| 164 | 0 | 89 |
| 下载次数 | 被引频次 | 阅读次数 |
利用尾矿固体废弃物制备吸附材料处理废水重金属污染是重要的技术手段，然而目前针对铅锌尾矿基吸附材料的系统性研究较为匮乏。通过热活化某铅锌尾矿(LZT)后复合海藻酸钠(SA)制备新型吸附材料并用于重金属Cu2+和Cd2+的处理。在850℃下短时热活化的铅锌尾矿(LZT850)结晶度提升，碳酸盐分解后形成的孔隙结构紧密相连，具有较高的比表面积(5.463 3 m2/g)。利用4g/LSA与LZT850在20℃下复合90 min后，得到的LZT850@SA呈现出复杂交联网络结构，具有最大比表面积(16.3109m2/g)，孔容量为0.111508cm3/g。LZT850@SA在pH=6时对Cu2+和Cd2+的饱和吸附量分别为223.15和228.05 mg/g，均在120min达到吸附平衡，适量升温有助于吸附性能提升。该方法为铅锌尾矿基重金属吸附材料的制备提供了新的思路和参考。
Abstract：Lead-zinc ore is an important part of non-ferrous mineral resources in the world. In the mining and flotation process of lead-zinc ore, a large amount of lead-zinc tailings(LZT) will be produced, which not only occupies scarce land resources, but also seriously pollutes the ecological environment around the mine. Therefore,the recycling and utilization of lead-zinc tailings based on resources has great potential and benefits. The leadzinc tailings were thermally modified at different temperatures to prepare adsorption materials. It is ultimately found that the lead-zinc tailings(LZT850) subjected to short-term high-temperature modification at 850 ℃ has a relatively high specific surface area of 5.463 3 m2/g. Lead-zinc tailings-based adsorption materials are similar to other types of tailings-based adsorption materials in practical applications. They still face two key challenges:insufficient structural stability and limited adsorption performance for heavy metal ions. Currently, tailingsbased materials are often modified by methods such as surface functionalization modification, polymer network construction, nanomaterial composite, and pore structure regulation to enhance the adsorption capacity, selectivity,and environmental stability of heavy metal ions. Natural high-molecular compounds have attracted extensive attention in the field of adsorbent modification due to their unique structures and functions. Sodium alginate(SA)is a natural polysaccharide extracted from brown algae. Its molecular chain is rich in carboxyl groups(— COOH)and hydroxyl groups(— OH) functional groups. These functional groups can form complexes with heavy metal ions, thereby significantly enhancing the adsorption performance. Moreover, SA has excellent biocompatibility,degradability and film-forming properties, making it an ideal modified material. To further enhance the adsorption performance, the natural polymer material SA was used to composite-modify LZT850(LZT850@SA). After exploring the composite conditions, it is finally determined that 4 g/L SA solution is used to prepare LZT850@SA adsorption material by magnetic stirring with LZT850 at 20 ℃ for 90 min. The leaching toxicity of LZT850@SA is far below the limit, making it reliable and harmless for application. The specific surface area of LZT850@SA increases from 5.463 3 m2/g to 16.310 9 m2/g compared to LZT850, and the pore volume increases from 0.038 162 cm3/g to 0.111 508 cm3/g. Based on the characteristic results of SEM and TEM, it can be seen that LZT850@SA generates some fibrous and long strip-like structures. The HRTEM image indicates that the amorphous layered structure of SA is closely combined with the crystal plane of LZT850, greatly expanding the specific surface area and porosity of the material. LZT850@SA has a wider applicable pH range. Its adsorption performance remains above 95% in a weakly acidic environment with pH value from 4 to 6. The saturated adsorption capacity for Cu2+ and Cd2+ is 224.37 mg/g and 230.06 mg/g respectively, and the adsorption equilibrium time is about 120 min. Appropriate temperature increase is beneficial to enhance the adsorption performance of LZT850@SA. The research results provide scientific basis and technical support for enhancing the adsorption performance of lead-zinc tailings-based adsorption materials for heavy metal wastewater, and also offer reference for the recycling and utilization of other tailings that has not been studied before.
[1] ZHAO R, WU X, ZHU G, et al. Revealing the release and migration mechanism of heavy metals in typical carbonate tailings, East China[J]. Journal of Hazardous Materials, 2024,464:132978. DOI:10.1016/j.jhazmat.2023.132978.
[2] JAMIL N A, PATAH M F A, JUNAIDI M U M, et al.Dolomite as a potential adsorbent in water treatment:pH,turbidity and Pb(Ⅱ)removal studies[J]. International Journal of Environmental Science and Technology, 2024(6):5669-5680.
[3] DHOKPANDE S R, DESHMUKH S M, KHANDEKAR A, et al. A review outlook on methods for removal of heavy metal ions from wastewater[J]. Separation and Purification Technology, 2024, 350:127868. DOI:10.1016/j.seppur.2024.127868.
