CN105214606A - A kind of method improving mesopore molecular sieve Adsorption of Heavy Metals usefulness - Google Patents
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 44
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 39
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
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- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 239000000356 contaminant Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000463 material Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
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- 150000002500 ions Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
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- 125000004494 ethyl ester group Chemical group 0.000 description 1
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- -1 octadecyl trimethyl ammonium bromide methyl ammonium bromide Chemical compound 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
技术领域technical field
本发明属于重金属污染治理技术领域，具体涉及一种提高介孔分子筛吸附重金属效能的方法。The invention belongs to the technical field of heavy metal pollution control, and in particular relates to a method for improving the heavy metal adsorption efficiency of mesoporous molecular sieves.
背景技术Background technique
随着城市的扩大和大规模工业的发展，大气、土壤、水环境中存在的重金属污染日益增加。重金属污染是水污染的主要问题之一，矿山开采、金属冶炼、化工生产废水、施用农药化肥和生活垃圾等人为污染，以及地质侵蚀、风化等天然因素均能导致重金属以各种形式进入水体。由于重金属具有毒性大、在环境中不易被代谢、易被生物富集并有生物放大效应等特点，使得水环境的重金属污染严重威胁水生生物的生存和人类健康。因此，水环境中重金属污染控制已成为关系到环境保护、可持续发展和居民生活水平提高的重要问题。With the expansion of cities and the development of large-scale industries, the heavy metal pollution in the atmosphere, soil and water environment is increasing day by day. Heavy metal pollution is one of the main problems of water pollution. Man-made pollution such as mining, metal smelting, chemical production wastewater, application of pesticides and fertilizers, and domestic garbage, as well as natural factors such as geological erosion and weathering, can cause heavy metals to enter water bodies in various forms. Because heavy metals are highly toxic, difficult to be metabolized in the environment, easy to be enriched by organisms, and have biomagnification effects, heavy metal pollution in the water environment seriously threatens the survival of aquatic organisms and human health. Therefore, the control of heavy metal pollution in the water environment has become an important issue related to environmental protection, sustainable development and improvement of residents' living standards.
吸附技术因其简单低耗、无化学药品投加成为研究者公认的重金属去除技术，研究人员开发出了多种吸附材料。其中，硅基介孔分子筛因其具有可控的结构形貌、和良好的结构基础备受青睐。然而，硅基介孔分子筛属于无机材料，对重金属离子吸附效能不佳。因此，研究适当的方法提高硅基介孔分子筛对重金属的吸附性能对拓展硅基介孔分子筛在重金属污染控制领域的应用具有较强的现实意义。Adsorption technology has become a recognized heavy metal removal technology for researchers because of its simplicity, low consumption, and no chemical addition. Researchers have developed a variety of adsorption materials. Among them, silicon-based mesoporous molecular sieves are favored because of their controllable structural morphology and good structural foundation. However, silicon-based mesoporous molecular sieves are inorganic materials, which have poor adsorption performance for heavy metal ions. Therefore, it is of great practical significance to study appropriate methods to improve the adsorption performance of silicon-based mesoporous molecular sieves for heavy metals to expand the application of silicon-based mesoporous molecular sieves in the field of heavy metal pollution control.
发明内容Contents of the invention
为解决硅基介孔分子筛对重金属吸附效能低的问题，同时实现了对重金属的选择性分离，本发明提供了一种提高硅基介孔分子筛吸附重金属效能的方法。In order to solve the problem of low adsorption efficiency of silicon-based mesoporous molecular sieves for heavy metals and realize selective separation of heavy metals, the present invention provides a method for improving the adsorption efficiency of silicon-based mesoporous molecular sieves for heavy metals.
具体的，该方法包括如下步骤：包括如下步骤：将保留模板剂的硅基介孔分子筛投入到含重金属的水中，投入量为0.5～1.5g/L，调节pH为中性，常温震荡2～4h，将分子筛从水中分离实现重金属污染物去除。Specifically, the method includes the following steps: including the following steps: put the silicon-based mesoporous molecular sieve that retains the template into the water containing heavy metals, the amount of which is 0.5-1.5g/L, adjust the pH to be neutral, and shake at room temperature for 2- 4h, the molecular sieve is separated from the water to realize the removal of heavy metal pollutants.
其中，所述的保留模板剂的硅基介孔分子筛采用如下方法制备得到：向水中加入季铵盐表面活性剂，用量为2～8g/L，充分溶解后依次加入乙醇和氨水，用量分别为200～300mL/L和50～100mL/L，混匀，搅拌下加入正硅酸乙酯，用量为10～30mL/L，进行脱水缩合反应，陈化12～36h，分离，洗涤得到到白色沉淀物，烘干，研磨即可。Wherein, the silicon-based mesoporous molecular sieve that retains the template is prepared by the following method: add quaternary ammonium salt surfactant to water, the dosage is 2-8g/L, after fully dissolving, add ethanol and ammonia water in turn, the dosage is respectively 200~300mL/L and 50~100mL/L, mix well, add tetraethyl orthosilicate under stirring, the dosage is 10~30mL/L, carry out dehydration condensation reaction, age for 12~36h, separate, wash to get white precipitate matter, dried and ground.
