied Catalysis A, 2009, 369:1-7.
[26] NETA P, HUIE R E, ROSS A B. Rate constants for reactions of inorganic radicals in aqueous solution[J]. Journal of Physical & Chemical Reference Data, 1988, 17(3):1027-1284.
[27] LIN H, ZHANG H, WANG X, et al. Electro-Fenton removal of Orange Ⅱ in a divided cell:Reaction mechanism, degradation pathway and toxicity evolution[J]. Separation and Purification Technology, 2014, 122(3):533-540.
相关文献:
1.唐玉朝, 尹汉雄, 黄健, 凌琪, 李卫华, 张萌.零价铁活化过硫酸钠对偶氮染料4BS的脱色机理[J]. 环境化学, 2018,37(5): 1071-1078
2.谷得明, 郭昌胜, 冯启言, 张远, 徐建.基于硫酸根自由基的高级氧化技术及其在环境治理中的应用[J]. 环境化学, 2018,37(11): 2489-2508
3.钟燕清, 张永清, 陈宪方, 黄少斌.不同螯合剂对零价铁活化过硫酸盐降解对氯苯胺的影响[J]. 环境化学, 2015,34(4): 685-691