地质聚合物在污水治理领域中的研究进展

摘要/Abstract

摘要： 地质聚合物指以铝硅酸盐类工业固体废弃物、烧黏土为原料,在化学激发作用下经“解聚-缩聚-重构”过程制备的新型无机胶凝材料。与传统硅酸盐水泥相比,地质聚合物制备过程低碳环保、结构可控、性能可调,被誉为21世纪最具发展前景的绿色胶凝材料。同时,地质聚合物因形成过程与人工合成沸石相似,具有沸石矿物的物质和结构遗传特性。基于沸石的离子交换吸附特性,以地质聚合物为吸附材料应用于污水治理迅速成为研究热点。本文归纳了地质聚合物的合成机理与结构特性,概述了地质聚合物在污水治理领域中的研究现状,探讨了地质聚合物在污水治理领域面临的问题与发展前景。

关键词: 地质聚合物, 合成机理, 结构特性, 污水治理

Abstract: Geopolymer is a novel type of inorganic cementitious material prepared from aluminosilicate industrial solid waste and burnt clay as raw materials through a process of “depolymerization-condensation-reconstruction” under the action of chemical excitation. Compared to traditional Portland cement, geopolymer is known as the most promising green cementitious material in the 21st century due to its low-carbon environmental protection, controllable structure, and adjustable performance during the preparation process. At the same time, geopolymer has the material and structural genetic characteristics of zeolite minerals due to the formation process similar to synthetic zeolite. Based on the ion exchange and adsorption properties of zeolite, the application of geopolymers as an adsorption material for sewage treatment is rapidly becoming a research hotspot. This paper summarizes the synthesis mechanisms and structural characteristics of geopolymers, outlines the current research status of geopolymers in the field of sewage treatment, and discusses the problems and development prospects of geopolymers in the field of sewage treatment.

Key words: geopolymer, synthesis mechanism, structural characteristic, sewage treatment

中图分类号:

TU528

刘博研, 彭新盼, 郭昭呈, 刘琦, 范丽花, 宋学锋. 地质聚合物在污水治理领域中的研究进展[J]. 硅酸盐通报, 2024, 43(11): 4083-4098.

LIU Boyan, PENG Xinpan, GUO Zhaocheng, LIU Qi, FAN Lihua, SONG Xuefeng. Research Progress of Geopolymers in Sewage Treatment[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2024, 43(11): 4083-4098.

