Performance and mechanism of Ni-EDTA decomplexing by three-dimensional electrocatalysis

doi:10.16085/j.issn.1000-6613.2023-1908

Abstract

Abstract:

Three-dimensional electrocatalysis is an efficient technology for treating organic wastewater containing metal complexes, but the decomplexation mechanism is still unclear. This study constructed a three-dimensional electrocatalytic system to decomplex simulated wastewater containing Ni-EDTA complex, with ruthenium and iridium coated titanium plate as the anode, and stainless steel plate as the cathode. The results indicated that the removal rate of Ni-EDTA is related to the type of electrolyte, electrolyte concentration, current density, and initial pH, and all complied with the second-order reaction kinetics. The highest removal rates of Ni-EDTA and COD were 85.05% and 80.48%, respectively with NaCl solution as the electrolyte and concentration of 0.25g/L, under 1.0mA/cm² current density, and an initial pH of 3.0. The rate constants were 0.0053min^-1 and R² was 0.9893. Electrochemical testing showed that the addition of particle electrodes increased the catalytic active sites, catalytic reaction mass transfer area, and charge storage sites, enhanced electron transfer, and improved the electrocatalytic performance. By using three-dimensional fluorescence spectroscopy, ultraviolet spectroscopy, and active component identification, the degradation process of EDTA was analyzed to reveal the efficient mechanism of three-dimensional electrocatalysis for Ni-EDTA decomplexing. This work provides a theoretical basis and technical support for the treatment of metal-complexed organic wastewater.

Key words: three-dimensional electrode system, Ni-EDTA wastewater, decomplexing mechanism, effect and energy consumption of decomplexation, kinetics

摘要：

三维电催化是处理金属络合物有机废水的高效技术，然而其破络机制尚不明晰。本研究以镀钌铱钛板为阳极，不锈钢板为阴极，引入颗粒电极，构建三维电催化体系，对含Ni-EDTA络合物的模拟废水进行破络处理。结果表明Ni-EDTA破络去除效果与电解质种类、电解质浓度、电流密度和初始pH有关，且均符合二级反应动力学。在电解质为NaCl，电解质浓度0.25g/L，电流密度1.0mA/cm²以及初始pH为3.0条件下Ni-EDTA和COD的去除率最高，分别达到85.05%和80.48%，其速率常数为0.0053min^-1，R²为0.9893。电化学测试表明颗粒电极的加入增加了催化活性位点、催化反应传质面积和电荷储存位点，增强了电子转移，提高了电催化性能。通过三维荧光光谱法、紫外光谱法、活性组分鉴定，分析EDTA降解过程，揭示了三维电催化对Ni-EDTA的高效破络机制，为金属络合有机废水处理提供理论基础和技术支撑。

关键词: 三维电极体系, Ni-EDTA废水, 破络机制, 破络效能, 动力学

CLC Number:

TQ15

ZHANG Shuo, FENG Yan, LU Yuyu, JIA Xinqiang, QIU Liping. Performance and mechanism of Ni-EDTA decomplexing by three-dimensional electrocatalysis[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6573-6582.

张硕, 冯岩, 卢玉玉, 贾新强, 邱立平. 三维电催化破络Ni-EDTA性能及机制[J]. 化工进展, 2024, 43(11): 6573-6582.

