浸渍热解法制备铁改性生物炭活化过硫酸盐去除2,4-二硝基甲苯

曹媛; 李晓东; 彭昌盛; 孙宗全; 沈佳伦; 马福俊; 谷庆宝

doi:10.13205/j.hjgc.202111017

浸渍热解法制备铁改性生物炭活化过硫酸盐去除2,4-二硝基甲苯

doi: 10.13205/j.hjgc.202111017

1. 中国海洋大学环境科学与工程学院, 山东青岛 266100;
2. 中国环境科学研究院固体废物污染控制技术研究所, 北京 100012;
3. 污染场地安全修复技术国家工程实验室, 北京 100015

基金项目:

污染场地安全修复技术国家工程实验室开放基金项目（NEL-SRT201706）；国家重点研发计划项目"东北重工业区场地复合污染综合治理技术与集成工程示范"（2019YFC3800）。

详细信息

作者简介:
曹媛(1995-),女,硕士,主要研究方向为水污染治理及农业废物资源化利用。17853480012@163.com

通讯作者:
沈佳伦(1996-),男,工程师,主要研究方向为土壤和地下水修复。1069024560@qq.com

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出版历程
- 收稿日期: 2021-02-04
- 网络出版日期: 2022-01-26

REMOVAL OF 2,4-DINITROTOLUENE BY PERSULFATE ACTIVATED WITH IRON MODIFIED BIOCHAR PREPARED BY DIPPING-PYROLYSIS PROCESS

1. Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China;
2. Research Institute of Solid Waste Pollution Control Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012, China;
3. National Engineering Laboratory for Site Remediation Technologies, Beijing 100015, China

摘要

摘要: 为探究并优化浸渍热解法制备铁改性生物炭（MBC）活化过硫酸盐（PS）对有机污染物去除的试验条件及影响因素，以2，4-二硝基甲苯（2，4-DNT）为目标污染物，考察了热解参数（热解温度、升温速率和停留时间）、FeCl₃浸渍浓度及初始pH值对2，4-DNT去除的影响，并采用电子自旋共振波谱技术及自由基猝灭试验鉴定了PS/MBC体系中生成的自由基。结果表明：1）热解温度对MBC活化PS去除2，4-DNT的影响最显著，其次为升温速率和停留时间；当热解温度、停留时间和升温速率分别为300℃、3 h和10℃/min时，热解制备的MBC对活化PS去除2，4-DNT的效果最佳；2）FeCl₃浸渍浓度是影响MBC活化性能的重要因素，随着FeCl₃浸渍浓度的升高，2，4-DNT的去除率先增后减，当FeCl₃的浸渍浓度为100 mmol/L时，5 h内2，4-DNT的去除率可达到100%，2，4-DNT去除的准一级动力学常数（k_obs）为1.373 min^-1；3）当初始pH值为5.0~9.0时，2，4-DNT均具有较好的去除效果，其去除率为94.5%~83.6%，k_obs为0.606~0.345 min^-1；4）PS/MBC体系中生成的·OH是2，4-DNT去除的主要原因，其强度随MBC的热解温度和FeCl₃浸渍浓度的不同差异较大。研究结果表明，浸渍热解法制备的MBC可有效活化PS实现污染物的高效去除，为PS化学氧化处理有机污染水体提供了新思路。
- 过硫酸盐 /
- 铁改性生物炭 /
- 浸渍热解法 /
- 2,4-二硝基甲苯
Abstract: To explore and optimize the experimental conditions and influence factors of the removal of organic pollutants by persulfate activated with iron modified biochar prepared by the dipping-pyrolysis process, 2,4-dinitrotoluene (2,4-DNT) was selected as the target pollutant to investigate the effects of pyrolysis parameters (pyrolysis temperature, heating rate, and residence time), FeCl₃ concentration and initial pH values on 2,4-DNT removal. The electron spin resonance and free radical quenching test were used to assess the intensity of SO₄^-· and ·OH in the PS/MBC system. The results showed that:1) The pyrolysis temperature had the most significant influence on removal of 2,4-DNT by PS activated with MBC, followed by heating rate and residence time. When the pyrolysis parameters were retained at 300℃, 3 h, and 10℃/min, the best removal of 2,4-DNT was obtained by PS/MBC oxidation. 2) The concentration of FeCl₃ was an important factor of MBC activation. The removal of 2,4-DNT first increased and then decreased with the increase of the FeCl₃ concentration. When the concentration of FeCl₃ was retained at 100 mmol/L, the removal efficiency of 2,4-DNT reached 100% after the reaction of 5 h, and the pseudo-first-order kinetic constant (k_obs) of 2,4-DNT removal was determined to be 1.373 min^-1. 3)When the initial pH ranged from 5.0 to 9.0, 2,4-DNT had a good removal by PS/MBC oxidation, the removal efficiencies were 94.5%~83.6%, and the k_obs values were 0.606~0.345 min^-1. 4) ·OH was the main factor for the removal of 2,4-DNT by PS/MBC oxidation. The signals of ·OH with different strengths were observed, with the addition of MBC prepared by different pyrolysis temperatures and FeCl₃ concentrations. The results showed that MBC prepared by dipping-pyrolysis could effectively activate PS to achieve the removal of organic pollutants, which provided a new idea for treatment of organically polluted water by PS based-advanced chemical oxidation.
- persulfate /
- iron modified biochar /
- dipping-pyrolysis /
- 2,4-dinitrotoluene

