PDF(799 KB)
活性炭强化热活化过硫酸盐降解对硝基苯酚
孙鹏, 柳佳鹏, 王维大, 李玉梅, 樊健, 韩剑宏, 张连科
中国环境科学 ›› 2020, Vol. 40 ›› Issue (11) : 4779-4785.
PDF(799 KB)
PDF(799 KB)
活性炭强化热活化过硫酸盐降解对硝基苯酚
Active carbon enhanced thermal activation of persulfate for degradation of p-nitrophenol
热活化过硫酸盐（PS）可降解有机污染物，但通常需要较高的反应温度，成为制约降解效率的关键因素之一.为提高热活化PS效率，向反应体系中加入活性炭（AC）并以对硝基苯酚（PNP）为目标污染物，考察AC强化热活化PS降解PNP的效率，分析pH值、PS浓度和AC投加量等因素对PNP降解的影响，确定最佳反应条件.结果表明，AC可以明显强化热活化PS降解PNP，在AC=1.0g/L，PS=2.0mmol/L，PNP=10.0mg/L，T=50℃和pH=3.5条件下，120min时AC/PS体系对PNP降解率可达100.00%，而PS体系对PNP降解率仅为31.69%.自由基猝灭实验表明，AC/PS/PNP体系为自由基反应，SO4·-和·OH共同参与PNP降解且以SO4·-为主导.机制分析阐明AC上的表面缺陷为活性位点，其与PS中O—O键作用导致O—O键键能降低，进而O—O在热活化下均裂形成SO4·-.PNP降解中间产物分析表明AC仅提高了热活化PS降解PNP反应速率，未改变PNP的降解路径.
Thermal activation of persulfate (PS) is an effective method for degradation of organic pollutants, but the high temperature has become restrictive factor. The effects of active carbon (AC) on the thermal activation of persulfate (PS) and the subsequent degradation of p-nitrophenol (PNP) in water was systematically investigated. The effects of critical parameters, including the initial pH, PS concentration and dose of AC were also investigated. AC could significant enhanced thermal activation of PS for high efficient degradation of PNP. The degradation efficiency of PNP reached 100.00% in AC/PS system, whereas only 31.69% in PS system with AC, PS, and PNP concentration of 1.0g/L, 2.0mmol/L, and 10.0mg/L, respectively, initial pH of 3.5, temperature of 50℃ and reaction time of 120min. Free radical quenching experiments demonstrated that the AC/PS/PNP system was radical reaction, and SO4·- and ·OH were involved in the AC/PS/PNP system, and the SO4·- were the main radical for the PNP degradation. The mechanism analysis revealed that the defective sites on AC were involved for weakening the O-O bond in PS and subsequently cleaving O-O bond by heat to generate sulfate radical. The analysis of degradation intermediates suggested that AC could only accelerate the degradation efficiency of PNP but not alter the reaction pathway in PS systems.
表面缺陷 / 对硝基苯酚 / 过硫酸盐 / 活性炭 / 降解
activated carbon / defective sites / degradation / persulfate / p-nitrophenol
[1] 代志峰,赵同谦,阴永光,等.硝酸纤维素膜光降解水中对硝基苯酚的机制[J]. 环境科学, 2019,40(2):685-692. Dai Z F, Zhao T Q, Yin Y G, et al. Photolysis mechanism of p-Nitrophenol by nitrocellulose membrane in aqueous solution[J]. Environmental Science, 2019,40(2):685-692.
[2] Mei X, Liu J, Guo Z W, et al. Simultaneous p-nitrophenol and nitrogen removal in PNP wastewater treatment:Comparison of two integrated membrane-aerated bioreactor systems[J]. Journal of Hazardous Materials, 2019,363:99-108.
[3] Zeng L Y, Gong J Y, Dan J F, et al. Novel visible light enhanced Pyrite-Fenton system toward ultrarapid oxidation of p-nitrophenol:Catalytic activity, characterization and mechanism[J]. Chemosphere, 2019,228:232-240.
[4] Zhao H H, Kong C H. Enhanced removal of p-nitrophenol in a microbial fuel cell after long-term operation and the catabolic versatility of its microbial community[J]. Chemical Engineering Journal, 2018,339:424-431.
[5] Yan J, Chen Y, Qian L, et al. Heterogeneously catalyzed persulfate with a CuMgFe layered double hydroxide for the degradation of ethylbenzene[J]. Journal of Hazardous Materials, 2017,338:372-380.
[6] 陈炜,张宇东,蔡珺晨,等.壳聚糖负载磺化酞菁钴催化过硫酸盐降解甲基橙的研究[J]. 中国环境科学, 2019,39(1):157-163. Chen Y, Zhang Y D, Cai J C, et al. Degradation of methyl orange by chitosan microsphere supported cobalt tetrasulfophthalocyanine activated persulfate[J]. China Environmental Science, 2019,39(1):157-163.
[7] Zou J, Ma J, Chen L, et al. Rapid acceleration of ferrous iron/peroxymonosulfate oxidation of organic pollutants by promoting Fe(Ⅲ)/Fe(Ⅱ) cycle with hydroxylamine[J]. Environment Science Pollution Research, 2013,47:11685-11691.
[8] Chen X, Murugananthan M, Zhang Y. Degradation of p-Nitrophenol by thermally activated persulfate in soil system[J]. Chemical Engineering Journal, 2016,283:1357-1365.
