油页岩灰基磁性分子筛的制备及其对亚甲基蓝的吸附性能

doi:10.11901/1005.3093.2024.290

材料研究学报

2025, Vol. 39

Issue (6): 463-473 DOI: 10.11901/1005.3093.2024.290

研究论文

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油页岩灰基磁性分子筛的制备及其对亚甲基蓝的吸附性能

段玉¹, 王倩¹(

), 刘宏臣¹, 车远军¹, 石磊¹, 白慧娟²(

)

^1.西安工程大学环境与化学工程学院西安 710048
^2.中国科学院过程工程研究所中国科学院绿色过程与工程重点实验室北京 100190

Methylene Blue Adsorption Performance of Magnetic Zeolite Prepared from Oil Shale Ash

DUAN Yu¹, WANG Qian¹(

), LIU Hongchen¹, CHE Yuanjun¹, SHI Lei¹, BAI Huijuan²(

)

^1.School of Environmental and Chemical Engineering, Xi'an Polytechnic University, Xi'an 710048, China
^2.CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

引用本文:

段玉, 王倩, 刘宏臣, 车远军, 石磊, 白慧娟. 油页岩灰基磁性分子筛的制备及其对亚甲基蓝的吸附性能[J]. 材料研究学报, 2025, 39(6): 463-473.
Yu DUAN, Qian WANG, Hongchen LIU, Yuanjun CHE, Lei SHI, Huijuan BAI. Methylene Blue Adsorption Performance of Magnetic Zeolite Prepared from Oil Shale Ash[J]. Chinese Journal of Materials Research, 2025, 39(6): 463-473.

全文: PDF(1261 KB) HTML

摘要:

以油页岩灰为原料用碱熔水热法制备了Fe₃O₄@NaX型磁性分子筛并用于吸附亚甲基蓝(MB)，研究了在不同条件下这种分子筛对MB的吸附性能并揭示其机理。结果表明：在2.0% Fe₃O₄@NaX (质量分数)型磁性分子筛用量为1 g/L、溶液的初始pH值为5.7、MB溶液的初始浓度为50 mg/L、吸附温度为25 ℃的条件下，分子筛对MB吸附60 min，MB的吸附率和平衡吸附量分别为96.98%和45.19 mg/g。这种分子筛在外磁场作用下能使染料溶液快速分离，且其再生重复使用的性能较好。Fe₃O₄@NaX型分子筛对MB的吸附遵循拟二级动力学和Langmuir等温线模型，是一个自发和放热的熵减过程。静电引力、氢键和孔隙扩散是吸附的主要推动力。

关键词 ：材料合成与加工工艺, 磁性分子筛, 碱熔水热法, 吸附, 油页岩灰, 亚甲基蓝

Abstract：

Fe₃O₄@NaX magnetic zeolite was prepared via alkaline fusion hydrothermal method with Fe₃O₄ particles and Beipiao oil shale ash as raw material, aiming to making magnetic absorbent substance for absorbing methylene blue (MB) from waste water. The adsorption performance of the magnetic zeolite for MB were studied in various processing conditions, and the adsorption mechanism was revealed. The results show that the removal efficiency and equilibrium adsorption capacity of 2.0% Fe₃O₄@NaX (mass fraction) zeolite for MB were 96.98% and 45.19 mg/g, respectively, in the following adsorption conditions: zeolite dosage of 1 g/L, initial pH of 5.7 of the solution, initial MB concentration of 50 mg/L, adsorption temperature of 25 °C and adsorption time of 60 min. The magnetic zeolite can be separated rapidly from dye solution by an applied external magnetic field, indicating its excellent recyclability. The MB adsorption on the zeolite is a spontaneous and exothermic process of entropy reduction, which follows the pseudo-second-order kinetics and Langmuir isotherm models. The electrostatic attraction, hydrogen bonds and pore diffusion are the main driving forces of the adsorption process.

Key words： synthesizing and processing technics for materials magnetic zeolite alkaline fusion hydrothermal method adsorption oil shale ash methylene blue

收稿日期: 2024-06-27

ZTFLH:

TQ09

基金资助:国家自然科学基金(22008187);国家自然科学基金(22208256);国家自然科学基金(22308269)

通讯作者: 王倩，shangjinzhe@163.com，研究方向为油页岩结构研究及其高值利用；
白慧娟，副研究员，huijuanbai@ipe.edu.cn，研究方向为多功能材料设计及应用

Corresponding author: WANG Qian, Tel: 13263280805, E-mail: shangjinzhe@163.com;
BAI Huijuan, Tel: 18811036008, E-mail: huijuanbai@ipe.edu.cn

