Preparation of modified polyethyleneimine chelating agents and treatment of heavy metals and organic wastewater

doi:10.19965/j.cnki.iwt.2025-0036

Abstract

Abstract:

A novel dithiocarbamate heavy metal chelating agent(PEI-DTC) was prepared using water-soluble polyethyleneimine(PEI) as the raw material and carbon disulfide (CS₂) under alkaline conditions. The presence of abundant dithiocarbamate groups in PEI-DTC was confirmed by UV spectroscopy, infrared spectroscopy, elemental analysis,and scanning electron microscopy. The effects of the preparation conditions of PEI-DTC and the chelation process on the removal of Cu²⁺ were investigated in detail through single-factor experiments using simulated wastewater containing Cu²⁺ and contaminated soil as treatment objects. Under pH≥3, PEI-DTC could remove 99.8% of Cu²⁺ from water and 99.9% of Cu²⁺ from soil. Compared with traditional commercial sodium dimethyldithiocarbamate(SDD) and sodium sulfide(Na₂S), PEI-DTC showed stronger heavy metal removal ability, wider adaptability(pH 1-9), and higher stability. The risk of secondary leaching of Cu²⁺ after treatment was low, meeting the national solid waste landfill treatment standards. Meanwhile, PEI-DTC chelated with Fe was used to activate persulfate for the degradation of oxytetracycline(OTC) in water. Under the optimal conditions, the degradation rate of OTC could reach 83.4%.

Key words: polyethyleneimine, chelating agent, heavy metal removal, degradation of oxytetracycline hydrochloride

摘要：

以水溶性聚乙烯亚胺（PEI）为原料，在碱性条件下经CS₂改性后制备出新型二硫代氨基甲酸盐类重金属螯合剂（PEI-DTC），并采用紫外光谱、红外光谱、元素分析、扫描电镜等表征方法证实了PEI-DTC具有丰富的二硫代氨基基团。以含Cu²⁺的模拟废水和污染土壤为处理对象，通过单因素实验深入探究了PEI-DTC制备条件和螯合工艺对其去除Cu²⁺的影响。pH≥3时，PEI-DTC可去除水体中99.8%的Cu²⁺，固化土壤中99.9%的Cu²⁺。相比于传统商用福美钠（SDD）和硫化钠（Na₂S），PEI-DTC展现出更强的重金属去除能力、更广的适应性（pH为1~9）和更高的稳定性。经处理后Cu²⁺二次浸出风险低，达到国家固废填埋处理标准。同时，将PEI-DTC螯合Fe后用于活化过硫酸盐降解水体中盐酸土霉素（OTC），最佳工艺条件下OTC降解率可达83.4%。

关键词: 聚乙烯亚胺, 螯合剂, 重金属去除, 降解盐酸土霉素

CLC Number:

X703.1

Yunliang FAN, Caiyi JIANG, Bo XING, Yi WANG, Min LI, Guo YANG, Fuping ZHANG, Siyang ZHANG. Preparation of modified polyethyleneimine chelating agents and treatment of heavy metals and organic wastewater[J]. Industrial Water Treatment, 2025, 45(12): 137-146.

樊云亮, 江彩义, 邢波, 王议, 李敏, 杨郭, 张福平, 张思洋. 改性聚乙烯亚胺螯合剂的制备及其对重金属与有机废水的处理[J]. 工业水处理, 2025, 45(12): 137-146.