其中，所述的季铵盐表面活性剂为十六烷基三甲基溴化铵、十二烷基三甲基溴化铵、十四烷基三甲基溴化铵或十八烷基三甲基溴化铵。Wherein, the quaternary ammonium salt surfactant is cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide methyl ammonium bromide.
其中，所述的脱水缩合反应时间为15～30min。Wherein, the dehydration condensation reaction time is 15-30 minutes.
其中，所述的陈化时间为10～30h。Wherein, the aging time is 10-30 hours.
其中，所述的重金属为铜、镉、锌或铅。Wherein, the heavy metal is copper, cadmium, zinc or lead.
本发明方法原理如下：通过保留硅基介孔分子筛合成过程中所使用的模板剂季铵盐阳离子表面活性剂，在介孔孔道内形成以季铵盐阳离子表面活性剂的阳离子端为主的阳离子界面层，进而通过阳离子界面层结合水中的阴离子提高硅基介孔分子筛对重金属离子的吸附效能。The principle of the method of the present invention is as follows: by retaining the template agent quaternary ammonium salt cationic surfactant used in the synthesis process of the silicon-based mesoporous molecular sieve, a cationic terminal mainly based on the cationic end of the quaternary ammonium salt cationic surfactant is formed in the mesoporous channel interface layer, and then through the cationic interface layer combined with anions in water to improve the adsorption efficiency of silicon-based mesoporous molecular sieves to heavy metal ions.
本发明不涉及化学药品消耗、能源消耗，是一种环境友好的材料性能调控方法，较采用化学改性等方法提高硅基介孔分子筛对重金属吸附性能具有明显优势。The invention does not involve the consumption of chemicals and energy, and is an environmentally friendly material performance control method, which has obvious advantages over the use of chemical modification and other methods to improve the adsorption performance of silicon-based mesoporous molecular sieves for heavy metals.
附图说明Description of drawings
图1是保留模板剂硅基介孔分子筛的结构表征：图A和B分别为不含模板剂和含有模板的硅基介孔分子筛剂的扫描电镜图；图C为材料的X射线衍射图，含有模板和不含模板剂的硅基介孔分子筛剂分别记为C16-MCM-41和MCM-41；图D为材料的红外光谱图，含有模板和不含模板剂的硅基介孔分子筛剂分别记为C16-MCM-41和MCM-41。Figure 1 is the structural characterization of the silicon-based mesoporous molecular sieve that retains the template: Figures A and B are the scanning electron microscope images of the silicon-based mesoporous molecular sieve agent without and containing the template, respectively; Figure C is the X-ray diffraction pattern of the material, The silica-based mesoporous molecular sieves containing templates and template-free agents are respectively denoted as C 16 -MCM-41 and MCM-41; Figure D is the infrared spectrum of the material, and the silica-based mesoporous molecular sieves containing templates and template-free The agents are denoted as C 16 -MCM-41 and MCM-41, respectively.
图2保留模板剂硅基介孔分子筛内部结构示意图。Figure 2 is a schematic diagram of the internal structure of a silica-based mesoporous molecular sieve that retains a template.
图3采用本方法对硅基介孔分子筛吸附典型重金属性能提高效果图，即含模板剂硅基介孔分子筛C16-MCM-41(●)和不含模板剂硅基介孔分子筛MCM-41(○)对重金属Cu2+的吸附效能对比。Figure 3 is the improvement effect diagram of typical heavy metal adsorption performance of silicon-based mesoporous molecular sieves by this method, that is, silicon-based mesoporous molecular sieve C 16 -MCM-41(●) containing template agent and silicon-based mesoporous molecular sieve MCM-41 without template agent (○) Comparison of adsorption performance on heavy metal Cu 2+ .
具体实施方式detailed description
实施例1分子筛的制备The preparation of embodiment 1 molecular sieve
本实施方式中模板剂以十六烷基三甲基溴化铵为例，但模板剂不受限于此例。In this embodiment, the template agent is cetyltrimethylammonium bromide as an example, but the template agent is not limited to this example.