作者简介: 段玉，女，2000年生，硕士生

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表1 BPA的化学组成

图1 BPA的XRD谱

图2 NaX分子筛的XRD谱和FTIR谱

图3 不同Fe3O4负载量的Fe3O4@NaX型分子筛的XRD谱

图4 NaX和Fe3O4@NaX型分子筛的SEM照片

图5 Fe3O4@NaX型分子筛的TEM照片和选定区域的元素分布

图6 Fe3O4负载量不同的Fe3O4@NaX型分子筛对MB的吸附率

图7 2.0% Fe3O4@NaX型分子筛的磁滞回线

图8 Fe3O4@NaX型分子筛的N2吸附-脱附等温线和孔径分布

图9 吸附条件对分子筛吸附性能的影响

图10 几种盐和盐度对分子筛吸附MB的影响

表2 不同吸附剂对MB的吸附性能

表3 Fe3O4@NaX型分子筛吸附MB的动力学参数

表4 Fe3O4@NaX型分子筛吸附MB的等温线参数

表5 Fe3O4@NaX型分子筛吸附MB的热力学参数

图11 Fe3O4@NaX型分子筛吸附前后的XPS谱

图12 Fe3O4@NaX型分子筛吸附前后的FTIR谱

图13 Fe3O4@NaX型分子筛吸附MB的机理

图14 Fe3O4@NaX型分子筛的可重复利用性能和洗脱前后的XRD谱

1	Liu Z J, Ma H T, Wang Z, et al. Experimental study on the thermophysical properties of Jimsar oil shale[J]. Oil Shale, 2023, 40(3): 194
2	Bai S X, Chu M, Zhou L M, et al. Modified oil shale ash and oil shale ash zeolite for the removal of Cd²⁺ ion from aqueous solutions[J]. Environ. Technol., 2019, 40(11): 1485
3	Hamadi A, Nabih K. Alkali activation of oil shale ash based ceramics[J]. E-J. Chem., 2012, 9(3): 1373
4	Ilman H S N M, Panatarani C, Faizal F, et al. Synthesis of mesoporous silica SBA-15 from geothermal sludge[J]. Materialia, 2023, 27: 101637
5	Shawabkeh R, Al-Harahsheh A, Hami M, et al. Conversion of oil shale ash into zeolite for cadmium and lead removal from wastewater[J]. Fuel, 2004, 83(7-8): 981
6	Bao W W, Zou H F, Gan S C, et al. Adsorption of heavy metal ions from aqueous solutions by zeolite based on oil shale ash: kinetic and equilibrium studies[J]. Chem. Res. Chin. Univ., 2013, 29(1): 126
7	Piri F, Mollahosseini A, Khadir A, et al. Enhanced adsorption of dyes on microwave-assisted synthesized magnetic zeolite-hydroxyapatite nanocomposite[J]. J. Environ. Chem. Eng., 2019, 7(5): 103338
8	Liu H Q, Wu Y J, Yang Y, et al. Adsorption and recovery of low concentration coal-bed methane by zeolite ZSM-5[J]. CIESC J., 2016, 67(5): 1931 doi: 10.11949/j.issn.0438-1157.20151684
8	刘海庆, 吴一江, 杨颖等. 沸石ZSM-5吸附回收低浓度煤层气中CH₄ [J]. 化工学报, 2016, 67(5): 1931 doi: 10.11949/j.issn.0438-1157.20151684
9	Tehubijuluw H, Subagyo R, Yulita M F, et al. Utilization of red mud waste into mesoporous ZSM-5 for methylene blue adsorption-desorption studies[J]. Environ. Sci. Pollut. Res., 2021, 28(28): 37354
10	Cheng Y, Xu L J, Jiang Z, et al. Feasible low-cost conversion of red mud into magnetically separated and recycled hybrid SrFe₁₂O₁₉@NaP1 zeolite as a novel wastewater adsorbent[J]. Chem. Eng. J., 2021, 417: 128090
11	Liu H B, Peng S C, Shu L, et al. Magnetic zeolite NaA: synthesis, characterization based on metakaolin and its application for the removal of Cu²⁺, Pb²⁺ [J]. Chemosphere, 2013, 91(11): 1539 doi: 10.1016/j.chemosphere.2012.12.038 pmid: 23340053
12	Shi L, Wang Q, Zhao X S, et al. The methyl blue adsorption performance and mechanism of NaX zeolite synthesized from Huadian oil shale ash[J]. J. Taiwan Inst. Chem. Eng., 2023, 147: 104904
13	Rajabi S K, Sohrabnezhad S. Synthesis and characterization of magnetic core with two shells: mordenite zeolite and CuO to form Fe₃O₄@MOR@CuO core-shell: as a visible light driven photocatalyst[J]. Micropor. Mesopor. Mater., 2017, 242: 136
14	Zeidan H, Can M, Marti M E. Synthesis, characterization, and use of an amine-functionalized mesoporous silica SBA-15 for the removal of Congo Red from aqueous media[J]. Res. Chem. Intermed., 2023, 49(1): 221
15	Jia W L, Wang S Y, Deng Y Y, et al. Characterization and application of lamellar zeolite-X prepared from kaolin[J]. Micro Nano Lett., 2024, 19(1): e12182
16	Zhang M S, Wang S Y, Hu Z, et al. Synthesis and characterization of zeolite X obtained from coal gangue for adsorption of Cu²⁺ [J]. Sci. Adv. Mater., 2021, 13(8): 1512
