Treatment methyl orange with persulfate activated by modified activated carbon

doi:10.19965/j.cnki.iwt.2021-0397

Abstract

Abstract:

For the low cost and high efficiency treatment of azo dyeing wastewater，modified activated carbon was applied to activate persulfate（PS） to degrade methyl orange wastewater. Single⁃factor experiments were performed to investigate the effects of the dosage of modified activated carbon，the concentration of PS and Fe²⁺ on methyl orange degradation. The degradation followed a pseudo⁃first⁃order kinetic model，with the pseudo first⁃order rate constant from 0.075 7 to 1.717 8 min^-1. The response surface method based on Box-Behnken Design was simulated，and the effects of various factors and their interactions on the degradation of methyl orange were studied. The factors contributed on the degradation were as follows：the dosage of modified activated carbon>the PS concentration>the Fe²⁺ concentration. The optimum condition was 0.73 g/L modified activated carbon，2.0 mmol/L PS and 1.08 mol/L Fe²⁺. The mechanism of methyl orange degradation was investigated. Hydroxyl and sulfate radicals were identified by electron paramagnetic resonance spectroscopy during methyl orange degradation. The surface⁃adsorbed hydroxyl radicals played important roles by radical scavenging tests.

Key words: methyl orange, persulfate, modified activated carbon, kinetics

摘要：

为获得低成本、高效率的偶氮染料废水处理方法，采用改性活性炭催化过硫酸盐（PS）氧化降解甲基橙染料废水。通过单因素实验分别研究改性活性炭、PS及Fe²⁺浓度对甲基橙降解的影响，降解过程遵循拟一级动力学模型，反应速率常数为0.075 7~1.717 8 min^-1。采用Box-Behnken Design响应面研究各因素及其交互作用对甲基橙降解的影响，各因素贡献排序为：催化剂投加量>PS浓度>Fe²⁺浓度，最佳反应条件：催化剂投加量为0.73 g/L、PS浓度为2.0 mmol/L、Fe²⁺浓度为1.08 mol/L。对改性活性炭催化PS氧化降解甲基橙染料废水的机理进行探究，电子顺磁共振波谱实验表明降解体系中存在羟基自由基和硫酸根自由基，自由基猝灭实验表明改性活性炭表面的羟基自由基在甲基橙降解过程中起重要作用。

关键词: 甲基橙, 过硫酸盐, 改性活性炭, 动力学

CLC Number:

X703.1

Juanjuan ZHAO, Yeling QIU, Yun HU, Huiying CHEN, Chengwei MA, Chao WANG, Jiayu XU. Treatment methyl orange with persulfate activated by modified activated carbon[J]. Industrial Water Treatment, 2022, 42(1): 115-120.

赵娟娟, 丘烨铃, 胡赟, 陈惠莹, 马承威, 王超, 许佳雨. 改性活性炭催化过硫酸盐处理甲基橙废水[J]. 工业水处理, 2022, 42(1): 115-120.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0397

