Surface Modification of Natural Mordenite and Its Application in Removal of Heavy Metals from Aqueous Solution
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摘要: 天然丝光沸石作为一种绿色廉价多孔材料广泛应用于环境治理中去除重金属，目前报道的天然沸石对重金属的去除率多在60%~90%，提升其去除效率已成为研究热点。本文采用正硅酸乙酯对天然丝光沸石进行表面重构改性，通过TEM、XRD、BET等手段表征其形貌和结构。结果表明：正硅酸乙酯水解生成的SiO2可与天然丝光沸石复合形成新颖的"SiO2/丝光沸石"，原沸石表面包覆了新生纳米SiO2孔结构，同时没有损坏原始沸石的多孔结构，使改性沸石材料兼具了天然丝光沸石和纳米SiO2孔结构优点，增强了对重金属离子的吸附能力。该改性材料对水中Pb2+、Cd2+、Zn2+和Mn2+的最高吸附率为99.3%、97.1%、98.3%和97.0%，且极少解吸，性能稳定。考虑经济成本并保证合适吸附率的情况下选择吸附效率最佳的投加量，得到改性材料对初始浓度10 mg/L的Pb2+、Cd2+、Zn2+、Mn2+溶液的最佳投加量分别为0.5 g/L、2 g/L、2 g/L、5 g/L，可为中试和规模应用提供参考。较之焙烧、酸、碱、盐和有机改性，本改性方式对多种重金属均有高的吸附率，并显现出操作简便、成本低和环境友好等优势，具有较好应用前景。Abstract:
BACKGROUNDNatural mordenite is widely used as a green and cheap porous material to remove heavy metals in environmental treatment. Currently, the removal rate of heavy metals by natural zeolites is from 60% to 90%, and improving its removal efficiency has been a hot topic. OBJECTIVESTo reconstruct and modify natural mordenite by tetraethyl orthosilicate, and determine its effect on the removal of heavy metals in water. METHODSThe morphology and structure of the modified mordenites were characterized by TEM, XRD and BET. RESULTSThe SiO2 hydrolyzed by tetraethyl orthosilicate can be combined with natural mordenite to form a new 'SiO2/mordenite'. The surface of the original mordenite is coated with the pore structure of the new nano-SiO2 without damaging the porous structure of the original mordenite. The modified mordenite combines the advantages of natural mordenite and nano-SiO2 pore structure, enhancing the adsorption of heavy metal ions. The highest adsorption rate of modified mordenite for Pb2+, Cd2+, Zn2+, and Mn2+ was 99.3%, 97.1%, 98.3%, and 97.0%, respectively. The modified mordenites were minimally desorbed during the entire process and have stable performance. Considering the cost and the appropriate adsorption rate, the best dosage of adsorption efficiency is selected. The optimal dosage of Pb2+, Cd2+, Zn2+ and Mn2+ solutions for the initial concentration of 10 mg/L is 0.5, 2, 2 and 5 g/L, respectively. It can provide a reference for a pilot experiment and scale applications. CONCLUSIONSCompared with roasting, acid, alkali, salt and organic modification, this modification method has a high adsorption rate for a variety of heavy metals, and shows the advantages of simple operation, low cost and environmental friendliness, making it a good application prospect. -
Key words:
- natural mordenites /
- silica /
- surface modification /
- heavy metals /
- adsorption
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表 1 不同天然沸石改性方法吸附去除水溶液中重金属效果比较
Table 1. Comparison of adsorption capacity of different modified methods of zeolites for removal of heavy metals from aqueous solution
天然沸石改性方法 改性过程或主要步骤 改性材料投加量 吸附率 参考文献 焙烧改性 沸石300℃焙烧1.5 h 10 g/L Pb：98%
Co：40%[26] 盐酸改性 10%盐酸浸泡24 h，再去离子水冲洗，105℃烘干 100 g/L Pb：95% [27] 氢氧化钠改性 2 mol/L氢氧化钠溶液浸泡，室温振荡2.5 h，抽滤，冲洗至中性，烘干 10 g/L Cd：99% [28] 氢氧化钠改性 2 mol/L氢氧化钠溶液浸泡，室温振荡2.5 h，抽滤，冲洗至中性，烘干 5 g/L Zn：95%
Cd：97%[29] 氯化钠改性 2 mol/L氯化钠溶液浸泡24 h，烘干 1 g/L Pb：90%
Cd：90%
Ni：90%[30] 硫酸/硫酸铜复合改性 1 mol/L硫酸浸泡10 h后洗净，105℃下烘干，再1 mol/L硫酸铜溶液浸泡10 h，105℃下烘干 40 g/L Cr：94% [31] 接枝氨基 沸石先酸碱活化，后与3-氨丙基三甲氧基硅烷混合于甲苯中80℃搅拌24 h，洗涤，干燥 Ni：1 g/L
Cu：1 g/L
Zn：1.6 g/L
Pb：0.6 g/LNi：90%
Cu：20%
Zn：34%
Pb：90%[25] 本研究
(正硅酸乙酯表面改性)沸石粉末与硅酸-乙酯溶液在乙醇中常温搅拌5 h，洗涤，烘干 Pb：0.5 g/L
Zn、Cd：2 g/L
Mn：5 g/LPb：99.3%
Cd：97.1%
Zn：98.3%
Mn：97.0%本研究 
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