Catalytic degradation of tetracycline hydrochloride with persulfate catalyzed by composite of carbon and steel slag

doi:10.19965/j.cnki.iwt.2021-0914

Abstract

Abstract:

Commercial activated carbon（AC） was used as carrier，series of GZ/AC composites were prepared by changing the addition ratio of steel slag（GZ）. The pore structure and surface properties of GZ/AC were characterized by N₂ adsorption/desorption，XRF，XRD and H₂?TPR. The prepared materials were used to degrade tetracycline hydrochloride（TC） wastewater by sodium persulfate activated. The results showed that the activated carbon had a reducing effect on steel slag during material preparation，thereby increased the content of zero-valence metals，and enhanced its catalytic activity. When the reaction temperature was 65 ℃，the removal rate of TC（100 mg/L） by 60% GZ/AC catalyst was 97%. The entire degradation process was a quasi-second-order kinetic process in which radicals on the catalyst surface，sulfate radicals（SO₄^?－） and hydroxyl radicals（·OH） participated in the reaction.

Key words: steel slag, activated carbon, persulfate, tetracycline hydrochloride

摘要：

选用商用活性炭（AC）为载体，通过改变钢渣（GZ）的添加比例制备了系列GZ/AC复合材料。采用N₂吸附/脱附、XRF、XRD和H₂?TPR等手段对制备的GZ/AC的孔结构与表面性质进行了表征，并将其用于活化过硫酸钠处理盐酸四环素废水。结果表明，活性炭在复合过程中对钢渣具有还原作用，从而提高了零价金属的含量，进而增强了其催化活性。在反应温度为65 ℃时，催化剂60%GZ/AC对盐酸四环素（100 mg/L）的去除率可达97%。整个降解过程是催化剂表面自由基、硫酸根自由基（SO₄^?－）和羟基自由基（·OH）共同参与反应的准二级动力学过程。

关键词: 钢渣, 活性炭, 过硫酸盐, 盐酸四环素

CLC Number:

X703

Yan HUANG,Bo XING,Guo YANG,Qiang ZHOU,Zhongcai PAN. Catalytic degradation of tetracycline hydrochloride with persulfate catalyzed by composite of carbon and steel slag[J]. Industrial Water Treatment, 2022, 42(3): 131-138.

黄艳,邢波,杨郭,周强,潘中才. 钢渣/活性炭复合材料催化过硫酸盐降解盐酸四环素[J]. 工业水处理, 2022, 42(3): 131-138.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2021-0914