https://www.iwt.cn/EN/Y2022/V42/I1/115

Figures/Tables 9

References 15

1	ROBATI D， MIRZA B， RAJABI M，et al. Removal of hazardous dyes-BR 12 and methyl orange using graphene oxide as an adsorbent from aqueous phase［J］. Chem. Eng. J.，2016，284：687-697. doi:10.1016/j.cej.2015.08.131
2	KONICKI W， ALEKSANDRZAK M， MOSZYŃSKI D，et al. Adsorption of anionic azo⁃dyes from aqueous solutions onto graphene oxide：Equilibrium，kinetic and thermodynamic studies［J］. J. Colloid Interf. Sci.，2017，496：188-200. doi:10.1016/j.jcis.2017.02.031
3	ZHAO Juanjuan， SUN Yujiao， ZHANG Yang，et al. Heterogeneous activation of persulfate by activated carbon supported iron for efficient amoxicillin degradation［J］. Environ. Technol. Innov.，2021，21：101259. doi:10.1016/j.eti.2020.101259
4	SUN Yujiao， ZHAO Juanjuan， ZHANG Botao，et al. Oxidative degradation of chloroxylenol in aqueous solution by thermally activated persulfate：Kinetics，mechanisms and toxicities［J］. Chem. Eng. J.，2019，368：553-563. doi:10.1016/j.cej.2019.02.208
5	GHAUCH A， BAALBAKI A， AMASHA M，et al. Contribution of persulfate in UV₂₅₄ activated systems for complete degradation of chloramphenicol antibiotic in water［J］. Chem. Eng. J.，2017，317：1012-1025. doi:10.1016/j.cej.2017.02.133
6	AYOUB G， GHAUCH A. Assessment of bimetallic and trimetallic iron⁃based systems for persulfate activation：Application to sulfamethoxazole degradation［J］. Chem. Eng. J.，2014，256：280-292. doi:10.1016/j.cej.2014.07.002
7	吕志超，宋秀兰，赵青云. 颗粒活性炭激活过硫酸盐氧化法深度处理焦化废水［J］. 工业水处理，2021，41（2）：88-91.
	Zhichao LÜ， SONG Xiulan， ZHAO Qingyun. Advanced treatment of coking wastewater by persulfate oxidation catalyzed by granular activated carbon［J］. Industrial Water Treatment，2021，41（2）：88-91.
8	ZHANG Yang， ZHANG Botao， TENG Yanguo，et al. Heterogeneous activation of persulfate by carbon nanofiber supported Fe₃O₄@carbon composites for efficient ibuprofen degradation［J］. J. Hazard. Mater.，2021，401：123428. doi:10.1016/j.jhazmat.2020.123428
9	杨生浛，毕文龙，张健，等. 硫酸根自由基对甲基橙的处理效果及机理［J］. 工业水处理，2020，40（4）：55-59. doi:10.11894/iwt.2019-0895
	YANG Shenghan， BI Wenlong， ZHANG Jian，et al. Effect and mechanism of sulfate radical on methyl orange treatment［J］. Industrial Water Treatment，2020，40（4）：55-59. doi:10.11894/iwt.2019-0895
10	FOROUZESH M， EBADI A， AGHAEINEJAD⁃MEYBODI A. Degradation of metronidazole antibiotic in aqueous medium using activated carbon as a persulfate activator［J］. Sep. Purif. Technol.，2019，210：145-151. doi:10.1016/j.seppur.2018.07.066
11	YANG Shiying， YANG Xin， SHAO Xueting，et al. Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature［J］. J. Hazard. Mater.，2011，186（1）：659-666. doi:10.1016/j.jhazmat.2010.11.057
12	YAO Chenhui， ZHANG Yongqing， DU Meimei，et al. Insights into the mechanism of non⁃radical activation of persulfate via activated carbon for the degradation of p-chloroaniline［J］. Chem. Eng. J.，2019，362：262-268. doi:10.1016/j.cej.2019.01.040
13	JIANG Shunfeng， LING Lili， CHEN Wenjing，et al. High efficient removal of bisphenol A in a peroxymonosulfate/iron functionalized biochar system：Mechanistic elucidation and quantification of the contributors［J］. Chem. Eng. J.，2019，359：572-583. doi:10.1016/j.cej.2018.11.124
14	ZHAO Dan， LIAO Xiaoyong， YAN Xiulan，et al. Effect and mechanism of persulfate activated by different methods for PAHs removal in soil［J］. J. Hazard. Mater.，2013，254/255：228-235. doi:10.1016/j.jhazmat.2013.03.056
15	王丽娟，张海潇，张锐，等. 石墨相氮化碳活化过硫酸钠暗反应降解亚甲基蓝［J］. 工业水处理，2020，40（8）：75-79. doi:10.1088/1757-899x/397/1/012094
	WANG Lijuan， ZHANG Haixiao， ZHANG Rui，et al. Degradation of methylene blue by sodium persulfate dark reaction activated with graphitic carbon nitride［J］. Industrial Water Treatment，2020，40（8）：75-79. doi:10.1088/1757-899x/397/1/012094

