高岭石基介孔复合材料的二氧化碳吸附性能

摘要/Abstract

摘要： 碳排放量的快速增长所引起的全球气候变暖问题越来越受到各国的关注,因此研发制备可行高效的二氧化碳(CO₂)捕获材料具有极其重要的意义。本文以高岭石为原材料,采用煅烧-碱活化-酸刻蚀的方法,制备出介孔氧化硅载体(KNH),再将KNH经过五乙烯六胺(PEHA)修饰后制备出介孔复合材料(KNH-PEHA)。通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、扫描电子显微镜(SEM)、N₂物理吸附等方法对样品进行表征,并进一步对样品进行CO₂吸附性能研究。结果表明,PEHA的浸渍修饰并未改变载体的结构,但显著提高了介孔复合材料对CO₂的吸附能力。吸附温度为25 ℃,KNH的CO₂吸附量为147.39 cm³/g,而PEHA质量分数为30%的KNH(KNH-P-30)平衡时的CO₂吸附量达到389 cm³/g,远高于未经PEHA修饰的KNH的吸附量,同时提出了该固体吸附剂对CO₂的吸附机理,为高岭石在气体吸附领域的应用提供一个新思路。

关键词: 高岭石, 介孔复合材料, 五乙烯六胺, 二氧化碳, 吸附性能

Abstract: The problem of global warming caused by the rapid growth of carbon emissions has attracted more and more attention in all countries, so it is of great importance to develop feasible CO₂ capture materials. In this paper, kaolinite is used as raw material, to prepare mesoporous silica carrier (KNH) with the method of calcination-alkali activation-acid etching. Then the pentaethylenehexaamine (PEHA) functionalized mesoporous silica (KNH-PEHA) was synthesized via impregnation. The prepared samples were characterized by X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and N₂ adsorption-desorption isotherms treated by BET (Brunauer-Emmett-Teller) analysis. And the solid adsorbent is also used to study the adsorption property of carbon dioxide (CO₂). The results indicate that the structure of PEHA-loaded KNH is not changed, but its carbon dioxide adsorption capacity is improved. When the adsorption temperature is 25 ℃, the CO₂ adsorption capacity of KNH is 147.39 cm³/g, and the CO₂ adsorption capacity of KNH (KNH-P-30) with a mass percentage of PEHA of 30% reaches 389 cm³/g, which is much higher than that without PEHA modified KNH adsorption. At the same time, it express the adsorption mechanism of the solid adsorbent for CO₂, which provides a new idea for the application of kaolinite in the field of gas adsorption.

Key words: kaolinite, mesoporous composite, pentaethylhexaamine, carbon dioxide, adsorption property

中图分类号:

TB33

陈心怡, 程宏飞, 赵炳新, 胡棉舒, 贾晓辉. 高岭石基介孔复合材料的二氧化碳吸附性能[J]. 人工晶体学报, 2021, 50(9): 1756-1764.

CHEN Xinyi, CHENG Hongfei, ZHAO Bingxin, HU Mianshu, JIA Xiaohui. Carbon Dioxide Adsorption Property of Kaolinite-Based Mesoporous Composites[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(9): 1756-1764.