https://www.iwt.cn/EN/Y2022/V42/I3/131

Figures/Tables 12

References 23

1	LI Guoting， GUO Yiping， ZHAO Weigao. Efficient adsorption removal of tetracycline by layered carbon particles prepared from seaweed biomass［J］. Environmental Progress & Sustainable Energy，2017， 36（1）：122-127. doi:10.1002/ep.12437 doi: 10.1002/ep.12437
2	郭喜丰，肖广全，马丽莉，等. 超声波降解四环素类抗生素废水［J］. 环境工程学报，2014， 8（4）：1503-1509.
	GUO Xifeng， XIAO Guangquan， MA Lili，et al. Degradation of tetracycline antibiotic wastewater by ultrasonic wave［J］. Chinese Journal of Environmental Engineering，2014，8（4）：1503-1509.
3	李志. 磁性碳材料的制备表征及对水中盐酸四环素吸附性能的研究［D］. 马鞍山：安徽工业大学，2019.
	LI Zhi. Preparation and characterization of magnetic carbon materials and study on adsorption properties of tetracycline hydrochloride in water［D］. Ma’anshan：Anhui University of Technology， 2019.
4	刘希，张宇峰，罗平. 改性花生壳对四环素类抗生素的吸附特性研究［J］. 环境污染与防治， 2013，35（5）：35-39. doi:10.3969/j.issn.1001-3865.2013.05.007 doi: 10.3969/j.issn.1001-3865.2013.05.007
	LIU Xi， ZHANG Yufeng， LUO Ping，et al. Adsorption characteristics of modified peanut shell for tetracycline antibiotics［J］. Environmental Pollution & Control，2013，35（5）：35-39. doi:10.3969/j.issn.1001-3865.2013.05.007 doi: 10.3969/j.issn.1001-3865.2013.05.007
5	VIENO N M， HÄRKKI H L， TUHKANEN T，et al. Occurrence of pharmaceuticals in river water and their elimination in a pilot-scale drinking water treatment plant［J］. Environmental Science & Technology，2007，41（14）：5077-5084. doi:10.1021/es062720x doi: 10.1021/es062720x
6	WANG Jianbing， ZHI Dan， ZHOU Hao，et al. Evaluating tetracycline degradation pathway and intermediate toxicity during the electrochemical oxidation over a Ti/Ti₄O₇ anode［J］. Water Research， 2018，137（10）：13649-13697. doi:10.1016/j.watres.2018.03.030 doi: 10.1016/j.watres.2018.03.030
7	LOU Yaoyin， YE Zhilong， CHEN Shaohua，et al. Influences of dissolved organic matters on tetracyclines transport in the process of struvite recovery from swine wastewater［J］. Water Research， 2018，134（5）：311-326. doi:10.1016/j.watres.2018.02.010 doi: 10.1016/j.watres.2018.02.010
8	SHEN Tao， WANG Qi， GUO Zhaoying，et al. Hydrothermal synthesis of carbon quantum dots using different precursors and their combination with TiO₂ for enhanced photocatalytic activity［J］. Ceramics International，2018，44（10）：11828-11834. doi:10.1016/j.ceramint.2018.03.271 doi: 10.1016/j.ceramint.2018.03.271
9	张霄，张静，闫春晖，等. CuO@C催化过二硫酸盐降解盐酸四环素研究［J］. 水处理技术， 2019，45（4）：17-20. doi:10.16796/j.cnki.1000-3770.2019.04.004 doi: 10.16796/j.cnki.1000-3770.2019.04.004
	ZHANG Xiao， ZHANG Jing， YAN Chunhui，et al. Catalytic degradation of tetracycline hydrochloride by perdisulfide with CuO@C［J］. Technology of Water Treatment，2019，45（4）：17-20. doi:10.16796/j.cnki.1000-3770.2019.04.004 doi: 10.16796/j.cnki.1000-3770.2019.04.004
10	JIANG Xia， GUO Yinghui， ZHANG Liangbo，et al. Catalytic degradation of tetracycline hydrochloride by persulfate activated with nano Fe⁰ immobilized mesoporous carbon［J］. Chemical Engineering Journal，2018，341：392-401. doi:10.1016/j.cej.2018.02.034 doi: 10.1016/j.cej.2018.02.034
11	林尤强. 过硫酸盐活化高级氧化技术在废水处理中的应用［D］. 长春：长春理工大学，2020.
	LIN Youqiang. Application of persulfate activated advanced oxidation technology to wastewater treatment［D］. Changchun：Changchun University of Science and Technology，2020.
12	贾要强，孙志敏，王星磊，等. 钢渣资源化利用现状分析［J］. 河北企业，2017，334（5）： 61-62. doi:10.3969/j.issn.1008-1968.2017.05.030 doi: 10.3969/j.issn.1008-1968.2017.05.030
	JIA Yaoqiang， SUN Zhimin， WANG Xinglei，et al. Analysis on the present situation of steel slag resource utilization［J］. Heibei Qiye，2017，334（5）：61-62. doi:10.3969/j.issn.1008-1968.2017.05.030 doi: 10.3969/j.issn.1008-1968.2017.05.030
13	郭婧怡，马扬帆，杨绍贵，等. 切割钢渣活化过硫酸盐降解偶氮类染料酸性红73［J］. 环境科学学报，2019，39（8）：2550-2558.
	GUO Jingyi， MA Yangfan， YANG Shaogui，et al. Degradetion of azo dyes acid red 73 by activates persulfate with cutting steel slag［J］. Acta Scientiae Circumstantiae，2019，39（8）：2550-2558.
14	程敏. 基于钢渣资源化利用的类Fenton反应去除有机污染物的机理研究［D］. 长沙：湖南大学，2018.
	CHENG Min. The mechanism of organic pollutants removal by Fenton-like reaction based on steel slag resource utilization［D］. Changsha：Hunan University，2018.
15	REY A， FARALDOS M， CASAS J A，et al. Catalytic wet peroxide oxidation of phenol over Fe/AC catalysts：Influence of iron precursor and activated carbon surface［J］. Applied Catalysis B：Environmental， 2009，86（1）：69-77. doi:10.1016/j.apcatb.2008.07.023 doi: 10.1016/j.apcatb.2008.07.023
16	BAI Jianfei， LIU Yong， YIN Xiaohong，et al. Efficient removal of nitrobenzene by Fenton-like process with Co-Fe layered double hydroxide［J］. Applied Surface Science，2017，416：45-50. doi:10.1016/j.apsusc.2017.04.117 doi: 10.1016/j.apsusc.2017.04.117
17	SING K S W， WILLIAMS R T. Physisorption hysteresis loops and the characterization of nanoporous materials［J］. Adsorption Science & Technology，2004，22（10）：773-782. doi:10.1260/0263617053499032 doi: 10.1260/0263617053499032
18	姚梅琴，余剑，郭凤，等. 氧化铁石墨固相还原非等温反应动力学［J］. 化工学报，2013，64（6）：2072-2079. doi:10.3969/j.issn.0438-1157.2013.06.024 doi: 10.3969/j.issn.0438-1157.2013.06.024
	YAO Meiqin， YU Jian， GUO Feng，et al. Kinetics of nonisothermal reaction of solid phase reduction of iron oxide graphite［J］. Journal of Chemical Industry and Engineering（China），2013，64（6）： 2072-2079. doi:10.3969/j.issn.0438-1157.2013.06.024 doi: 10.3969/j.issn.0438-1157.2013.06.024
19	郑柏存，胡黎明，杨纪民，等. α-Fe₂O₃还原过程的TPR研究［J］. 信息记录材料，1993（3）： 6-8.
	ZHENG Bocun， HU Liming， YANG Jimin，et al. Study on TPR of α-Fe₂O₃ reduction process［J］. Xinxi Jilu Cailiao，1993（3）：6-8.
20	LIU Hongxia， YAO Jiayi， WANG Lianhong，et al. Effective degradation of fenitrothion by zero-valent iron powder Fe⁰ activated persulfate in aqueous solution：Kinetic study and product identification［J］. Chemical Engineering Journal，2019，358：1479-1488. doi:10.1016/j.cej.2018.10.153 doi: 10.1016/j.cej.2018.10.153
21	LUO Wei， ZHU Lihua， WANG Nan，et al. Efficient removal of organic pollutants with magnetic nanoscaled BiFeO₃ as a reusable heterogeneous Fenton-like catalyst［J］. Environment Science & Technology，2010，44（5）：1786-1791. doi:10.1021/es903390g doi: 10.1021/es903390g
22	PEYTON G R. The free-radical chemistry of persulfate-based total organic carbon analyzers［J］. Marine Chemistry，1993，41（1）：91-103. doi:10.1016/0304-4203(93)90108-z doi: 10.1016/0304-4203(93)90108-z
23	YANG D S， BHATTACHARJYA D， SONG M Y，et al. Nitrogen-doped ordered mesoporous carbon with different morphologies for the oxygen reduction reaction：Effect of iron species and synergy of textural properties［J］. ChemCatChem，2015，7（18）：2882-2990. doi:10.1002/cctc.201500340 doi: 10.1002/cctc.201500340