参考文献

[1] DAVIDOVITS J. Geopolymers[J]. Journal of Thermal Analysis, 1991, 37(8): 1633-1656.
[2] DAVIDOVITS J. Geopolymers and geopolymeric materials[J]. Journal of Thermal Analysis, 1989, 35(2): 429-441.
[3] 杨达, 卢明阳, 宋迪, 等. 地质聚合物水泥的研究进展[J]. 材料导报, 2021, 35(增刊1): 644-649.
YANG D, LU M Y, SONG D, et al. Research progress of geological polymer cement[J]. Materials Guide, 2021, 35 (supplement 1): 644-649 (in Chinese).
[4] STURM P, GLUTH G J G, SIMON S, et al. The effect of heat treatment on the mechanical and structural properties of one-part geopolymer-zeolite composites[J]. Thermochimica Acta, 2016, 635: 41-58.
[5] 崔学民, 唐青, 李纯民, 等. 地质聚合物中类沸石结构的形成及应用[J]. 稀有金属材料与工程, 2015, 44(11): 600-603.
CUI X M, TANG Q, LING C M, et al. Formation and application of zeolite-like structures in geopolymers[J]. Rare Metal Materials & Engineering, 2015, 44(11): 600-603 (in Chinese).
[6] GLUKHOVSKY V D. Soil silicates: their properties, technology and manufacturing and fields of application[D]. Uraine: Civil Engineering Institute, 1965.
[7] PROVIS J L, LUKEY G C, VAN DEVENTER J S J. Do geopolymers actually contain nanocrystalline zeolites? A reexamination of existing results[J]. Chemistry of Materials, 2005, 17(12): 3075-3085.
[8] YAN H, CUI X M, JIN M, et al. The hydrothermal transformation of solid geopolymers into zeolites[J]. Microporous and Mesoporous Materials, 2012, 161: 187-192.
[9] ZHANG J, HE Y, WANG Y P, et al. Synthesis of a self-supporting faujasite zeolite membrane using geopolymer gel for separation of alcohol/water mixture[J]. Materials Letters, 2014, 116: 167-170.
[10] ZHENG G J, CUI X M, ZHANG W P, et al. Preparation of geopolymer precursors by sol-gel method and their characterization[J]. Journal of Materials Science, 2009, 44(15): 3991-3996.
[11] WENG L, SAGOE-CRENTSIL K. Dissolution processes, hydrolysis and condensation reactions during geopolymer synthesis: part I—low Si/Al ratio systems[J]. Journal of Materials Science, 2007, 42(9): 2997-3006.
[12] DAVIDOVITS J. Properties of geopolymer cements[A]. First international conference on alkaline cements and concretes, 1994, 1: 131-149.
[13] BIRANCHI P. 3D printing of high-volume fly ash mixtures for digital concrete construction[D]. Singapore: Nanyang Technological University, 2019.
[14] ELGARAHY A M, MAGED A, ELOFFY M G, et al. Geopolymers as sustainable eco-friendly materials: classification, synthesis routes, and applications in wastewater treatment[J]. Separation and Purification Technology, 2023, 324: 124631.
[15] PARATHI S, NAGARAJAN P, PALLIKKARA S A. Ecofriendly geopolymer concrete: a comprehensive review[J]. Clean Technologies and Environmental Policy, 2021, 23(6): 1701-1713.
[16] 徐庆, 李秋, 陈伟, 等. 碱激发剂模数对地质聚合物透水混凝土的性能影响研究[J]. 硅酸盐通报, 2018, 37(11): 3575-3580+3586.
XU Q, LI Q, CHEN W, et al. Effect of modulus of alkali-activator on the properties of GGBS-based geopolymer pervious concrete[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(11): 3575-3580+3586 (in Chinese).
[17] 黄学满, 饶吉来, 杜凯. 煤矸石基地质聚合物的制备与性能优化研究[J]. 矿业安全与环保, 2023, 50(6): 92-97+103.
HUANG X M, RAO J L, DU K. Preparation and performance optimization of coal gangue-based geopolymer[J]. Mining Safety & Environmental Protection, 2023, 50(6): 92-97+103 (in Chinese).
[18] 包申旭, 周海林, 张一敏, 等. 地质聚合物的制备与应用研究现状[J].有色金属(冶炼部分), 2024, 5: 126-135.
BAO S X, ZHOU H L, ZHANG Y M, et al. Current status of preparation and application of geological polymers[J]. Non-Ferrous Metals (Smelting Part), 2024, 5: 126-135 (in Chinese).
[19] SHI S, LI H, ZHOU Q Z, et al. Alkali-activated fly ash cured with pulsed microwave and thermal oven: a comparison of reaction products, microstructure and compressive strength[J]. Cement and Concrete Research, 2023, 166: 107104.
[20] YUAN J K, HE P G, JIA D C. The effect of Si/Al on mechanical properties and fracture behavior of stainless steel mesh/Cr_p reinforced geopolymer composites[J]. MATEC Web of Conferences, 2017, 97: 01011.
[21] LI Z F, GAO Y F, ZHANG J, et al. Effect of particle size and thermal activation on the coal gangue based geopolymer[J]. Materials Chemistry and Physics, 2021, 267: 124657.
[22] 魏玮, 杨涛. 高流动性3D打印水泥基材料制备及性能研究[J]. 混凝土与水泥制品, 2021(2): 8-12.
WEI W, YANG T. Study on preparation and properties of high fluidity 3D printed cement-based materials[J]. China Concrete and Cement Products, 2021(2): 8-12 (in Chinese).
[23] 胡金浪, 丁国新, 张仕成, 等. 多孔地质聚合物发泡工艺及吸附性能研究进展[J]. 化工新型材料, 2023, 51(11): 272-277.
HU J L, DING G X, ZHANG S C, et al. Research progress on foaming process and adsorption performance of porous geopolymers[J]. New Chemical Materials, 2023, 51(11): 272-277 (in Chinese).
[24] LAN T, LI P F, REHMAN F U, et al. Efficient adsorption of Cd²⁺ from aqueous solution using metakaolin geopolymers[J]. Environmental Science and Pollution Research, 2019, 26(32): 33555-33567.
[25] MALEKI A, HAJIZADEH Z, SHARIFI V, et al. A green, porous and eco-friendly magnetic geopolymer adsorbent for heavy metals removal from aqueous solutions[J]. Journal of Cleaner Production, 2019, 215: 1233-1245.
[26] BOUNA L, FAKIR A A E, BENLHACHEMI A, et al. Synthesis and characterization of mesoporous geopolymer based on Moroccan kaolinite rich clay[J]. Applied Clay Science, 2020, 196: 105764.