[4] QU J H, LI Y H, SUN H B, et al. Ball-milled sepiolite/phosphate rock for simultaneous remediation of cadmiumcontaminated farmland and alleviation of phosphorus deficiency symptoms in pepper[J]. Chemical Engineering Journal, 2024, 488:150925. DOI:10.1016/j.cej.2024.150925.
[5] SABLE H, SINGH V, KUMAR V, et al. Toxicological and bioremediation profiling of nonessential heavy metals(mercury,chromium, cadmium, aluminium)and their impact on human health:a review[J]. Toxicologie Analytique et Clinique, 2024,36(3):205-234.
[6] JIANG J X, SHI Y, MA N L, et al. Utilizing adsorption of wood and its derivatives as an emerging strategy for the treatment of heavy metal-contaminated wastewater[J].Environmental Pollution, 2024, 340:122830. DOI:10.1016/j.envpol.2023.122830.
[7] MA M Y, KE X, WANG T, et al. A novel double-network hydrogel made from electrolytic manganese slag and polyacrylic acid-polyacrylamide for removal of heavy metals in wastewater[J]. Journal of Hazardous Materials, 2024, 462:132722. DOI:10.1016/j.jhazmat.2023.132722.
[8] CHAI W S, CHEUN J Y, KUMAR P S, et al. A review on conventional and novel materials towards heavy metal adsorption in wastewater treatment application[J]. Journal of Cleaner Production, 2021, 296:126589. DOI:10.1016/j.jclepro.2021.126589.
[9] LEE H S, SHIN H S. Competitive adsorption of heavy metals onto modified biochars:comparison of biochar properties and modification methods[J]. Journal of Environmental Management, 2021, 299:113651. DOI:10.1016/j.jenvman.2021.113651.
[10] MARGHADE D, SHELARE S, PRAKASH C, et al. Innovations in metal-organic frameworks(MOFs):pioneering adsorption approaches for persistent organic pollutant(POP)removal[J].Environmental Research, 2024, 258:119404. DOI:10.1016/j.envres.2024.119404.
[11] RAMRAJ S M, KUBAIB A, IMRAN P M, et al. Utilizing Sida acuta leaves for low-cost adsorption of chromium(Ⅵ)heavy metal with activated charcoal[J]. Journal of Hazardous Materials, 2023, 11:100338. DOI:10.1016/j.hazadv.2023.100338.
[12] TRAN H T, BOLAN N S, LIN C, et al. Succession of biochar addition for soil amendment and contaminants remediation during co-composting:a state of art review[J]. Journal of Environmental Management, 2023, 342:118191. DOI:10.1016/j.jenvman.2023.118191.
[13] TIAN Y F, DONG X S, DENG C S, et al. Preparation and characterization of high-ash coal slime-based soil amendment as well as investigations of its adsorption performance and mechanisms towards heavy metals in soil[J]. Chemosphere, 2024, 359:142295. DOI:10.1016/j.chemosphere.2024.142295.
[14] BUZUKASHVILI S, SOMMERVILLE R, HU W, et al. Zeolite synthesis from coal fly ash and its application to heavy metals remediation from water contaminated with Pb, Cu, Zn and Ni ions[J]. Minerals Engineering, 2024, 209:108619. DOI:10.1016/j.mineng.2024.108619.
[15] YIN Z Z, WANG G, WANG L, et al. An effective way to utilize solid waste resources:The application of modified fly ash in removing Cu2+and Pb2+in wastewater[J]. Separation and Purification Technology, 2024, 350:127948. DOI:10.1016/j.seppur.2024.127948.
[16] WANG M L, WANG X M, ZHANG M, et al. Treatment of Cd(Ⅱ)and As(Ⅴ)co-contamination in aqueous environment by steel slag-biochar composites and its mechanism[J]. Journal of Hazardous Materials, 2023, 447:130784. DOI:10.1016/j.jhazmat.2023.130784.
[17] CHENG J C, HUA X L, ZHANG G H, et al. Synthesis of highcrystallinity Zeolite A from rare earth tailings:investigating adsorption performance on typical pollutants in rare earth mines[J]. Journal of Hazardous Materials, 2024, 468:133730.DOI:10.1016/j.jhazmat.2024.133730.
[18] WEI H, SONG B, HUAN Q, et al. Preparation of iron tailings-based porous ceramsite and its application to lead adsorption:characteristic and mechanism[J]. Separation and Purification Technology, 2024, 342:126839. DOI:10.1016/j.seppur.2024.126839.
[19] LUCACI A R, BULGARIU D, AHMAD I, et al. Equilibrium and kinetics studies of metal ions biosorption on alginate extracted from marine red algae biomass(Callithamnion corymbosum sp.)[J]. Polymers, 2020, 12(9):1888. DOI:10.3390/polym12091888.