Figures/Tables 12

References 28

1	ZHUANG Ping, MCBRIDE Murray B, XIA Hanping, et al. Health risk from heavy metals via consumption of food crops in the vicinity of Dabaoshan mine, South China[J]. Science of the Total Environment, 2009, 407(5): 1551-1561.
2	DONG Xiaoqing, LI Chaolin, LI Ji, et al. Application of a system dynamics approach for assessment of the impact of regulations on cleaner production in the electroplating industry in China[J]. Journal of Cleaner Production, 2012, 20(1): 72-81.
3	Olcay TÜNAY, KABDASLI Isik, Rüya TASLI. Pretreatment of complexed metal wastewaters[J]. Water Science and Technology, 1994, 29(9): 265-274.
4	关智杰. 臭氧催化氧化-重金属捕集深度处理化学镀镍废水的研究[D]. 广州: 广东工业大学, 2019.
	GUAN Zhijie. Study on advanced treatment of electroless nickel plating wastewater by ozone catalytic oxidation-heavy metal chelation[D]. Guangzhou: Guangdong University of Technology, 2019.
5	戎关镛. 关于金属-EDTA络合物的条件稳定常数[J]. 冶金分析, 1990, 10(3): 59-61.
	RONG Guanyong. Conditional stability constants of metal-EDTA complexes [J]. Metallurgical Analysis, 1990, 10(3): 59-61.
6	HE Hongping, WU Deli, ZHAO Linghui, et al. Sequestration of chelated copper by structural Fe(Ⅱ): Reductive decomplexation and transformation of CuII-EDTA[J]. Journal of Hazardous Materials, 2016, 309: 116-125.
7	贾鹏, 俞马宏. SBR间歇活性污泥法处理络合铜废水试验研究[J]. 水处理技术, 2012, 38(S1): 76-79.
	JIA Peng, YU Mahong. Study on the treatment of complexation of copper by active sludge on SBR[J]. Technology of Water Treatment, 2012, 38(S1): 76-79.
8	YANG Xin, WANG Jinnan, CHENG Cheng. Preparation of new spongy adsorbent for removal of EDTA-Cu(Ⅱ) and EDTA-Ni(Ⅱ) from water [J]. Chinese Chemical Letters, 2013, 24(5): 383-385.
9	MOHSEN-NIA M, MONTAZERI P, MODARRESS H. Removal of Cu²⁺ and Ni²⁺ from wastewater with a chelating agent and reverse osmosis processes[J]. Desalination, 2007, 217(1/2/3): 276-281.
10	ZHAO Wei, LIU Zicheng, YUAN Yuan, et al. Insight into Cu(Ⅱ) adsorption on polyamine resin in the presence of HEDP by tracking the evolution of amino groups and Cu(‍Ⅱ‍)-HEDP complexes[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(5): 5256-5263.
11	OZTURK Dilara, YILMAZ Alper Erdem. Treatment of slaughterhouse wastewater with the electrochemical oxidation process: Role of operating parameters on treatment efficiency and energy consumption[J]. Journal of Water Process Engineering, 2019, 31: 100834.
12	MARTÍNEZ-HUITLE Carlos Alberto, PANIZZA Marco. Electrochemical oxidation of organic pollutants for wastewater treatment[J]. Current Opinion in Electrochemistry, 2018, 11: 62-71.
13	符远航, 刘安迪, 黄纬斌, 等. 负载多壁碳纳米管的多孔Ti/SnO₂-Sb-Ni电极电催化氧化双酚A[J]. 环境科学, 2022, 43(5): 2640-2649.
	FU Yuanhang, LIU Andi, HUANG Weibin, et al. Electrocatalytic oxidation of bisphenol A by porous Ti/SnO₂-Sb-Ni electrode loaded with multi-wall carbon nanotubes[J]. Environmental Science, 2022, 43(5): 2640-2649.
14	石秋俊, 刘安迪, 唐柏彬, 等. Ni掺杂Sb-SnO₂瓷环粒子电极电催化氧化磺胺嘧啶[J]. 环境科学, 2020, 41(4): 1725-1733.
	SHI Qiujun, LIU Andi, TANG Bobin, et al. Electrocatalytic oxidation of sulfadiazine with Ni-doped Sb-SnO₂ceramic ring particle electrode[J]. Environmental Science, 2020, 41(4): 1725-1733.
