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沸石是一种天然多孔材料，具有较强的吸附性能，被广泛应用于环境修复领域。文章通过化学沉淀法制备了不同比例的锰改性沸石(x%Mn-NZ, x=1, 2, 5, 10)，用于水体中低浓度Cr(Ⅵ)的吸附和转化。在常温条件下，以初始Cr(Ⅵ)浓度为0.5 mg/L的模拟地表水为对象，对比了锰改性沸石对Cr(Ⅵ)的吸附性能。实验表明，当锰改性沸石投加量为20 mg/L时，5%Mn-NZ对Cr(Ⅵ)的去除率达到80.40%，溶液中Cr(Ⅵ)浓度降至国家标准限值以下。动力学分析表明，锰改性沸石吸附Cr(Ⅵ)的过程更符合准二级动力学模型(R2 > 0.99)，表明其吸附过程以化学吸附为主，平衡吸附量为23.81 mg/g。通过系统评价pH和共存离子对锰改性沸石吸附Cr(Ⅵ)性能的影响，发现5%Mn-NZ在pH=6～9范围和共存离子干扰下均保持最优吸附性能。XPS、FT-IR分析表明，锰改性沸石吸附Cr(Ⅵ)的主要机理为表面Mn2+和Mn3+提供电子，将Cr(Ⅵ)还原为Cr(Ⅲ)。本研究为金属改性沸石去除水体中低浓度Cr(Ⅵ)污染提供了技术支持。
Abstract：Zeolite is a natural porous material with adsorption properties and is widely used in environmental remediation. In this study, different ratios of manganese-modified zeolites(x% Mn-NZ, x = 1, 2, 5, 10) were prepared by chemical precipitation method for the adsorption and transformation of low concentrations of Cr(Ⅵ) in water. The adsorption performance of manganese-modified zeolites for Cr( Ⅵ) was compared for simulated surface water with an initial chromium concentration of 0.5 mg/L under ambient conditions. The experiments showed that when the dosage of manganese-modified zeolite was 20 mg/L, the removal rate of Cr(Ⅵ) by 5% MnNZ reached 80.40%, and the concentration of Cr(Ⅵ) in the solution was reduced to below the national standard limit. The kinetic analysis showed that the adsorption of Cr(Ⅵ) by the manganese-modified zeolite was more in line with the quasi-secondary kinetic model(R2 > 0.99), indicating that the adsorption process was dominated by chemical adsorption, and the equilibrium adsorption amount was 23.81 mg/g. By systematically evaluating the effects of pH and coexisting ions on the performance of manganese-loaded zeolites for the adsorption of Cr(Ⅵ), the results showed that the adsorption of Cr(Ⅵ) by 5% Mn-NZ remained optimal in the range of pH 6 to 9, and in the case of coexisted ions, both of them remained optimal in the pH range. It was found that 5% Mn-NZ maintained the optimum adsorption performance in the pH range of 6 to 9 and in the presence of coexisting ions. The main mechanism of Cr(Ⅵ) adsorption by Mn-modified zeolite was revealed by XPS and FT-IR analyses, in which Mn2+ and Mn3+ on the surface provided electrons to reduce Cr(Ⅵ) to Cr(Ⅲ). This study provides technical support for metal-modified zeolite to remove low concentration of Cr(Ⅵ) pollution in water bodies.
1张帆帆,蔡元韬,陶剑波,等. Zn,C引入量和煅烧温度对ZnO/C/CeO2光催化还原Cu2+效率的影响[J].化学学报, 2024, 82(8):871-878.
2 Kasera N, Kolar P, Hall S G. Nitrogen-doped biochars as adsorbents for mitigation of heavy metals and organicsfrom water:A review[J]. Biochar, 2022, 4(1):17.
3 Alluhaybi A A, Alharbi A, Hameed A M, et al. A novel triazole schiff base derivatives for remediation ofchromium contamination from tannery waste water[J]. Molecules, 2022, 27(16):5087.
4 Kumar V, DwivedI S K. A review on accessible techniques for removal of hexavalent chromium and divalentnickel from industrial wastewater:Recent research and future outlook[J]. Journal of Cleaner Production, 2021,295:126229.
5 Kumar V, Dwivedi S K, Oh S. A review on microbial-integrated techniques as promising cleaner option forremoval of chromium, cadmium and lead from industrial wastewater[J]. Journal of Water Process Engineering,2022, 47:102727.
6 Tastanov Y, Serzhanova N, Ultarakova A, et al. Recycling of chrome-containing waste from a mining andprocessing plant to produce industrial products[J]. Processes, 2023, 11(6):1659.
7赵国栋,熊卓,赵永椿,等.焚烧飞灰中六价铬化合物碳热还原脱毒[J].化工学报, 2024, 75(10):3730-3741.
8 Bri?o G D V, Da Costa T B, Antonelli R, et al. Electrochemical processes for the treatment of contaminant-richwastewater:A comprehensive review[J]. Chemosphere, 2024, 355:141884.