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参考文献(39)

[1]	王璇. 硝基苯类有机污染物在环境中的来源与归趋行为研究[J]. 科技视界,2013(26):513.
[2]	KEITH L H, TELLIARD W A. Priority pollutants I-a perapective view[J]. ES&T Special Report, 1979,13(4):416-423.
[3]	LI X D, WU B, ZHANG Q, et al. Mechanisms on the impacts of humic acids on persulfate/Fe²⁺-based groundwater remediation[J]. Chemical Engineering Journal, 2019,378:122142.
[4]	张琦,王静贤,于鸽方,等. 不同方式活化过硫酸盐处理含油污泥及机理探究[J]. 现代化工,2020,40(10):120-130.
[5]	FANG J Y, SHANG C. Bromate formation from bromide oxidation by the UV/persulfate process[J]. Environmental Science & Technology, 2012,46(16):8976-8983.
[6]	ANIOSITAKIS G P, DIONYSIOU D D. Radical generation by the interaction of transition metals with common oxidants[J]. Environmental Science & Technology, 2004,13(38):3705-3712.
[7]	WANG J L, WANG S Z. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018,334(15):1502-1517.
[8]	HUANG K C, COUTTENEY R A, HOAG G E. Kinetics of heat-assisted persulfate oxidation of methyl tert-butyl ether (MTBE)[J]. Chemosphere, 2002,49(4):413-420.
[9]	ZHANG Y X, LIU H L, XIN Y J, et al. Erythromycin degradation and ERY-resistant gene inactivation in erythromycin mycelial dreg by heat-activated persulfate oxidation[J]. Chemical Engineering Journal, 2019,358(15):1446-1453.
[10]	THINES K R, ABDULLAH E C, MUBARAK N M, et al. Synthesis of magnetic biochar from agricultural waste biomass to enhancing route for waste water and polymer application:a review[J]. Renewable and Sustainable Energy Reviews, 2017,67:257-276.
[11]	FANG G D, LIU C, GAO J, et al. Manipulation of persistent free radicals in biochar to activate persulfate for contaminant degradation[J]. Environmental Science & Technology, 2015,49(9):5645-5653.
[12]	YUAN Y, NAUTHI B, ANTONIN P, et al. Applications of biochar in redox-mediated reactions[J]. Bioresource Technology, 2017, 246:271-281.
[13]	ZHU S S, HUANG X C, MA F, et al. Catalytic removal of aqueous contaminants on N-doped graphitic biochars:inherent roles of adsorption and nonradical mechanisms[J]. Environmental Science & Technology, 2018,52(15):8649-8658.
[14]	KEMMOU L, FRONTISTIS Z, VAKROS J, et al. Degradation of antibiotic sulfamethoxazole by biochar-activated persulfate:factors affecting the activation and degradation processes[J]. Catalysis Today, 2018,313(1):128-133.
[15]	许端平,姜紫微,张朕. 磁性生物炭对铅和镉离子的竞争吸附动力学[J]. 安徽农业科学,2020,22(48):67-72.
[16]	WANG S Y, TANG Y K, LI K, et al. Combined performance of biochar sorption and magnetic separation processes for treatment of chromium-contained electroplating wastewater[J]. Bioresource Technology, 2014,174:67-73.
[17]	LIU W J, TIAN K, JIANG H, et al. Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste[J]. Scientific Reports, 2013,3(1):2419.
[18]	ZHU X D, LIU Y C, QIAN F, et al. Preparation of magnetic porous carbon from waste hydrochar by simultaneous activation and magnetization for tetracycline removal[J]. Bioresource Technology, 2014,154:209-214.
[19]	YI Y Q, TU G Q, TSANG P E, et al. Insight into the influence of pyrolysis temperature on Fenton-like catalytic performance of magnetic biochar[J]. Chemical Engineering Journal, 2020, 380(15):122518.
[20]	梁宇飞,薛振华. 沙柳的低温热解特性研究[J]. 木材加工机械,2014,25(4):48-58.
[21]	RONG X, XIE M, KONG L S, et al. The magnetic biochar derived from banana peels as a persulfate activator for organic contaminants degradation[J]. Chemical Engineering Journal, 2019,372(15):294-303.
