向日葵秸秆基炭材料活化过一硫酸盐降解土壤中苯胺

doi:10.16085/j.issn.1000-6613.2023-1794

摘要/Abstract

摘要：

以农业废弃物向日葵秸秆为原料，采用慢速热解法制备了向日葵秸秆基炭材料（BC），通过比表面积分析仪（BET）、扫描电镜（SEM）、X射线衍射仪（XRD）和X射线光电子能谱仪（XPS）等手段对BC进行表征，并研究其活化过一硫酸盐（PMS）降解土壤中苯胺（AN）的性能，探究了pH、BC投加量、PMS浓度、有机质和共存阴离子对AN降解的影响，并考察了BC的重复利用性能。结果表明，BC可高效活化PMS降解土壤中AN，在BC=0.1g/L、PMS=0.5mmol/L、AN=10mg/kg和pH=7的条件下，30min内BC/PMS体系对AN的降解率可达100%。自由基猝灭实验与电子顺磁共振（EPR）测试结果表明，BC/PMS体系为非自由基反应，¹O₂为该体系的活性物种。机制分析阐明C $̿$ O为BC上的活性点位，其与PMS相互作用产生活性物种¹O₂。循环稳定性实验表明BC具有重复使用性。

关键词: 向日葵, 炭材料, 过一硫酸盐, 苯胺, 非自由基

Abstract:

Sunflower straw-based carbon material (BC) was prepared from agricultural waste sunflower straw by slow pyrolysis. BC was characterized by specific surface area analyzer (BET), scanning electron microscope (SEM), X-ray diffractometer (XRD), and X-ray photoelectron spectroscopy (XPS), and its performance in activating persulfate (PMS) to degrade aniline (AN) in soil was investigated. The effects of pH, BC dosage, PMS concentration, organic matter and co-existing anions on AN degradation were investigated, and the reuse performance of BC was examined. The results showed that BC could efficiently activate PMS to degrade AN in soil, and the degradation rate of AN by BC/PMS system reached 100% in 30 min under the conditions of BC=0.1g/L, PMS=0.5mmol/L, AN=10mg/kg and pH=7. The results of free radical quenching experiments and electron paramagnetic resonance (EPR) tests indicated that the BC/PMS system was a non-radical reaction and ¹O₂ is the active species of the system. Mechanistic analysis elucidates that C $̿$ O was the active site on BC, which interacted with PMS to produce the active species ¹O₂. Cyclic stability experiments demonstrated the reusability of BC.

Key words: sunflower, carbon material, persulfate, aniline, non-free radicals

中图分类号:

孙鹏, 金子涵, 张连科. 向日葵秸秆基炭材料活化过一硫酸盐降解土壤中苯胺[J]. 化工进展, 2024, 43(11): 6493-6503.

SUN Peng, JIN Zihan, ZHANG Lianke. Aniline degradation in soil by activation of persulfate with sunflower straw-based carbon material[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6493-6503.

图/表 14

表1 不同热解温度下制备的炭材料产率、比表面积和孔径

样品	产率/%	S_A/m²·g^-1	S_mic/m²·g^-1	V_tot/m³·g^-1	V_mic/m³·g^-1	V_meso/m³·g^-1
BC700	27.4	349	324	0.181	0.163	0.018
BC800	22.6	766	711	0.434	0.356	0.078
BC900	18.4	872	772	0.508	0.390	0.118
BC1000	15.6	249	188	0.140	0.097	0.043

图1 样品的SEM图谱

图2 BC样品XRD谱图

图3 BC样品的XPS分析结果

图4 BC活化PMS降解[BC] = 0.1g/L, [PMS] = 0.5mmol/L, [AN] = (10±0.5)mg/kg, pH = 7, T = 25℃

图5 两种体系下苯胺降解

图6 pH对苯胺降解的影响[BC]= 0.1g/L, [PMS] = 0.5mmol/L, [AN]= (10±0.5)mg/kg, T = 25℃

图7 BC投加量对苯胺降解的影响[PMS] = 0.5 mmol/L, [AN] = (10±0.5) mg/kg, pH = 7, T = 25℃

图8 PMS浓度对苯胺降解的影响[BC] = 0.1 g/L, [AN] = (10±0.5) mg/kg, pH = 7, T = 25℃

图9 有机质和阴离子对BC900活化PMS降解土壤中苯胺的影响[AN] = (10±0.5)mg/kg, [pH] =7, [PMS] = 0.5 mmol/L, [BC900] = 0.1g/L, T = 25℃