[9] Zhang K J, Zhou X Y, Zhang T Q, et al. Degradation of the earthy and musty odorant 2,4,6-tricholoroanisole by persulfate activated with iron of different valences[J]. Environment Science Pollution Research, 2018,25:3435-3445.
[10] 张饮江,相元泉,鲁仙,等.零价铁激活过硫酸盐降解水中铬黑T特性[J]. 中国环境科学, 2020,40(2):653-660. Zhang Y J, Xiang Y Q, Lu X, et al. Characteristics on the eriochrome black T (EBT) degradation in aquatics by Fe/persulfate system[J]. China Environmental Science, 2020,40(2):653-660.
[11] An D, Westerhoff P, Zheng M X, et al. UV-activated persulfate oxidation and regeneration of NOM-Saturated granular activated carbon[J]. Water Research, 2015,73:304-310.
[12] Furman O S, Teel A L, Watts R J. Mechanism of base activation of persulfate[J]. Environmental Science and Technology, 2010,44(16):6423-6428.
[13] Duan X, Ao Z, Zhou L, et al. Occurrence of radical and nonradical pathways from carbocatalysts for aqueous and nonaqueous catalytic oxidation[J]. Applied catalysis B:Environmental, 2016,188:98-105.
[14] Zrinyi N, Pham A L. Oxidation of benzoic acid by heat-activated persulfate:Effect of temperature on transformation pathway and product distribution[J]. Water Research, 2017,120:43-51.
[15] Zhang M, Chen X Q, Zhou H, et al. Degradation of p-nitrophenol by heat and metal ions co-activated persulfate[J]. Chemical Engineering Journal, 2015,264:39-47.
[16] Chen Y Q, Deng P Y, Xie P C, et al. Heat-activated persulfate oxidation of methyl-and ethyl-parabens:Effect, kinetics, and mechanism[J]. Chemosphere, 2017,168:1628-1636.
[17] Lke I, Linden K G, Orbell J D, et al. Critical review of the science and sustainability of persulphate advanced oxidation processes[J]. Chemical Engineering Journal, 2018,338:651-669.
[18] Jans U, Hoigné J. Activated carbon and carbon black catalyzed transformation of aqueous ozone into OH-Radicals[J]. Ozone:Science & Engineering, 1998,20(1):67-90.
[19] Sánchez-Polo M; Gunten V U. Rivera-Utrilla J Efficiency of activated carbon to transform ozone into OH radicals:Influence of operational parameters[J]. Water Research, 2005,39(14):3189-3198.
[20] Sun P, Zhang K K, Gong J Y, et al. Sunflower stalk-derived biochar enhanced thermal activation of persulfate for high efficient oxidation of p-nitrophenol[J]. Environmental Science and Pollution Research, 2019,26(26):27482-27493.
[21] Wang Y X, Ao Z M. Activation of peroxymonosulfate by carbonaceous oxygen groups:experimental and density functional theory calculations[J]. Applied catalysis B:Environmental, 2016, 198:295-302.
[22] Duan X G, Sun H Q, Ao Z, et al. Unveiling the active sites of graphene-catalyzed peroxymonosulfate activation[J]. Carbon, 2016,107:371-378.
[23] Duan X, Ao Z, Zhou L, et al. Occurrence of radical and nonradical pathways from carbocatalysts for aqueous and nonaqueous catalytic oxidation[J]. Applied catalysis B:Environmental, 2016,188:98-105.
[24] 李晶,鲍建国,杜江坤,等.Fe/Cu双金属活化过一硫酸盐降解四环素的机制[J]. 环境科学, 2018,39(7):3203-3211. Li J, Bao J G, Du J K, et al. Degradation mechanism of tetracycline using Fe/Cu oxides as heterogeneous activators of peroxymonosulfate[J]. Environmental Science, 2018,39(7):3203-3211.
[25] 姚淑华,马锡春,李士凤.秸秆生物炭活化过硫酸盐氧化降解苯酚[J]. 中国环境科学, 2018,38(11):4166-4172. Yao S H, Ma X C, Li S F. Straw biochar activated persulfate oxidation and degradation of phenol[J]. China Environmental Science, 2018, 38(11):4166-4172.
[26] 李蒋,王雁,张秀芳,等.Co3O4/BiVO4复合阳极活化过一硫酸盐强化光电催化降解双酚A[J]. 环境科学, 2018,39(8):3713-3718. Li J, Wang Y, Zhang X F, et al. Enhancement of photoelectrocatalytic degradation of bisphenol A with peroxymonosulfate activated by a Co3O4/BiVO4 composite photoanode[J]. Environmental Science, 2018,39(8):3713-3718.
[27] Su C L, Acik M, Takia M, et al. Probing the catalytic activity of porous graphene oxide and the origin of this behaviour[J]. Nature Communications, 2012,3:1298.
[28] Chen J B, Hong W, Huang T Y, et al. Activated carbon fiber for heterogeneous activation of persulfate:implication for the decolorization of azo dye[J]. Environmental Science and Pollution Research, 2016,23:18564-18574.
[29] Fang G, Gao J, Liu C, et al. Key role of persistent free radicals in hydrogen peroxide activation by biochar:implications to organic contaminant degradation[J]. Environmental Science & Technology, 2014,48(3):1902-1910.
内蒙古自然科学基金资助项目（2019LH02006）
京公网安备 11010802030352号 /
| 〈 |
|
〉 |