[22]	LI Q Q, HUANG X C, SUN G J, et al. The regular/persistent free radicals and associated reaction mechanism for the degradation of 1,2,4-trichlorobenzene over different MnO₂ polymorphs[J]. Environmental Science & Technology, 2018,52(22):13351-13360.
[23]	郑凯琪,王俊超,刘姝彤,等. 不同热解温度污泥生物炭对Pb²⁺、Cd²⁺的吸附特性[J]. 环境工程学报,2016,10(12):7277-7282.
[24]	SUN X M, LI Y D. Colloidal carbon spheres and their core/shell structures with noble-metal nanoparticles[J]. Angewandte Chemie, 2004,116(5):607-611.
[25]	ZHANG K K, SUN P, MARIE C A S F, et al. Characterization of biochar derived from rice husks and its potential in chlorobenzene degradation[J]. Carbon, 2018,130:730-740.
[26]	JIA C J, SUN D L, LUO F, et al. Large-scale synthesis of single-crystalline iron oxide magnetic nanorings[J]. Journal of American Chemical Society, 2008,130(50):16968-16977.
[27]	郭明帅,王菲,张学良,等. 改性生物炭活化过硫酸盐对水中苯和氯苯的去除机制[J]. 中国环境科学,2020,12(40):5280-5289.
[28]	YANG J P, ZHAO Y C, MA S M, et al. Mercury removal by magnetic biochar derived from simultaneous activation and magnetization of sawdust[J]. Environmental Science & Technology, 2016,50(21):12040-12047.
[29]	BU L J, SHI Z, ZHOU S Q. Modeling of Fe(Ⅱ)-activated persulfate oxidation using atrazine as a target contaminant[J]. Separation and Purification Technology, 2016,169(1):59-65.
[30]	KUSIC H, PETERNEL I, UKIC S, et al. Modeling of iron activated persulfate oxidation treating reactive azo dye in water matrix[J]. Chemical Engineering Journal, 2011,172(1):109-121.
[31]	SONG Q, FENG Y P, LIU G G, et al. Degradation of the flame retardant triphenyl phosphate by ferrous ionactivated hydrogen peroxide and persulfate:kinetics, pathways, and mechanisms[J]. Chemical Engineering Journal, 2019,361:929-936.
[32]	SHANG W T, DONG Z J, LI M, et al. Degradation of diatrizoate in water by Fe (Ⅱ)-activated persulfate oxidation[J]. Chemical Engineering Journal, 2019,361(1):1333-1334.
[33]	LAU T K, CHU W, GRAHAM N J D. The aqueous degradation of butylated hydroxyanisole by UV/S₂O₈^2-:study of reaction mechanisms via dimerization and mineralization[J]. Environmental Science & Technology, 2007,41(2):613-619.
[34]	FANG G D, CHEN X R, WU W H, et al. Mechanisms of interaction between persulfate and soil constituents:activation, free radical formation, conversion, and identification[J]. Environmental Science & Technology, 2018,52(24):14352-14361.
[35]	FANG G D, DIONYSIOU D D, ZHOU D M, et al. Transformation of polychlorinated biphenyls by persulfate at ambient temperature[J]. Chemosphere, 2013,90(5):1573-1580.
[36]	LIANG C J, LIN Y T, SHIH W H. Treatment of trichloroethylene by adsorption and persulfate oxidation in batch studies[J]. Industrial & Engineering Chemistry Research, 2009,48(18):8373-8380.
[37]	OUYANG D, YAN J C, QIAN L B, et al. Degradation of 1,4-dioxane by biochar supported nano magnetite particles activating persulfate[J]. Chemosphere, 2017,184:609-617.
[38]	YANG L, CHEN Y, OUYANG D, et al. Mechanistic insights into adsorptive and oxidative removal of monochlorobenzene in biochar-supported nanoscale zero-valent iron/persulfate system[J]. Chemical Engineering Journal, 2020,400(15):125811.
[39]	NGUYEN T B, DOONG R, HUANG C P, et al. Activation of persulfate by CoO nanoparticles loaded on 3D mesoporous carbon nitride (CoO@meso-CN) for the degradation of methylene blue (MB)[J]. Science of the Total Environment, 2019,675(20):531-541.