15	HU Xinxin, YANG Shuai, YOU Xinyu, et al. Electrocatalytic decomplexation of Cu-EDTA and simultaneous recovery of Cu with Ni/GO-PAC particle electrode[J]. Chemical Engineering Journal, 2022, 428: 131468.
16	唐益洲. 三维电催化氧化处理柠檬酸络合镍废水的研究[D]. 长沙: 湖南师范大学, 2017.
	TANG Yizhou. Study on the advanced treatment of nickel citrate by three-dimensional electrocatalytic oxidation[D]. Changsha: Hunan Normal University, 2017.
17	杨舒敏. 三维电催化生物滤池深度处理含抗生素畜禽养殖废水效能及机制研究[D]. 济南: 济南大学, 2021.
	YANG Shumin. Study on the efficiency and mechanism of advanced treatment of antibiotic-containing livestock wastewater by three-dimensional electrocatalytic biological filter[D]. Jinan: University of Jinan, 2021.
18	DURANTE Christian, CUSCOV Marco, ISSE Abdirisak Ahmed, et al. Advanced oxidation processes coupled with electro-coagulation for the exhaustive abatement of Cr-EDTA[J]. Water Research, 2011, 45(5): 2122-2130.
19	YANG Xiupei, ZOU Ruyi, HUO Feng, et al. Preparation and characterization of Ti/SnO₂-Sb₂O₃-Nb₂O₅/PbO₂ thin film as electrode material for the degradation of phenol[J]. Journal of Hazardous Materials, 2009, 164(1): 367-373.
20	ZHOU Minghua, WANG Wei, CHI Meiling. Enhancement on the simultaneous removal of nitrate and organic pollutants from groundwater by a three-dimensional bio-electrochemical reactor[J]. Bioresource Technology, 2009, 100(20): 4662-4668.
21	DUAN Tigang, WEN Qing, CHEN Ye, et al. Enhancing electrocatalytic performance of Sb-doped SnO₂ electrode by compositing nitrogen-doped graphene nanosheets[J]. Journal of Hazardous Materials, 2014, 280: 304-314.
22	THOMAS R A, LAWLOR K, BAILEY M, et al. Biodegradation of metal-EDTA complexes by an enriched microbial population[J]. Applied and Environmental Microbiology, 1998, 64(4): 1319-1322.
23	ZHAO Xu, GUO Libao, HU Chengzhi, et al. Simultaneous destruction of Nickel(Ⅱ)-EDTA with TiO₂/Ti film anode and electrodeposition of nickel ions on the cathode[J]. Applied Catalysis B: Environmental, 2014, 144: 478-485.
24	卫昶, 陈霞玲, 周伟舫. Pb及Pb-7w/OSb合金在氧析出电位区生长的阳极膜[J]. 化学学报, 1992(5): 467-472.
	WEI Chang, CHEN Xialing, ZHOU Weifang. Anodic films grown at oxygen evolved potential range on Pb and Pb-7w/OSb alloy [J]. Acta Chimica Sinica, 1992， 50(5): 467-472.
25	NI Congcong, WANG Jingru, GUAN Yuxin, et al. Self-powered peroxi-coagulation for the efficient removal of p-arsanilic acid: pH-dependent shift in the contributions of peroxidation and electrocoagulation[J]. Chemical Engineering Journal, 2020, 391: 123495.
26	ZHU Xiuping, NI Jinren, XING Xuan, et al. Synergies between electrochemical oxidation and activated carbon adsorption in three-dimensional boron-doped diamond anode system[J]. Electrochimica Acta, 2011, 56(3): 1270-1274.
27	孟昭瑞, 高宁. 有机化合物的紫外光谱分析[J]. 西部资源, 2017(6): 179-182.
	MENG Zhaorui, GAO Ning. Ultraviolet spectral analysis of organic compounds [J]. Western Resources, 2017(6): 179-182.
28	刘泽坤. UV/H₂O₂工艺处理Ni-EDTA废水效能研究[D]. 哈尔滨: 哈尔滨工业大学, 2018.
	LIU Zekun. Treatment of Ni-EDTA containing wastewater by UV/H₂O₂ process[D]. Harbin: Harbin Institute of Technology, 2018.