催化剂投加量/（g·L^-1）	动力学方程	速率常数/min^-1	R ²
0.3	C_t /C ₀=e^{-0.075 7} ^t	0.075 7±0.003 2	0.983 8
0.6	C_t /C ₀=e^{-0.169 9} ^t	0.169 9±0.010 6	0.977 8
0.9	C_t /C ₀=e^{-0.476 2} ^t	0.476 2±0.013 6	0.998 1
1.2	C_t /C ₀=e^{-0.955 3} ^t	0.955 3±0.011 0	0.999 9
1.5	C_t /C ₀=e^{-1.717 8} ^t	1.717 8±0.076 0	0.999 8

催化剂投加量/（g·L^-1）	动力学方程	速率常数/min^-1	R ²
0.3	C_t /C ₀=e^{-0.075 7} ^t	0.075 7±0.003 2	0.983 8
0.6	C_t /C ₀=e^{-0.169 9} ^t	0.169 9±0.010 6	0.977 8
0.9	C_t /C ₀=e^{-0.476 2} ^t	0.476 2±0.013 6	0.998 1
1.2	C_t /C ₀=e^{-0.955 3} ^t	0.955 3±0.011 0	0.999 9
1.5	C_t /C ₀=e^{-1.717 8} ^t	1.717 8±0.076 0	0.999 8

编号	A：催化剂投加量/（g·L^-1）	B：PS浓度/（mmol·L^-1）	C：Fe²⁺浓度/（mol·L^-1）	降解率/%
1	0.60	1.05	0.75	95.73
2	0.60	1.05	0.75	95.21
3	0.60	2.00	1.08	99.43
4	0.60	1.05	0.75	91.74
5	0.60	1.05	0.75	93.74
6	0.30	2.00	0.75	76.77
7	0.60	0.10	0.41	95.51
8	0.30	1.05	0.41	65.53
9	0.90	1.05	0.41	99.95
10	0.60	0.10	1.08	95.76
11	0.30	0.10	0.75	52.10
12	0.60	2.00	0.41	94.54
13	0.30	1.05	1.08	64.91
14	0.90	0.10	0.75	99.23
15	0.90	1.05	1.08	99.96
16	0.60	1.05	0.75	96.95
17	0.90	2.00	0.75	99.93

编号	A：催化剂投加量/（g·L^-1）	B：PS浓度/（mmol·L^-1）	C：Fe²⁺浓度/（mol·L^-1）	降解率/%
1	0.60	1.05	0.75	95.73
2	0.60	1.05	0.75	95.21
3	0.60	2.00	1.08	99.43
4	0.60	1.05	0.75	91.74
5	0.60	1.05	0.75	93.74
6	0.30	2.00	0.75	76.77
7	0.60	0.10	0.41	95.51
8	0.30	1.05	0.41	65.53
9	0.90	1.05	0.41	99.95
10	0.60	0.10	1.08	95.76
11	0.30	0.10	0.75	52.10
12	0.60	2.00	0.41	94.54
13	0.30	1.05	1.08	64.91
14	0.90	0.10	0.75	99.23
15	0.90	1.05	1.08	99.96
16	0.60	1.05	0.75	96.95
17	0.90	2.00	0.75	99.93

数据来源	平方和	自由度	均方	F	p
模型	3 425.62	9	380.62	31.52	<0.000 1
A	2 441.61	1	2 441.61	202.21	<0.000 1
B	98.49	1	98.49	8.16	0.024 5
C	2.57	1	2.57	0.212 4	0.658 8
AB	143.64	1	143.64	11.90	0.010 7
AC	0.099 2	1	0.099 2	0.008 2	0.930 3
BC	5.38	1	5.38	0.445 8	0.525 7
A ²	733.03	1	733.03	60.71	0.000 1
B ²	1.17	1	1.17	0.097 2	0.764 3
C ²	5.17	1	5.17	0.428 1	0.533 8
剩余	84.52	7	12.07
失拟	68.46	3	22.82	5.68	0.063
纯误差	16.06	4	4.02
总和	3 510.15	16

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