9 Fei Y, Hu Y H. Recent progress in removal of heavy metals from wastewater:A comprehensive review[J].Chemosphere, 2023, 335:139077.
10张梦,聂广泽,仲兆祥.宽层间距MoS2纳米片对水中重金属Cu(Ⅱ)的吸附性能研究[J].离子交换与吸附,2024, 40(6):469-480.
11 Yang X, Ji Y, Jian M, et al. Fabrication of metal-organic frameworks macro-structures for adsorption applicationsin water treatment:A review[J]. Separation and Purification Technology, 2025, 354:129376.
12 Wan J, Yu M, Bi W, et al. Research on chromium removal mechanism by electrochemical method from wastewater[J]. Journal of Water Process Engineering, 2024, 68:106447.
13 Li S, Hu P, Zhang Y, et al. Comprehensive recovery of valuable elements from vanadium precipitation liquor usingselective impurity removal-reduction precipitation process[J]. Journal of Cleaner Production, 2024, 467:143013.
14 Yuan Y, Wei X, Zhu M, et al. Unravelling the removal mechanisms of trivalent arsenic by sulfidated nanoscalezero-valent iron:The crucial role of reactive oxygen species and the multiple effects of citric acid[J]. Science ofthe Total Environment, 2024, 916:170275.
15 Yuan Z, Peng A, Chu Z, et al. Sustainable remediation of Cr(Ⅵ)-contaminated soil by soil washing andsubsequent recovery of washing agents using biochar supported nanoscale zero-valent iron[J]. Science of the TotalEnvironment, 2024, 921:171107.
16 Fang Y, Wen J, Zhang H, et al. Enhancing Cr(Ⅵ) reduction and immobilization by magnetic core-shell structuredNZVI@MOF derivative hybrids[J]. Environmental Pollution, 2020, 260:114021.
17 Suazo-hernández J, Sepúlveda P, Manquián-cerda K, et al. Synthesis and characterization of zeolite-basedcomposites functionalized with nanoscale zero-valent iron for removing arsenic in the presence of selenium fromwater[J]. Journal of Hazardous Materials, 2019, 373:810-819.
18 Wei X, You Y, Fan Z, et al. Controllable integration of nano zero-valent iron into MOFs with different structuresfor the purification of hexavalent chromium-contaminated water:Combined insights of scavenging performanceand potential mechanism investigations[J]. Science of the Total Environment, 2024, 935:173395.
19 Fu H, Li Y, Yu Z, et al. Ammonium removal using a calcined natural zeolite modified with sodium nitrate[J].Journal of Hazardous Materials, 2020, 393:122481.
20 Regmi U, Boyer T H. Ammonium and potassium removal from undiluted and diluted hydrolyzed urine usingnatural zeolites[J]. Chemosphere, 2021, 268:128849.
21 Dosa M, Grifasi N, Galletti C, et al. Natural zeolite clinoptilolite application in wastewater treatment:methyleneblue, zinc and cadmium abatement tests and kinetic studies[J]. Materials, 2022, 15(22):8191.
22 SvobodováE, Ti?ler Z, PeroutkováK, et al. Adsorption of heavy metals on alkali-activated zeolite foams[J].Materials, 2024, 17(3):685.
23 Shi Y, Wang X, Feng C, et al. Adsorption properties of natural zeolite supported by chitosan on Cd(Ⅱ) inmicropolluted irrigation water[J]. ACS Omega, 2024, 9(1):573-584.
24 Adam M R, Salleh N M, Othman M H D, et al. The adsorptive removal of chromium(Ⅵ) in aqueous solution bynovel natural zeolite based hollow fibre ceramic membrane[J]. Journal of Environmental Management, 2018, 224:252-262.
25 Rud?ionis?, Adhikary S K, Manhanga F C, et al. Natural zeolite powder in cementitious composites and itsapplication as heavy metal absorbents[J]. Journal of Building Engineering, 2021, 43:103085.
26 Luo Q, Jiang D, Hou D, et al. Effective adsorption of metal ions by modified clinoptilolite zeolite from simulatedradioactive solution[J]. Journal of Radioanalytical and Nuclear Chemistry, 2019, 319(3):1069-1081.
27 Hong M, Yu L, Wang Y, et al. Heavy metal adsorption with zeolites:The role of hierarchical pore architecture[J].Chemical Engineering Journal, 2019, 359:363-372.
28 Gopalakrishnan A, Asare S, Adu-boahene F, et al. Uranium adsorption by iron modified zeolite and zeolitecomposite membranes[J]. Chemosphere, 2024, 368:143711.
29 Feke K, Alula M T, Spende H, et al. Synthesis of a recoverable CuS/Fe3O4 composite structure with enhancedoxidase-like activity for detection of chromium(Ⅵ)[J]. Journal of Cluster Science, 2023, 34(2):1009-1018.