图10 BC循环次数对苯胺降解率的影响[BC900] = 0.1g/L, [AN] = (10±0.5)mg/kg, pH = 7, T = 25℃

图11 自由基猝灭剂对苯胺降解的影响和EPR谱图[AN] = (10±0.5)mg/kg, pH = 7, [PMS] = 0.5mmol/L, [BC900] = 0.1g/L, [DMPO] = 0.1mol/L, T = 25℃

图12 糠醇和NaN3对BC900/PMS体系中苯胺降解的影响以及PMS体系和BC900/PMS体系中TEMP-1O2的EPR光谱[AN] = (10±0.5)mg/kg, pH = 7, [PMS] = 0.5mmol/L, [BC900] = 0.1g/L, [TEMP] = 20mmol/L, T = 25℃

图13 BC活化PMS降解土壤中苯胺机制图

参考文献 35

1	环境保护部和国土资源部发布全国土壤污染状况调查公报[J]. 油田气环境保护, 2014, 24(3): 66.
	Ministry of Environmental Protection (MEP) and Ministry of Land and Resources (MLR) released the National Soil Pollution Survey Bulletin[J]. Environmental Protection of Oil & Gas Fields, 2014, 24(3): 66.
2	翟亚男. 土壤有机污染治理研究[J]. 资源节约与环保，2020(11): 95-96.
	ZHAI Yanan. Study on treatment of soil organic pollution[J]. Resources Economization & Environmental Protection, 2020 (11): 95-96.
3	刘国强, 顾轩竹, 胡哲伟, 等. 农业土壤有机污染生物修复技术研究进展[J]. 江苏农业科学, 2022, 50(1): 27-33.
	LIU Guoqiang, GU Xuanzhu, HU Zhewei, et al. Research progress on bioremediation technology of organic pollution in agricultural soil[J]. Jiangsu Agricultural Science, 2022, 50(1): 27-33.
4	SUN Lulu, LIN Chaoba, ZHOU Zengxing, et al. Characteristics of organic pollutants and their effects on the microbial composition and activity in the industrial soils of Pearl River Delta, China[J]. Ecotoxicology and Environmental Safety, 2023, 256: 114844.
5	LV Yayue, WU Sifan, LIAO Junbin, et al. An integrated adsorption- and membrane-based system for high-salinity aniline wastewater treatment with zero liquid discharge[J]. Desalination, 2022, 527: 115537.
6	杨振兴, 郭绍辉. 苯胺废水处理技术综述[J]. 油气田环境保护, 2022, 32(4): 1-6.
	YANG Zhenxing, GUO Shaohui. Review of aniline wastewater treatment technology[J]. Environmental Protection of Oil & Gas Fields, 2022,32(4): 1-6.
7	张华, 张子鹏, 张澜澜, 等. H₂O₂强化光催化处理苯胺化工废水的应用试验[J]. 化工进展, 2020, 39(12): 5299-5308.
	ZHANG Hua, ZHANG Zipeng, ZHANG Lanlan, et al. In situ test of aniline wastewater degradation by photocatalytic treatment combined with H₂O₂ [J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5299-5308.
8	徐天缘, 郑茜, 王连娟, 等. 焦粉高效活化过硫酸盐对苯胺的降解性能[J]. 化工进展, 2022, 41(6): 3314-3323.
	XU Tianyuan, ZHENG Xi, WANG Lianjuan, et al. Persulfate activation by coke powder for aniline degradation[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3314-3323.
9	LUO Jiayi, YI Yunqiang, FANG Zhanqiang. Nitrogen-rich magnetic biochar prepared by urea was used as an efficient catalyst to activate persulfate to degrade organic pollutants[J]. Chemosphere, 2023, 339: 139614.
10	FAN Yan, JI Yuefei, KONG Deyang, et al. Kinetic and mechanistic investigations of the degradation of sulfamethazine in heat-activated persulfate oxidation process[J]. Journal of Hazardous Materials, 2015, 300: 39-47.
11	DOMINGUEZ Carmen M, RODRIGUEZ Vanesa, MONTERO Esperanza, et al. Methanol-enhanced degradation of carbon tetrachloride by alkaline activation of persulfate: Kinetic model[J]. Science of the Total Environment, 2019, 666: 631-640.