17	Yan K Z, Zhang J Y, Liu D D, et al. Feasible synthesis of magnetic zeolite from red mud and coal gangue: preparation, transformation and application[J]. Powder Technol., 2023, 423: 118495
18	Zhang T, Peng X L, Li J, et al. Structural, magnetic and electromagnetic properties of SrFe₁₂O₁₉ ferrite with particles aligned in a magnetic field[J]. J. Alloy. Compd., 2017, 690: 936
19	Singh P, Sharma K, Hasija V, et al. Systematic review on applicability of magnetic iron oxides-integrated photocatalysts for degradation of organic pollutants in water[J]. Mater. Today Chem., 2019, 14: 100186
20	Cao J, Sun Q, Wang P, et al. Synthesize and characterize of Fe₃O₄/zeolite 4A magnetic nanocomposite[J]. J. Dispersion Sci. Technol., 2022, 43(4): 517
21	Yan J S, Li Y, Li H R, et al. Effective removal of ruthenium (III) ions from wastewater by amidoxime modified zeolite X[J]. Microchem. J., 2019, 145: 287
22	Awala H, Leite E, Saint-Marcel L, et al. Properties of methylene blue in the presence of zeolite nanoparticles[J]. New J. Chem., 2016, 40(5): 4277
23	Belachew N, Hinsene H. Preparation of zeolite 4A for adsorptive removal of methylene blue: optimization, kinetics, isotherm, and mechanism study[J]. Silicon, 2022, 14(4): 1629 doi: 10.1007/s12633-020-00938-9
24	Ioannou Z, Karasavvidis C, Dimirkou A, et al. Adsorption of methylene blue and methyl red dyes from aqueous solutions onto modified zeolites[J]. Water Sci. Technol., 2013, 67(5): 1129 doi: 10.2166/wst.2013.672 pmid: 23416607
25	Dadashi R, Bahram M, Farhadi K, et al. Photodecoration of tungsten oxide nanoparticles onto eggshell as an ultra-fast adsorbent for removal of MB dye pollutant[J]. Sci. Rep., 2024, 14(1): 14478 doi: 10.1038/s41598-024-65573-5 pmid: 38914725
26	Majid Z, Abdulrazak A A, Noori W A H. Modification of zeolite by magnetic nanoparticles for organic dye removal[J]. Arab. J. Sci. Eng., 2019, 44(6): 5457
27	Hor K Y, Chee J M C, Chong M N, et al. Evaluation of physicochemical methods in enhancing the adsorption performance of natural zeolite as low-cost adsorbent of methylene blue dye from wastewater[J]. J. Clean. Prod., 2016, 118: 197
28	Li C X, Zhong H, Wang S, et al. Removal of basic dye (methylene blue) from aqueous solution using zeolite synthesized from electrolytic manganese residue[J]. J. Ind. Eng. Chem., 2015, 23: 344
29	Alhogbi B G, Al Balawi G S. An investigation of a natural biosorbent for removing methylene blue dye from aqueous solution[J]. Molecules, 2023, 28(6): 2785
30	Guo Y F, Deng J, Zhu J Y, et al. Removal of mercury(II) and methylene blue from a wastewater environment with magnetic graphene oxide: adsorption kinetics, isotherms and mechanism[J]. RSC Adv., 2016, 6(86): 82523
31	Zhang Y M, Dai T L, Zhang F, et al. Fe₃O₄@UiO-66-NH₂ core-shell nanohybrid as stable heterogeneous catalyst for Knoevenagel condensation[J]. Chin. J. Catal., 2016, 37(12): 2106
31	张艳梅, 戴田霖, 张帆等. 核壳结构Fe₃O₄@UiO-66-NH₂磁性纳米复合材料的合成及其催化Knoevenagel缩合反应性能[J]. 催化学报, 2016, 37(12): 2106 doi: 10.1016/S1872-2067(16)62562-7
32	Cao J S, Lin J X, Fang F, et al. A new absorbent by modifying walnut shell for the removal of anionic dye: kinetic and thermodynamic studies[J]. Bioresour. Technol., 2014, 163: 199
33	Nezamzadeh-Ejhieh A, Karimi-Shamsabadi M. Comparison of photocatalytic efficiency of supported CuO onto micro and nano particles of zeolite X in photodecolorization of methylene blue and methyl orange aqueous mixture[J]. Appl. Catal., 2014, 477: 83
34	Bai S X, Zhou L M, Chang Z B, et al. Synthesis of Na-X zeolite from Longkou oil shale ash by alkaline fusion hydrothermal method[J]. Carbon Resour. Convers., 2018, 1(3): 245

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