/ / Recommend / Download Citations

URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2025-0036

https://www.iwt.cn/EN/Y2025/V45/I12/137

Figures/Tables 15

Fig.1 UV analysis of the PEI-DTC

Fig.2 IR analysis of the PEI-DTC

Table 1 Elemental content analysis of PEI-DTC and PEI

主要成分

元素质量分数/%

C/N

（物质的量比）

N/S—S

（物质的量比）

Fig.3 PEI-DTC thermogravimetric analysis

Fig.4 SEM analysis of PEI-DTC and PEI-DTC-Cu

Fig.5 SEM analysis of PEI-DTC and PEI-DTC-Cu

Fig.6 XRD analysis of PEI-DTC and PEI-DTC-Cu

Fig.7 BET analysis of PEI-DTC and PEI-DTC-Cu

Fig.8 Effects of preparation conditions on the chelation performance of PEI-DTC

Fig.9 Effects of initial pH and chelation time of Cu²⁺solution

Fig.10 Chelation stability analysis

Fig.11 Cu²⁺curing analysis in soil

Fig.12 PEI-DTC-Fe catalytic degradation of OTC by PS

Fig.13 Effects of degradation conditions and stability analysis

Fig.14 Quenching experiment

References 28

[1]	WANG Xingmin， QI Feilan， XIONG Jie，et al. Synthesis of a novel dithiocarbamate surfactant derivative adsorbent for efficient removal of heavy metal ions［J］. ACS Omega，2023，8（44）：41512-41522. doi:10.1021/acsomega.3c05476
[2]	DAS A， ADAK M K. Photo-catalyst for wastewater treatment：A review of modified Fenton，and their reaction kinetics［J］. Applied Surface Science Advances，2022，11：100282. doi:10.1016/j.apsadv.2022.100282
[3]	ZHU Zihan， GUO Yanyan， ZHAO Youcai，et al. A novel waste-recycled chelating agent for the stabilization of lead in municipal solid waste incineration fly ash：Preparation，feasibility，and mechanism analysis［J］. Journal of Hazardous Materials，2022，427：127914. doi:10.1016/j.jhazmat.2021.127914
[4]	LI Bojun， GUO Xuejun， ZHANG Xiangyuan，et al. A new strategy to stabilize the heavy metals in carbonized MSWI-fly ash using an acid-resistant oligomeric dithiocarbamate chelator［J］. Journal of Hazardous Materials，2024，467：133686. doi:10.1016/j.jhazmat.2024.133686
[5]	MURUGAVEL R， CHOUDHURY A， WALAWALKAR M G，et al. Metal complexes of organophosphate esters and open-framework metal phosphates：Synthesis，structure，transformations，and applications［J］. Chemical Reviews，2008，108（9）：3549-3655. doi:10.1021/cr000119q
[6]	SHI Yifeng， NAREN G， ZHANG Ying，et al. Synthesis，Structures，optical properties and DFT studies of neodymium complexes containing octanoyl amino carboxylic acids［J］. Optics & Laser Technology，2022，155：108445. doi:10.1016/j.optlastec.2022.108445
[7]	YAN Pingfang， YE Maoyou， GUAN Zhijie，et al. Synthesis of magnetic dithiocarbamate chelating resin and its absorption behavior for ethylenediaminetetraacetic acid copper［J］. Process Safety and Environmental Protection，2019，123：130-139. doi:10.1016/j.psep.2018.12.026
[8]	ZHAO Menglan， WANG Yu， ZHAO Hui，et al. Effective adsorption of heavy metals on layered double hydroxides modify through dithiocarbamate prepared by CS₂ and different molecular weight of polyethyleneimine［J］. Separation and Purification Technology，2023，327：124886. doi:10.1016/j.seppur.2023.124886
[9]	耿继光，张树艳，刘佳欣，等. DTC类重金属螯合剂制备研究进展［J］. 应用化工，2021，50（9）：2540-2544.
	GENG Jiguang， ZHANG Shuyan， LIU Jiaxin，et al. Research progress in the preparation of DTC heavy metal chelating agents［J］. Applied Chemical Industry，2021，50（9）：2540-2544.
[10]	房孟，杨浩. 多胺基聚乙烯亚胺页岩抑制性能研究［J］. 应用化工，2022，51（12）：3434-3439.
	FANG Meng， YANG Hao. Property study of polyethyleneimine as shale inhibitor［J］. Applied Chemical Industry，2022，51（12）：3434-3439.
[11]	桑芳娟，王刚，王雪，等. 高分子絮凝剂DT（PEI-PAM）的优化制备及其除Cu（Ⅱ）性能与机理［J］. 工业水处理，2024，44（12）：67-76.
	SANG Fangjuan， WANG Gang， WANG Xue，et al. Optimized preparation of dithiocarboxylated polyethyleneimine-polyacrylamide and its Cu（Ⅱ） removal performance and mechanism［J］. Industrial Water Treatment，2024，44（12）：67-76.
[12]	HJ/T 300—2007 固体废物浸出毒性浸出方法：醋酸缓冲溶液法［S］. doi:10.3390/inorganics11030090
	HJ/T 300—2007 Solid waste. Leaching toxicity leaching method：Acetic acid buffer solution method ［S］. doi:10.3390/inorganics11030090