12	HU Peidong, LONG Mingce. Cobalt-catalyzed sulfate radical-based advanced oxidation: A review on heterogeneous catalysts and applications[J]. Applied Catalysis B: Environmental, 2016, 181: 103-117.
13	李旭光, 郭彦秀, 王婷婷, 等. 玉米秸秆生物炭活化过硫酸盐催化降解罗丹明B的性能研究[J]. 水处理技术, 2022, 48(4): 46-49, 53.
	LI Xuguang, GUO Yanxiu, WANG Tingting, et al. The catalytic performance of persulfate for aqueous rhodamine B activated by corn stalk biochar[J]. Technology of Water Treatment, 2022, 48(4): 46-49, 53.
14	孙鹏, 柳佳鹏, 王维大, 等. 活性炭强化热活化过硫酸盐降解对硝基苯酚[J]. 中国环境科学, 2020, 40(11): 4779-4785.
	SUN Peng, LIU jiapeng, WANG Weida, et al. Active carbon enhanced thermal activation of persulfate for degradation of p-nitrophenol[J]. China Environmental Science, 2020, 40(11): 4779-4785.
15	LEE Yuchi, Shang-Lien LO, KUO Jeff, et al. Persulfate oxidation of perfluorooctanoic acid under the temperatures of 20—40℃[J]. Chemical Engineering Journal, 2012, 198/199: 27-32.
16	王宇航, 邓德明. 氮掺杂生物炭活化过硫酸盐去除罗丹明B[J]. 武汉大学学报(理学版), 2022, 68(2): 137-145.
	WANG Yuhang, DENG Deming. Removal of rhodamine B by persulfate activated with N-doped biochar[J]. Journal of Wuhan University (Natural Science Edition), 2022, 68(2): 137-145.
17	肖鹏飞, 安璐, 韩爽. 炭质材料在活化过硫酸盐高级氧化技术中的应用进展[J]. 化工进展, 2020, 39(8): 3293-3306.
	XIAO Pengfei, AN Lu, HAN Shuang. Research advances on applying carbon materials to activate persulfate in advanced oxidation technology[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3293-3306.
18	王宇航, 邓德明. 改性生物炭活化过硫酸盐去除罗丹明B[J]. 水处理技术, 2022, 48(6): 85-89.
	WANG Yuhang, DENG Deming. Removal of rhodamine B by activated persulfate with modified biochar[J]. Technology of Water Treatment, 2022, 48(6): 85-89.
19	ZHOU Xuerong, ZENG Zhuotong, ZENG Guangming, et al. Persulfate activation by swine bone char-derived hierarchical porous carbon: Multiple mechanism system for organic pollutant degradation in aqueous media[J]. Chemical Engineering Journal, 2020, 383: 123019.
20	孙鹏, 张凯凯, 张玉, 等. 生物炭/过一硫酸盐体系同时去除Cu²⁺和对硝基苯胺[J]. 化工进展, 2020, 39(10): 4268-4274.
	SUN Peng, ZHANG Kaikai, ZHANG Yu, et al. Simultaneous removal of Cu²⁺ and p-nitroaniline from aqueous solution by biochar/peroxymonosulfate system[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4268-4274.
21	AVRAMIOTIS Efstathios, FRONTISTIS Zacharias, MANARIOTIS Ioannis D, et al. Oxidation of sulfamethoxazole by rice husk biochar-activated persulfate[J]. Catalysts, 2021, 11(7): 850.
22	GIANNAKIS Stefanos, LIN Kun-Yi Andrew, GHANBARI Farshid. A review of the recent advances on the treatment of industrial wastewaters by Sulfate Radical-based Advanced Oxidation Processes (SR-AOPs)[J]. Chemical Engineering Journal, 2021, 406: 127083.
23	SHAKYA Amita, VITHANAGE Meththika, AGARWAL Tripti. Influence of pyrolysis temperature on biochar properties and Cr（Ⅵ) adsorption from water with groundnut shell biochars: Mechanistic approach[J]. Environmental Research, 2022, 215: 114243.