向700mL水中加入6g的季铵盐表面活性剂十六烷基三甲基溴化铵，充分搅拌溶解后，依次加入250mL乙醇和80mL氨水，充分混匀后，搅拌下加入入20的正硅酸乙酯进行脱水缩合反应20min，陈化24h后对分离、洗涤所得白色沉积物，烘干后研磨制得保留模板剂的硅基介孔分子筛，并取部分样品在540℃下煅烧6h，制得不含模板剂的硅基介孔分子筛。材料表征见图1，材料结构示意图见图2。如图1A和1B所示，所合成的材料呈现出300nm直径的球形颗粒；如图1C示，所合成的材料呈现出四个小角度X射线衍射峰，说明材料具有良好的介孔结构特征；如图1D示，所合成材料的红外光谱现实未经煅烧的分子筛呈现出烷基吸收峰(2920，2851和1474cm-1)，说明模板剂成功保留在分子筛内部。所合成的分子筛内部结构示意图见图2，内部孔道的硅基骨架呈六棱柱形。Add 6g of quaternary ammonium salt surfactant cetyltrimethylammonium bromide to 700mL of water, stir well to dissolve, then add 250mL of ethanol and 80mL of ammonia water in turn, after fully mixing, add 20% orthosilicic acid under stirring Carry out dehydration condensation reaction of ethyl ester for 20 minutes, after aging for 24 hours, separate and wash the white sediment obtained, dry and grind to obtain a silicon-based mesoporous molecular sieve that retains the template agent, and take some samples and calcinate at 540°C for 6 hours to obtain A template-free silica-based mesoporous molecular sieve. The material characterization is shown in Figure 1, and the schematic diagram of the material structure is shown in Figure 2. As shown in Figures 1A and 1B, the synthesized material presents spherical particles with a diameter of 300nm; as shown in Figure 1C, the synthesized material presents four small-angle X-ray diffraction peaks, indicating that the material has good mesoporous structure characteristics; As shown in Figure 1D, the infrared spectrum of the synthesized material shows that the uncalcined molecular sieve exhibits alkyl absorption peaks (2920, 2851 and 1474 cm -1 ), indicating that the template is successfully retained inside the molecular sieve. The schematic diagram of the internal structure of the synthesized molecular sieve is shown in Figure 2, and the silicon-based framework of the internal channel is in the shape of a hexagonal prism.
实施例2吸附实验Embodiment 2 adsorption experiment
本实施方式中含模板剂硅基介孔分分子筛以采用十六烷基三甲基溴化铵制备的分子筛为例，重金属以Cu2+为例，但模板剂和重金属种类不受限于此例。In this embodiment, the template-containing silicon-based mesoporous molecular sieve is taken as an example of a molecular sieve prepared by cetyltrimethylammonium bromide, and Cu 2+ is used as an example of a heavy metal, but the types of templates and heavy metals are not limited to this example.
通过吸附实验验证保留模板剂对硅基介孔分分子筛吸附重金属性能的提高效果。分别称取上述两种分子筛0.02g置于50mL玻璃离心管中，依次加入30mL蒸馏水和一定体积的重金属离子代表Cu2+，最终调节体系体积为32mL并调节pH为中性后，常温震荡2小时达到吸附平衡。取样测定Cu2+残留量，评价材料的吸附性能，从而验证采用保留模板剂方式提高硅基介孔分子筛吸附重金属的效果，效果对比见附图3。结果表明：随初始Cu2+浓度的增加，平衡吸附量Qe不断增加，当初始浓度增加到一定值时，平衡吸附量稳定在一个固定的值，即饱和吸附量。对比含有模板剂和不含有模板剂的硅基介孔分子筛，保留模板剂的分子筛具有更高的饱和吸附量，说明保留模板剂能够显著提高硅基介孔分子筛对重金属Cu2+的吸附效能。The effect of retaining template agent on the adsorption of heavy metals by silica-based mesoporous molecular sieves was verified by adsorption experiments. Weigh 0.02g of the above two molecular sieves and place them in a 50mL glass centrifuge tube, add 30mL of distilled water and a certain volume of heavy metal ions to represent Cu 2+ in turn, finally adjust the volume of the system to 32mL and adjust the pH to neutral, then shake at room temperature for 2 hours reached adsorption equilibrium. Sampling was taken to measure Cu 2+ residues, and the adsorption performance of the material was evaluated, so as to verify the effect of using the template retention method to improve the adsorption of heavy metals by silicon-based mesoporous molecular sieves. See Figure 3 for the effect comparison. The results show that: with the increase of the initial Cu 2+ concentration, the equilibrium adsorption capacity Qe increases continuously, and when the initial concentration increases to a certain value, the equilibrium adsorption capacity stabilizes at a fixed value, that is, the saturated adsorption capacity. Comparing the silica-based mesoporous molecular sieves with and without templates, the molecular sieves retaining templates have a higher saturated adsorption capacity, indicating that retaining templates can significantly improve the adsorption efficiency of silica-based mesoporous molecular sieves for heavy metal Cu 2+ .
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| JPS6369511A (en) * | 1986-09-10 | 1988-03-29 | Idemitsu Kosan Co Ltd | Method for adsorbing and separating oxides |
| CN1554582A (en) * | 2003-12-28 | 2004-12-15 | 王燕春 | Method for producing mesoporous silicon gel |
| CN102241406A (en) * | 2010-05-11 | 2011-11-16 | 哈尔滨工业大学 | Carboxylated MCM-41 mesoporous molecular sieve for adsorbing heavy metal ions, and preparation method thereof |
| CN102908982A (en) * | 2012-10-24 | 2013-02-06 | 陕西省石油化工研究设计院 | Preparation method of novel mesoporous material for absorbing heavy metal ions in wastewater |
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| CN109678278A (en) * | 2019-01-21 | 2019-04-26 | 河南城建学院 | A kind of Groundwater Treatment Methodss of contaminated site |
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