摘要
以红土镍矿和无烟煤为原料,利用碳热还原法制备硅酸盐负载铁镍双金属材料(SiO_(2)@Fe-Ni),并将其用于活化过硫酸盐(PS)去除四环素。首先利用X射线衍射仪、扫描电子显微镜和能谱分析仪对SiO_(2)@Fe-Ni进行表征,结果表明,SiO_(2)@Fe-Ni中主要物相为铁纹石、镍纹石、石英、镁铁橄榄石等,Fe-Ni合金颗粒尺寸呈微纳米尺度(数十至数百纳米),且均匀分散在硅酸盐矿物表面。研究了反应条件对SiO_(2)@Fe-Ni/PS体系去除四环素的影响,结果表明,在溶液温度为30℃、SiO_(2)@Fe-Ni用量0.2 g/L、溶液初始pH值7.3、PS用量2 mM、四环素初始浓度为50 mg/L的条件下,60 min后四环素去除率达到68 36%。对活性自由基种类进行鉴定,并阐述其产生以及作用机理,结果表明,SiO_(2)@Fe-Ni/PS体系中硫酸根自由基(SO_(4)^(-)·)和羟基自由基(·OH)均存在,且·OH是主要的活性自由基;SO_(4)^(-)·的产生是通过材料表面的Fe^(2+)和Ni^(2+)活化PS得来的,·OH是通过SO_(4)^(-)·与溶液中的H_(2)O或OH^(-)反应生成的。总有机碳分析仪结果表明四环素矿化率60 24%。
Research purpose:Tetracycline,a widely used antibiotic with frequent environmental detection,poses significant ecological risks due to antibiotic resistance and human health threats.Conventional wastewater treatment methods exhibit limited efficacy in tetracycline removal,necessitating the development of cost-effective advanced oxidation technologies.A silicate-supported Fe-Ni bimetallic material(SiO_(2)@Fe-Ni)via carbothermal reduction of laterite nickel ore and anthracite was synthesized,and its performance in activating persulfate(PS)for tetracycline degradation was evaluated.The research also investigated the mechanism of reactive radical generation and the system's environmental safety.Research methods:SiO_(2)@Fe-Ni was prepared by ball-milling laterite nickel ore(45.91%Fe,0.89%Ni)and anthracite(80.98%fixed carbon),followed by pelletization,drying,and carbothermal reduction at 1000℃ for 60 min in a muffle furnace.The material was characterized using X-ray diffraction(XRD),scanning electron microscopy with energy-dispersive X-ray spectroscopy(SEM-EDS),and a total organic carbon analyzer(TOC).Tetracycline removal experiments were conducted in a thermostatic water bath with mechanical stirring(400 rpm)under varying conditions(pH:3.0-11.0 adjusted by 0.1 M NaOH/H_(2)SO_(4);temperature:20-40℃;PS:1-4 mM;SiO_(2)@Fe-Ni dosage:0.05-0.3 g/L).Reactive radicals(SO_(4)^(-)·and·OH)were identified via electron spin resonance spectroscopy(ESR)and quenching experiments with methanol and tert-butanol.Metal leaching and mineralization efficiency were assessed to evaluate environmental compatibility.Results:The SiO_(2)@Fe-Ni exhibites micro-nano Fe-Ni alloy particles(96.22%Fe,3.78%Ni)uniformly dispersed on a silicate matrix(54.88%Si,41.62%O),enhancing active site exposure and electron transfer.Optimal conditions(0.2 g/L SiO_(2)@Fe-Ni,2 mM PS,pH 7.3,30℃)achieve 68.36%tetracycline removal and 60.24%mineralization within 60 min.Acidic conditions(pH 5.0)improve removal to 81.47%,while HCO3-inhibits degradation(20.71%removal).Radical quenching confirms·OH as the dominant species(25.70%removal with tert-butanol vs.68.36%control),generated via SO_(4)^(-)·reaction with H2O/OH-.The system maintains 54.78%efficiency after three cycles,with negligible Ni leaching(<1.0 mg/L),complying with discharge standards.Conclusion:The SiO_(2)@Fe-Ni/PS system demonstrates high efficacy and environmental safety for tetracycline degradation.The silicate matrix stabilizes Fe-Ni nanoparticles,while micro-galvanic interactions between Fe0 and Ni0 promote sustained Fe^(2+)release for PS activation.Dominant·OH radicals ensure efficient mineralization,with minimal interference from Cl^(-)or NO_(3)^(-).Despite reduced recyclability due to active site loss,the low-cost synthesis,neutral pH operability,and compliance with secondary pollution regulations highlight its potential for practical wastewater treatment.This study provides a novel strategy for utilizing laterite nickel ore in advanced oxidation processes,bridging resource utilization and environmental remediation.
作者
陈江安
黄金秋
万志豪
余文
CHEN Jiangan;HUANG Jinqiu;WAN Zhihao;YU Wen(School of Resources and Environmental Engineering,Jiangxi University of Science and Technology,Ganzhou 341000,Jiangxi,China)
出处
《有色金属(中英文)》
北大核心
2025年第8期1430-1438,共9页
Nonferrous Metals
基金
国家自然科学基金资助项目(52364026)
江西省主要学科学术技术带头人培养计划项目(20212BCJL23051)。
关键词
红土镍矿
碳热还原法
铁镍双金属
过硫酸盐
四环素
laterite nickel ore
carbothermal reduction method
Fe-Ni bimetal
persulfate
tetracycline