[13]	HJ 557—2010 固体废物浸出毒性浸出方法：水平振荡法［S］. HJ 557—. doi:10.3403/bsen12457
	2010 Solid waste leaching toxic leaching method：Horizontal oscillation method ［S］. doi:10.3403/bsen12457
[14]	甄豪波. 重金属捕集剂DTC（TBA）的制备及处理含铜废水的研究［D］. 广州：华南理工大学，2011.
	ZHEN Haobo. Preparation of heavy metal collector DTC（TBA） and its treatment of copper containing wastewater［D］. Guangzhou：South China University of Technology，2011.
[15]	童立志. 焚烧飞灰螯合效果评价方法优化及新型高分子螯合剂合成［D］. 哈尔滨：哈尔滨工业大学，2020.
	TONG Lizhi. Optimization of chelating effect evaluation method of incineration fly ash and synthesis of novel polymer chelating agent［D］. Harbin：Harbin Institute of Technology，2020.
[16]	BOBINIHI F F， OSUNTOKUN J， ONWUDIWE D C. Syntheses and characterization of nickel（Ⅱ） dithiocarbamate complexes containing NiS₄ and NiS₂PN moieties：Nickel sulphide nanoparticles from a single source precursor［J］. Journal of Saudi Chemical Society，2018，22（4）：381-395. doi:10.1016/j.jscs.2017.10.001
[17]	CHEN Hui， ZHAO Yue， YANG Qiuyu，et al. Preparation of poly-ammonium/sodium dithiocarbamate for the efficient removal of chelated heavy metal ions from aqueous environments［J］. Journal of Environmental Chemical Engineering，2018，6（2）：2344-2354. doi:10.1016/j.jece.2018.03.029
[18]	CORALLI I， FABBRI D， FACCHIN A，et al. Analytical pyrolysis of polyethyleneimines［J］. Journal of Analytical and Applied Pyrolysis，2023，169：105838. doi:10.1016/j.jaap.2022.105838
[19]	AHMAD K S， MEHMOOD R F， JAFFRI S B，et al. DTC-［MnS₂∶LaS］complexes of diethyldithiocarbamates：Single source precursor in situ mode synthesis，characterization，and investigation of capacitive functionality for supercapacitor electrodes［J］. Journal of Inorganic and Organometallic Polymers and Materials，2025，1（1）：1-19.
[20]	AYALEW Z M， ZHANG Xiangyuan， GUO Xuejun，et al. Removal of Cu，Ni and Zn directly from acidic electroplating wastewater by Oligo-Ethyleneamine dithiocarbamate（OEDTC）［J］. Separation and Purification Technology，2020，248：117114. doi:10.1016/j.seppur.2020.117114
[21]	宋倩楠. 二硫代氨基甲酸盐类螯合剂的合成及飞灰稳定化效果研究［D］. 北京：北京化工大学，2020.
	SONG Qiannan. Study on synthesis of dithiocarbamate chelating agents and stabilization effect of fly ash［D］. Beijing：Beijing University of Chemical Technology，2020.
[22]	CUI Wenwen， LI Xiaoqiang， DUAN Wei，et al. Heavy metal stabilization remediation in polluted soils with stabilizing materials：A review［J］. Environmental Geochemistry and Health，2023，45（7）：4127-4163. doi:10.1007/s10653-023-01522-x
[23]	GAO Jun， HAN Haoxuan， GAO Chang，et al. Organic amendments for in situ immobilization of heavy metals in soil：A review［J］. Chemosphere，2023，335：139088. doi:10.1016/j.chemosphere.2023.139088
[24]	QU Lili， XU Jiayang， DAI Zhihua，et al. Selenium in soil-plant system：Transport，detoxification and bioremediation［J］. Journal of Hazardous Materials，2023，452：131272. doi:10.1016/j.jhazmat.2023.131272
[25]	MÉSZÁROS R， VARGA I， GILÁNYI T. Adsorption of poly（ethyleneimine） on silica surfaces：Effect of pH on the reversibility of adsorption［J］. Langmuir，2004，20（12）：5026-5029. doi:10.1021/la049611l
[26]	GAO Wenyan， ROGER RAZANAJATOVO M， SONG Yaran，et al. Efficient heavy metal sequestration from water by Mussel-inspired polystyrene conjugated with polyethyleneimine（PEI）［J］. Chemical Engineering Journal，2022，429：132599. doi:10.1016/j.cej.2021.132599
[27]	张拔群，罗仙平，唐学昆，等. 天然矿物纤维水镁石活化过一硫酸盐降解亚甲基蓝［J］. 工业水处理，2025，45（2）：85-95.
	ZHANG Baqun， LUO Xianping， TANG Xuekun，et al. Degradation of methylene blue by activated peroxymonosulfate by natural mineral fibrous brucite［J］. Industrial Water Treatment，2025，45（2）：85-95.
[28]	LIU Wei， LU Yanrong， DONG Yingbo，et al. A critical review on reliability of quenching experiment in advanced oxidation processes［J］. Chemical Engineering Journal，2023，466：143161. doi:10.1016/j.cej.2023.143161

Please choose a citation manager

Content to export