反应级数	动力学方程	速率常数	相关系数
零级	C_t =-0.0545t+6.5187	0.0545	0.7205
一级	ln(C₀/C_t )=0.0152t+0.3337	0.0152	0.8943
二级	1/C_t =0.0053t+0.1334	0.0053	0.9893

反应级数	动力学方程	速率常数	相关系数
零级	C_t =-0.0545t+6.5187	0.0545	0.7205
一级	ln(C₀/C_t )=0.0152t+0.3337	0.0152	0.8943
二级	1/C_t =0.0053t+0.1334	0.0053	0.9893

反应体系	R_e/Ω	R_ct/Ω	C_dl/F
二维体系	7.700	33.300	3.000×10^-8
三维体系	7.981	10.940	4.360×10^-8

反应体系	R_e/Ω	R_ct/Ω	C_dl/F
二维体系	7.700	33.300	3.000×10^-8
三维体系	7.981	10.940	4.360×10^-8

[1]	HE Haixia, WAN Yameng, LI Fanfan, NIU Xinyu, ZHANG Jingwen, LI Tao, REN Baozeng. Kinetics and crystallization process of naphazoline hydrochloride in methanol-ethyl acetate system [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4230-4245.
[2]	YIN Chenyang, LIU Yongfeng, CHEN Ruizhe, ZHANG Lu, SONG Jin’ou, LIU Haifeng. Kinetic simulation of n-hexane pyrolysis reaction based on quantitative calculations [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4273-4282.
[3]	LIU Yucan, GAO Zhonglu, XU Xinyi, JI Xianguo, ZHANG Yan, SUN Hongwei, WANG Gang. Adsorption performance and mechanism of diuron from water by calcium-modified water hyacinth-based biochar [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4630-4641.
[4]	ZENG Wuqing, WANG Yu, BU Qingguo, MA Shuo, BAI Dongming, ZHANG Zongjian, ZHANG Peng, MA Dandan, WANG Shengbo, WANG Runqi, WU Liwen, LIU Chen, MA Hongting. Influence of mixed burning of aged refuse on the incineration characteristics of waste furnace [J]. Chemical Industry and Engineering Progress, 2024, 43(8): 4642-4653.
[5]	CAO Jingpei, YAO Naiyu, PANG Xinbo, ZHAO Xiaoyan, ZHAO Jingping, CAI Shijie, XU Min, FENG Xiaobo, YI Fengjiao. Research progress and development history of coal pyrolysis [J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3620-3636.
[6]	GU Songqi, SUN Fanfei, WEI Yao, SONG Xingfei, NAN Bing, LI Lina, HUANG Yuying. Time-resolved thermochemical in-situ XAFS methodology [J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3747-3755.
[7]	MA Dong, XIE Guilin, TIAN Zhihua, WANG Qinhui, ZHANG Jianguo, SONG Huilin, ZHONG Jin. Analysis of high temperature reduction process of phosphogypsum by coal gasification fine slag in fluidized bed [J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3479-3491.
[8]	WANG Debin, LIN Mengyu, YANG Xue, DONG Dianquan. Preparation and adsorption properties of zinc-doped titanium-based cesium ion sieves [J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1953-1961.
[9]	ZHU Yanni, WANG Wei, SUN Yanchenhao, WEI Gang, ZHANG Dawei. Numerical simulation of centrifugal spray drying based on single-droplet evaporation [J]. Chemical Industry and Engineering Progress, 2024, 43(4): 1700-1710.
[10]	HUANG Meng, SUN Zhigao, XU Wenchao, ZHANG Huanran, YANG Yang. Promotion of HCFC-141b hydrate production by lactone sophorolipids [J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1199-1205.
[11]	ZHANG Jinrong, PENG Changhong, LIN Jinxiu, JIANG Yang, QIU Zairong, ZHOU Hao, HU Zhenguang. Optimization of leaching conditions and macroscopic kinetics of spent LiFePO₄/C powder [J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6504-6513.
[12]	LIU Wenchen, HUANG Qiyu, XIE Yan, LYU Yang, WANG Yijie, XU Zhenkang, HAN Jipu. Research progress of low-temperature gathering and transportation of high water cut crude oil [J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5427-5440.
[13]	GU Yongzheng, ZHANG Yongsheng. Dynamic behavior and kinetic model of Hg⁰ adsorption by HBr-modified fly ash [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 498-509.
[14]	WANG Peng, ZHANG Yang, FAN Bingqiang, HE Dengbo, SHEN Changshuai, ZHANG Hedong, ZHENG Shili, ZOU Xing. Process and kinetics of hydrochloric acid leaching of high-carbon ferrochromium [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 510-517.
[15]	WANG Junjie, PAN Yanqiu, NIU Yabin, YU Lu. Molecular level catalytic reforming model construction and application [J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3404-3412.