催化剂	S_BET/ （m²·g^-1）	V_t/ （cm³·g^-1）	V_micro/ （cm³·g^-1）	（V_micro/V_t）/ %	D/nm
GZ	6.3	0.016	0	0	10.12
AC	1 039.3	0.620	0.447	72.1	2.39
20%GZ/AC	870.7	0.516	0.381	73.8	2.37
40%GZ/AC	763.8	0.565	0.273	48.3	2.96
60%GZ/AC	672.6	0.509	0.231	45.4	3.03
80%GZ/AC	578.0	0.437	0.201	46.0	3.02

催化剂	S_BET/ （m²·g^-1）	V_t/ （cm³·g^-1）	V_micro/ （cm³·g^-1）	（V_micro/V_t）/ %	D/nm
GZ	6.3	0.016	0	0	10.12
AC	1 039.3	0.620	0.447	72.1	2.39
20%GZ/AC	870.7	0.516	0.381	73.8	2.37
40%GZ/AC	763.8	0.565	0.273	48.3	2.96
60%GZ/AC	672.6	0.509	0.231	45.4	3.03
80%GZ/AC	578.0	0.437	0.201	46.0	3.02

样品	主要成分/%
样品	Fe₂O₃	SiO₂	CaO	ZnO	CuO	Al₂O₃	MnO	MgO	P₂O₅	TiO₂
GZ	56.66	13.80	11.04	4.40	3.59	2.71	0.63	0.63	0.57	0.50
80%GZ/AC	55.40	13.70	11.75	4.16	3.40	2.46	0.59	0.61	1.13	0.68
60%GZ/AC	54.92	14.60	11.69	3.97	3.12	2.56	0.57	0.47	1.25	0.73
40%GZ/AC	52.66	15.30	12.00	3.86	3.19	3.04	0.50	0.69	1.56	0.83
20%GZ/AC	51.15	16.10	12.60	3.25	2.43	3.00	0.46	0.34	2.21	1.02
AC	2.96	1.48	0.97	—	—	0.22	—	—	0.26	0.21

样品	主要成分/%
样品	Fe₂O₃	SiO₂	CaO	ZnO	CuO	Al₂O₃	MnO	MgO	P₂O₅	TiO₂
GZ	56.66	13.80	11.04	4.40	3.59	2.71	0.63	0.63	0.57	0.50
80%GZ/AC	55.40	13.70	11.75	4.16	3.40	2.46	0.59	0.61	1.13	0.68
60%GZ/AC	54.92	14.60	11.69	3.97	3.12	2.56	0.57	0.47	1.25	0.73
40%GZ/AC	52.66	15.30	12.00	3.86	3.19	3.04	0.50	0.69	1.56	0.83
20%GZ/AC	51.15	16.10	12.60	3.25	2.43	3.00	0.46	0.34	2.21	1.02
AC	2.96	1.48	0.97	—	—	0.22	—	—	0.26	0.21