参考文献

[1] ZHANG X F, ELSAYED I, SONG X Z, et al. Microporous carbon nanoflakes derived from biomass cork waste for CO₂ capture[J]. Science of the Total Environment, 2020, 748: 142465.
[2] JAFARI B, RAHIMI M R, GHAEDI M, et al. CO₂ capture by amine-based aqueous solution containing atorvastatin functionalized mesocellular silica foam in a counter-current rotating packed bed: central composite design modeling[J]. Chemical Engineering Research and Design, 2018, 129: 64-74.
[3] 刘勇军,巩梦丹,王雪娇,等.有机胺改性多孔材料制备固体胺二氧化碳吸附剂的研究进展[J].四川化工,2014,17(5):25-28.
LIU Y J, GONG M D, WANG X J, et al. The research progress of solid amine CO₂ adsorbent prepared by amine-modified porous materials[J]. Sichuan Chemical Industry, 2014, 17(5): 25-28(in Chinese).
[4] VENNA S R, CARREON M A. Metal organic framework membranes for carbon dioxide separation[J]. Chemical Engineering Science, 2015, 124: 3-19.
[5] WANG Y S, DU T, SONG Y L, et al. Amine-functionalized mesoporous ZSM-5 zeolite adsorbents for carbon dioxide capture[J]. Solid State Sciences, 2017, 73: 27-35.
[6] WANG X, GUO Q J, ZHAO J, et al. Mixed amine-modified MCM-41 sorbents for CO₂ capture[J]. International Journal of Greenhouse Gas Control, 2015, 37: 90-98.
[7] WANG Y, YANG R T. Template removal from SBA-15 by ionic liquid for amine grafting: applications to CO₂ capture and natural gas desulfurization[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(22): 295-304.
[8] GHOLIDOUST A, ATKINSON J D, HASHISHO Z. Enhancing CO₂ adsorption via amine-impregnated activated carbon from oil sands coke[J]. Energy & Fuels, 2017, 31(2): 1756-1763.
[9] JIANG X, KONG Y, ZHAO Z Y, et al. Spherical amine grafted silica aerogels for CO₂ capture[J]. RSC Advances, 2020, 10(43): 25911-25917.
[10] LIU Y M, SHI J J, CHEN J, et al. Dynamic performance of CO₂ adsorption with tetraethylenepentamine-loaded KIT-6[J]. Microporous and Mesoporous Materials, 2010, 134(1/2/3): 16-21.
[11] WEI L, JING Y, GAO Z M, et al. Development of a pentaethylenehexamine-modified solid support adsorbent for CO₂ capture from model flue gas[J]. Chinese Journal of Chemical Engineering, 2015, 23(2): 366-371.
[12] FUJIKI J, YAMADA H, YOGO K. Enhanced adsorption of carbon dioxide on surface-modified mesoporous silica-supported tetraethylenepentamine: role of surface chemical structure[J]. Microporous and Mesoporous Materials, 2015, 215: 76-83.
[13] 褚效中,周守勇,张兴振,等.胺基功能化凹土材料制备及其对CO₂和N₂吸附性能研究[C]//第十八届全国二氧化硫、氮氧化物、汞污染防治暨细颗粒物(PM_2.5)治理技术研讨会论文集.洛阳,2014:100-104.
CHU X Z, ZHOU S Y, ZHANG X Z, et al. Preparation of amine based functionalized attapulgite materials and their adsorption properties for CO₂ and N₂[C]//Proceedings of the 18th National Symposium on prevention and control of sulfur dioxide, nitrogen oxides and mercury pollution and fine particulate matter (PM_2.5) treatment technology. Luoyang, 2014: 100-104(in Chinese).
[14] 赵唯君,张华丽,严春杰,等.乙醇胺和N,N-二甲基乙醇胺改性埃洛石对CO₂的吸附行为[J].武汉工程大学学报,2017,39(5):420-426.
ZHAO W J, ZHANG H L, YAN C J, et al. Adsorption behavior of carbon dioxide with halloysite modified by ethanol amineand N, N-dimethyl ethanolamine[J]. Journal of Wuhan Institute of Technology, 2017, 39(5): 420-426(in Chinese).
[15] CHEN Y H, LU D L. Amine modification on kaolinites to enhance CO₂ adsorption[J]. Journal of Colloid and Interface Science, 2014, 436: 47-51.
[16] LIU Q, LI F, LU H, et al. Enhanced dispersion stability and heavy metal ion adsorption capability of oxidized starch nanoparticles[J]. Food Chemistry, 2018, 242: 256-263.
[17] SHABAN M, SAYED M I, SHAHIEN M G, et al. Adsorption behavior of inorganic- and organic-modified kaolinite for Congo red dye from water, kinetic modeling, and equilibrium studies[J]. Journal of Sol-Gel Science and Technology, 2018, 87(2): 427-441.
[18] YADAV V B, CADI R, KALRA S. Adsorption bentonite carbon nanotube (CNT) heavy metals kaolinite montmorillonite water pollution [J]. Journal of environmental management, 2018, 232: 803-817.
[19] HOUNFODJI J W, KANHOUNNON W G, KPOTIN G, et al. Molecular insights on the adsorption of some pharmaceutical residues from wastewater on kaolinite surfaces[J]. Chemical Engineering Journal, 2021, 407: 127176.
[20] ZHANG Y M, LIU Q F, ZHANG S L, et al. Characterization of kaolinite/styrene butadiene rubber composite: mechanical properties and thermal stability[J]. Applied Clay Science, 2016, 124/125: 167-174.
[21] SPENCE A, KELLEHER B P. FT-IR spectroscopic analysis of kaolinite-microbial interactions[J]. Vibrational Spectroscopy, 2012, 61: 151-155.
[22] OUYANG J, GU W, ZHANG Y, et al. CO₂ capturing performances of millimeter scale beads made by tetraethylenepentamine loaded ultra-fine palygorskite powders from jet pulverization[J]. Chemical Engineering Journal, 2018, 341: 432-440.
[23] 王晓光,刘岱,陈绍云,等.五乙烯六胺改性金属有机骨架材料MIL-101(Cr)对CO₂的吸附性能[J].燃料化学学报,2017,45(4):484-490.
WANG X G, LIU D, CHEN S Y, et al. Performance of pentaethylenehexamine modified MIL-101(Cr) metal-organic framework in CO₂ adsorption[J]. Journal of Fuel Chemistry and Technology, 2017, 45(4): 484-490(in Chinese).
[24] 冯星星,谢菁,胡庚申,等.五乙烯六胺修饰的MCF基吸附剂的制备及其CO₂吸附性能研究[J].物理化学学报,2013,29(6):1266-1272.
FENG X X, XIE J, HU G S, et al. Preparation of pentaethylenehexamine-functionalized mesocellular silica foams and their application for CO₂ adsorption[J]. Acta Physico-Chimica Sinica, 2013, 29(6): 1266-1272(in Chinese).
[25] 李天天.基于高岭土的高比表面积介孔材料的无模板法制备新工艺[D].武汉:中国地质大学,2016.
LI T T. Novel approaches for template-free synthesis of Kaolin-derived mesoporous materials with large specific surface areas[D]. Wuhan: China University of Geosciences, 2016(in Chinese).
[26] 王正,郑林会,牛三鑫,等.高比表面积偏高岭土制备及其对Cr(Ⅵ)、Ni(Ⅱ)吸附性能研究[J].应用化工,2020,49(3):624-627.
WANG Z, ZHENG L H, NIU S X, et al. Preparation of metakaolin of high specific surface area and its adsorption properties for Cr(Ⅵ) and Ni(Ⅱ)[J]. Applied Chemical Industry, 2020, 49(3): 624-627(in Chinese).
[27] HU X Y, LIU L B, LUO X, et al. A review of N-functionalized solid adsorbents for post-combustion CO₂ capture[J]. Applied Energy, 2020, 260: 114244.
[28] YAN X L, ZHANG L, ZHANG Y, et al. Amine-modified SBA-15: effect of pore structure on the performance for CO₂ capture[J]. Industrial & Engineering Chemistry Research, 2011, 50(6): 3220-3226.