30 Ahmed A, Singh A, Padha B, et al. UV-vis spectroscopic method for detection and removal of heavy metal ions inwater using Ag doped ZnO nanoparticles[J]. Chemosphere, 2022, 303:135208.
31 Guo Q E, Li B G, Nan L L, et al. Spatial and temporal variation of salt ions in the surface water of Shule RiverValley in Gansu Province, China[J]. Water Supply, 2018, 19(2):662-670.
32 Wahono S K, Suwanto A, Prasetyo D J, et al. Plasma activation on natural mordenite-clinoptilolite zeolite forwater vapor adsorption enhancement[J]. Applied Surface Science, 2019, 483:940-946.
33 Yang B, Sun G, Quan B, et al. An Experimental study of fluoride removal from wastewater by Mn-Ti modifiedzeolite[J]. Water, 2021, 13(23):3343.
34 Tamizhdurai P, Ramesh A, Krishnan P S, et al. Effect of acidity and porosity changes of dealuminated mordeniteon n-pentane, n-hexane and light naphtha isomerization[J]. Microporous and Mesoporous Materials, 2019, 287:192-202.
35 Saharan P, Sharma A K, Kumar V, et al. Multifunctional CNT supported metal doped MnO2 composite foradsorptive removal of anionic dye and thiourea sensing[J]. Materials Chemistry and Physics, 2019, 221:239-249.
36 Hu J, Li Y, Nan S, et al. Catalytic ozonation of nitrobenzene by manganese-based Y zeolites[J]. Frontiers inChemistry, 2020(1):8.
37 Ilton E S, Post J E, Heaney P J, et al. XPS determination of Mn oxidation states in Mn(hydr)oxides[J]. AppliedSurface Science, 2016, 366:475-485.
38 Zhuang G, Zhang Z, Sun J, et al. The structure and rheology of organo-montmorillonite in oil-based system agedunder different temperatures[J]. Applied Clay Science, 2016(124/125):21-30.
39 Kanani-jazi M H, Akbari S. Quantitative XPS analysis of amine-terminated dendritic functionalized halloysitenanotubes decorated on PAN nanofibrous membrane and adsorption/filtration of Cr(Ⅵ)[J]. Chemical EngineeringJournal, 2024, 482:148746.
40 Lin X, Shen T, Li M, et al. Synthesis, characterization, and utilization of poly-amino acid-functionalized lignin forefficient and selective removal of lead ion from aqueous solution[J]. Journal of Cleaner Production, 2022, 347:131219.
41 Rodriguez M, Hanon F, Devred F, et al. Mn and Co decorated biomorphic ceria fiber catalysts for soot andbenzene total oxidation[J]. Chemosphere, 2024, 359:142247.
42 Wei X, Ke Q, Cheng H, et al. Seed-assisted synthesis of Cu-(Mn)-UZM-9 zeolite as excellent NO removal andN2O inhibition catalysts in wider temperature window[J]. Chemical Engineering Journal, 2020, 391:123491.
43 Song Z, Wang B, Yang W, et al. Simultaneous removal of NO and SO2 through heterogeneous catalytic oxidation-absorption process using magnetic Fe2.5M0.5O4(M=Fe, Mn, Ti and Cu) catalysts with vaporized H2O2[J].Chemical Engineering Journal, 2020, 386:123883.
44 Choppala G, Kunhikrishnan A, Seshadri B, et al. Comparative sorption of chromium species as influenced by pH,surface charge and organic matter content in contaminated soils[J]. Journal of Geochemical Exploration, 2018,184:255-260.
45 Shen T, Bao H, Su W, et al. Manganese containing oxides catalytic ozonation in aqueous solution:Catalyticmechanism on acid sites[J]. Separation and Purification Technology, 2022, 282:120053.
46 Zhang L, Zhang Y, Gao X, et al. Insights on the effects of p H and Fe(II) regeneration during the chromatesequestration by sulfidated zero-valent iron[J]. Chemical Engineering Journal, 2019, 378:122115.
47 Rivera G L D, Hernández A M, Cabello A F P, et al. Removal of chromate anions and immobilization usingsurfactant-modified zeolites[J]. Journal of Water Process Engineering, 2021, 39:101717.
48 Bekchanov D, Mukhamediev M, Babojonova G, et al. Anion exchange material based on polyvinylchloride andurea for the removal of chromium(Ⅵ) ions from aqueous solutions[J]. Clean, 2023, 51(10):2200411.
基本信息:
DOI：10.16026/j.cnki.iea.2025010025
中图分类号:TQ424.25;X703
引用信息:
[1]李自豪,石建军,谢彦雄.锰改性沸石对铬的吸附性能及机理研究[J].离子交换与吸附,2025,41(05):379-389.DOI:10.16026/j.cnki.iea.2025010025.
基金信息:
安徽省科技重大专项(项目号201903a020003)