24	LU Fangjie, WANG Qinqin, ZHU Mingyuan, et al. Deactivation and regeneration of nitrogen doped carbon catalyst for acetylene hydrochlorination[J]. Molecules, 2023, 28(3): 956.
25	Didem ÖZÇIMEN, Ayşegül ERSOY-MERIÇBOYU. Characterization of biochar and bio-oil samples obtained from carbonization of various biomass materials[J]. Renewable Energy, 2010, 35(6): 1319-1324.
26	孙浩, 陈晨, 刘兆煐, 等. 氮改性生物炭活化过一硫酸盐降解水体中2,4-二氯酚的机制研究[J]. 世界地质, 2022, 41(2): 420-427.
	SUN Hao, CHEN Chen, LIU Zhaoying, et al. Degradation mechanism of 2,4-dichlorophenol in water by activated peroxomonosulfate from nitrogen-modified biochar[J]. World Geology, 2022, 41(2): 420-427.
27	YU Bocji, MAN Yanli, WANG Pingping, et al. Catalytic degradation of dimethomorph by nitrogen-doped rice husk biochar[J]. Ecotoxicology and Environmental Safety, 2023, 257: 114908.
28	INYANG Mandu, GAO Bin, PULLAMMANAPPALLIL Pratap, et al. Biochar from anaerobically digested sugarcane bagasse[J]. Bioresource Technology, 2010, 101(22): 8868-8872.
29	GOLSHAN Masoumeh, KAKAVANDI Babak, AHMADI Mehdi, et al. Photocatalytic activation of peroxymonosulfate by TiO₂ anchored on cupper ferrite (TiO₂@CuFe₂O₄) into 2,4-D degradation: Process feasibility, mechanism and pathway[J]. Journal of Hazardous Materials, 2018, 359: 325-337.
30	相里鹏, 崔佳丽, 张峰, 等. 磁性生物炭活化过硫酸盐去除水中罗丹明B[J]. 中国环境科学, 2023, 43(4): 1672-1687.
	XIANG Lipeng, CUI Jiali, ZHANG Feng, et al. Removal of Rhodamine B from aqueous solutions by magnetic biochar activated persulfate[J]. China Environmental Science, 2023, 43(4): 1672-1687.
31	OYEKUNLE Daniel T, ZHOU Xinquan, SHAHZAD Ajmal, et al. Review on carbonaceous materials as persulfate activators: Structure-performance relationship, mechanism and future perspectives on water treatment[J]. Journal of Materials Chemistry A, 2021, 9(13): 8012-8050.
32	HUANG, Baocheng, JIANG Jun, HUANG Guixiang, et al. Sludge biochar-based catalysts for improved pollutant degradation by activating peroxymonosulfate[J]. Journal of Materials Chemistry A, 2018, 6(19): 8978-8985.
33	王磊, 黄帅, 路长远, 等. 氮掺杂生物炭(N/BC)活化过硫酸盐机理研究[J]. 化学研究, 2023, 34(5): 455-462.
	WANG Lei, HUANG Shuai, LU Changyuan, et al. Study on mechanism of N-doped biocarbon (N/BC) toward activating persulfate[J]. Chemical Research, 2023, 34(5): 455-462.
34	ZOU Yubin, LI Wentao, YANG Lian, et al. Activation of peroxymonosulfate by sp²-hybridized microalgae-derived carbon for ciprofloxacin degradation: Importance of pyrolysis temperature[J]. Chemical Engineering Journal, 2019, 370: 1286-1297.
35	SHAO Penghui, TIAN Jiayu, YANG Feng, et al. Identification and regulation of active sites on nanodiamonds: Establishing a highly efficient catalytic system for oxidation of organic contaminants[J]. Advanced Functional Materials, 2018, 28(13): 1705295.

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