[1]	Wenhao WANG, Yexing CHENG, Yuyin WANG, Tingting HOU, Xiaofeng WU, Yucai LI. Effect of different types of activated carbon on the adsorption- reduction of Cr(Ⅵ) by mZVI/activated carbon [J]. Industrial Water Treatment, 2025, 45(2): 150-158.
[2]	Xianchun PENG, Lili ZHENG, Haoran LU, Zhefeng WANG, Zheng ZHU, Wenyan LIANG. Performance of sulfur/steel slag composite matrix in removing nitrate from surface water with low-carbon content [J]. Industrial Water Treatment, 2025, 45(1): 41-48.
[3]	Xiangyu FU, Yafeng LI, Yihan LIU, Keqing CUI, Lingping WANG. Tributyl phosphate modified biochar activated PMS for degradation of bisphenol A [J]. Industrial Water Treatment, 2025, 45(1): 87-93.
[4]	Weiye ZHANG, Jing SHEN, Zihe PAN, Yipeng SONG, Huaigang CHENG, Huirong ZHANG. Analysis of heel formation and influencing factors during the thermal regeneration process of saturated activated carbon [J]. Industrial Water Treatment, 2025, 45(1): 17-25.
[5]	Ziang CHEN, Yiting YANG, Qian CHI, Jingjing YANG, Guangsen XIA, Juhong ZHAN. Effect of electrocatalytic ozone coupled with bioactived carbon process on removal of carbamazepine and microbial community in wastewater [J]. Industrial Water Treatment, 2024, 44(9): 91-97.
[6]	Yuhao GAO, Yongrong DUAN, Hong LI, Jianjun WANG, Yingchun WEI, Qiang LI, Furen KANG, Liqing REN. High-efficient treatment of phenol-containing wastewater with iron-loaded fine coal gasification slag activated carbon [J]. Industrial Water Treatment, 2024, 44(7): 119-124.
[7]	Xiongqiang YANG. Exploration of process design for biochemical treatment of coking wastewater [J]. Industrial Water Treatment, 2024, 44(7): 197-202.
[8]	Jie ZHAO, Junfeng WU, Yanyan DOU, Fedorov Svyatoslav VIKTOROVICH, Xianli WANG, Biao LIU, Xinfeng ZHU, Yanli MAO, Hongbin GAO. Research progress on degradation of organic pollutants by single atom activated persulfate [J]. Industrial Water Treatment, 2024, 44(7): 38-46.
[9]	Xiling ZHANG, Lifang CHEN, Jiangping LIAO, Liting SONG, Jia XIONG, Congcong ZHEN. Experimental study on treatment of Pb ion wastewater by alkali fusion modified steel slag [J]. Industrial Water Treatment, 2024, 44(7): 89-95.
[10]	Bin TAN, Huiru HAO, Yutong XIANG, Yuning LIU, Qian ZHANG. Degradation of Enrofloxacin by photocatalytic system based on BC-BiOI/PMS [J]. Industrial Water Treatment, 2024, 44(6): 143-150.
[11]	Jin CHAI, Xue BAI, Zhiyao ZHANG, Min HU, Juan SHI, Pengkang JIN. Study on degradation of dye organics by maleic acid activated persulfate [J]. Industrial Water Treatment, 2024, 44(6): 151-157.
[12]	Xufeng LI, Shaopo WANG, Yao ZHOU, Jing CHANG, Rongguang LI. Enhanced treatment technology for Yangtze River water in a water purification plant in Tianjin [J]. Industrial Water Treatment, 2024, 44(5): 132-140.
[13]	Zhen LIU, Lang LIU, Peng ZHENG, Rong LIU, Shaochun YUAN, Cong LI, Yao CHEN. Research progress of regenerated activated carbon in electrochemical advanced oxidation process [J]. Industrial Water Treatment, 2024, 44(5): 42-51.
[14]	Zhen YANG, Yang LI, Shiying YANG. Efficient treatment of diazodinitrophenol industrial wastewater by a sequential zero-valent aluminum reduction- persulfate oxidation process [J]. Industrial Water Treatment, 2024, 44(4): 98-104.
[15]	Wenqi LI, Caigui LUO, Yuting XIONG, Xianping LUO. Degradation of Orange Ⅱ by persulfate activated with nitrogen-doped porous sludge carbon [J]. Industrial Water Treatment, 2024, 44(3): 133-141.

Please choose a citation manager

Content to export