[20] DARADMARE S, XIA M, LE V N, et al. Metal-organic frameworks/alginate composite beads as effective adsorbents for the removal of hexavalent chromium from aqueous solution[J]. Chemosphere, 2021, 270:129487. DOI:10.1016/j.chemosphere.2020.129487.
[21] XU C L, FENG Y L, LI H R, et al. Adsorption of heavy metal ions by iron tailings:behavior, mechanism, evaluation and new perspectives[J]. Journal of Cleaner Production, 2022, 344:131065. DOI:10.1016/j.jclepro.2022.131065.
[22] WEN X Y, HUANG F, GAO W Y, et al. Three-dimensional observation of porous materials prepared from iron tailings and their pore wall site adsorption function[J]. Ceramics International, 2023, 50(5):7663-7672.
[23] ZHOU J W, LIU Z Y, LI Z, et al. Heavy metals release in leadzinc tailings:effects of weathering and acid rain[J]. Journal of Hazardous Materials, 2025, 483:136645. DOI:10.1016/j.jhazmat.2024.136645.
[24] TAO M, ZHANG X, WANG S F, et al. Life cycle assessment on lead-zinc ore mining and beneficiation in China[J]. Journal of Cleaner Production, 2019, 237:117833. DOI:10.1016/j.jclepro.2019.117833.
[25] JI M T, LV L Q, ZHANG A, et al. Research on dolomite-based shape-stabilized phase change materials for thermal energy storage:feasibility study of raw and calcined dolomite as skeleton support materials[J]. Journal of Energy Storage, 2024,75:109745. DOI:10.1016/j.est.2023.109745.
[26] JAMIL N A, PATAH M F A, JUNAIDI M U M, et al.Dolomite as a potential adsorbent in water treatment:pH,turbidity and Pb(Ⅱ)removal studies[J]. International Journal of Environmental Science&Technology, 2024, 21(6):5669-5680.
[27] WANG J W, FENG Y L, LI H R, et al. Fixation behavior of oceanic manganese nodule-sodium alginate composite microspheres for heavy metal release during manganese nodule mining[J]. Environmental Pollution, 2024, 363:125120. DOI:10.1016/j.envpol.2024.125120.
[28] G?DE J N, MALARET F J, HALLETT J P, et al.Phosphonium-based ionic liquid immobilised in sodium alginate as a novel adsorbent:kinetics, thermodynamics, and toxicity study on 2, 4-dichlorophenol removal[J]. Chemical Engineering Research and Design, 2024, 205:161-173.
[29] LIU Y, XIN Z W, TIAN L, et al. Fabrication of peptideencapsulated sodium alginate hydrogel for selective gallium adsorption[J]. International Journal of Biological Macromolecules, 2024, 263:130436. DOI:10.1016/j.ijbiomac.2024.130436.
[30] XU Y X, LI Y, WANG G X, et al. Dual-use of sodium alginate to prepare sodium algenate-derived carbon dots sodium algenate hydrogel composite for Pb2+removal[J].Applied Surface Science, 2024, 654:159416. DOI:10.1016/j.apsusc.2024.159416.
[31] YANG X Y, ZHANG Z, LIU J S, et al. Green crosslinking with oxidized sodium alginate for enhanced Mo(Ⅵ)adsorption in alginate-based membranes[J]. International Journal of Biological Macromolecules, 2025, 307:142126. DOI:10.1016/j.ijbiomac.2025.142126.
[32] LI Y, XU Y X, ZHU J Y, et al. Immobilization nitrogen-doped sodium alginate-derived carbon quantum dots on sodium alginate hydrogel for enhanced Pb(Ⅱ)removal[J]. Diamond and Related Materials, 2024, 149:111576. DOI:10.1016/j.diamond.2024.111576.
[33] SHANG D W, ZENG S J, ZHANG X P, et al. Highly efficient and reversible absorption of NH3 by dual functionalised ionic liquids with protic and Lewis acidic sites[J]. Journal of Molecular Liquids, 2020, 312:113411. DOI:10.1016/j.molliq.2020.113411.
[34] YIN T N, LEI Y, ZHANG W, et al. Iron monodentate ligand substituted calcium cross-linking gel beads and mechanism to enhance phosphate adsorption[J]. Journal of Polymers and the Environment, 2024, 32:6320-6336.
基本信息:
DOI：10.20237/j.issn.1007-7545.2025.10.023
中图分类号:X705;TQ424
引用信息:
[1]周鑫煜,孟奇,董鹏.新型铅锌尾矿基复合吸附材料的制备及性能研究[J].有色金属(冶炼部分),2025(10):245-255.DOI:10.20237/j.issn.1007-7545.2025.10.023.
基金信息:
云南省科技重大专项资助项目（202202AG050003）
2025-03-31
2025
2025-04-11
2025-04-14
2025
1
2025-09-28
2025-09-28