[27] ACISLI O, ACAR I, KHATAEE A. Preparation of a fly ash-based geopolymer for removal of a cationic dye: isothermal, kinetic and thermodynamic studies[J]. Journal of Industrial and Engineering Chemistry, 2020, 83: 53-63.
[28] ACISLI O, ACAR I, KHATAEE A. Preparation of a surface modified fly ash-based geopolymer for removal of an anionic dye: parameters and adsorption mechanism[J]. Chemosphere, 2022, 295: 133870.
[29] SELKÄLÄ T, SUOPAJÄRVI T, SIRVIÖ J A, et al. Surface modification of cured inorganic foams with cationic cellulose nanocrystals and their use as reactive filter media for anionic dye removal[J]. ACS Applied Materials & Interfaces, 2020, 12(24): 27745-27757.
[30] CHEN X, GUO Y G, DING S, et al. Utilization of red mud in geopolymer-based pervious concrete with function of adsorption of heavy metal ions[J]. Journal of Cleaner Production, 2019, 207: 789-800.
[31] MALEKI A, MOHAMMAD M, EMDADI Z, et al. Adsorbent materials based on a geopolymer paste for dye removal from aqueous solutions[J]. Arabian Journal of Chemistry, 2020, 13(1): 3017-3025.
[32] 鄢茹月, 秦伟伟, 曾俊楠, 等. 地质聚合物用于废水处理的现状与发展趋势研究——基于文献计量分析[J]. 环境科学学报, 2023, 43(12): 194-205.
YAN R Y, QIN W W, ZENG J N, et al. The current status and development trend of geopolymers used in wastewater treatment based on bibliometric analysis[J]. Acta Scientiae Circumstantiae, 2023, 43(12): 194-205 (in Chinese).
[33] ZHANG Y J, HE P Y, YANG M Y, et al. A new graphene bottom ash geopolymeric composite for photocatalytic H₂ production and degradation of dyeing wastewater[J]. International Journal of Hydrogen Energy, 2017, 42(32): 20589-20598.
[34] INNOCENTINI M D M, BOTTI R F, BASSI P M, et al. Lattice-shaped geopolymer catalyst for biodiesel synthesis fabricated by additive manufacturing[J]. Ceramics International, 2019, 45(1): 1443-1446.
[35] 张凯铭, 杨浪, 饶峰, 等. 地质聚合物多孔材料的制备及应用研究进展[J]. 金属矿山, 2022, 10: 226-237.
ZHANG K M, YANG L, RAO F, et al. Progress in the preparation and application of geological polymer porous materials [J]. Metal Mine, 2022, 10: 226-237 (in Chinese).
[36] CHINDAPRASIRT P, JITSANGIAM P, CHALEE W, et al. Case study of the application of pervious fly ash geopolymer concrete for neutralization of acidic wastewater[J]. Case Studies in Construction Materials, 2021, 15: e00770.
[37] EL ALOUANI M, ALEHYEN S, EL ACHOURI M, et al. Preparation, characterization, and application of metakaolin-based geopolymer for removal of methylene blue from aqueous solution[J]. Journal of Chemistry, 2019, 2019(1): 4212901.
[38] NOVAIS R M, ASCENS Ã O G, TOBALDI D M, et al. Biomass fly ash geopolymer monoliths for effective methylene blue removal from wastewaters[J]. Journal of Cleaner Production, 2018, 171: 783-794.
[39] GE Y Y, CUI X M, LIAO C L, et al. Facile fabrication of green geopolymer/alginate hybrid spheres for efficient removal of Cu(II) in water: batch and column studies[J]. Chemical Engineering Journal, 2017, 311: 126-134.
[40] CHENG T W, LEE M L, KO M S, et al. The heavy metal adsorption characteristics on metakaolin-based geopolymer[J]. Applied Clay Science, 2012, 56: 90-96.
[41] LIU Y, YAN C J, ZHANG Z H, et al. A comparative study on fly ash, geopolymer and faujasite block for Pb removal from aqueous solution[J]. Fuel, 2016, 185: 181-189.
[42] ROŻEK P, KRÓL M, MOZGAWA W. Spectroscopic studies of fly ash-based geopolymers[J]. Spectrochimica Acta Part A, Molecular and Biomolecular Spectroscopy, 2018, 198: 283-289.
[43] TANG Q, WANG K T, YASEEN M, et al. Synthesis of highly efficient porous inorganic polymer microspheres for the adsorptive removal of Pb²⁺ from wastewater[J]. Journal of Cleaner Production, 2018, 193: 351-362.
[44] TIAN Q Z, SASAKI K. Application of fly ash-based geopolymer for removal of cesium, strontium and arsenate from aqueous solutions: kinetic, equilibrium and mechanism analysis[J]. Water Science and Technology, 2019, 79(11): 2116-2125.
[45] SIYAL A A, SHAMSUDDIN M R, KHAHRO S H, et al. Optimization of synthesis of geopolymer adsorbent for the effective removal of anionic surfactant from aqueous solution[J]. Journal of Environmental Chemical Engineering, 2021, 9(1): 104949.
[46] PADMAPRIYA M, RAMESH S T, BIJU V M. Synthesis of seawater based geopolymer: characterization and adsorption capacity of methylene blue from wastewater[J]. Materials Today: Proceedings, 2022, 51: 1770-1776.
[47] EL ALOUANI M, ALEHYEN S, EL ACHOURI M, et al. Comparative study of the adsorption of micropollutant contained in aqueous phase using coal fly ash and activated coal fly ash: kinetic and isotherm studies[J]. Chemical Data Collections, 2019, 23: 100265.
[48] NOVAIS R M, BURUBERRI L H, SEABRA M P, et al. Novel porous fly-ash containing geopolymer monoliths for lead adsorption from wastewaters[J]. Journal of Hazardous Materials, 2016, 318: 631-640.
[49] AKAR S T, KOC E, SAYIN F, et al. Design and modeling of the decolorization characteristics of a regenerable and eco-friendly geopolymer: batch and dynamic flow mode treatment aspects[J]. Journal of Environmental Management, 2021, 298: 113548.
[50] NJIMOU J R, PENGOU M, TCHAKOUTE H K, et al. Removal of lead ions from aqueous solution using phosphate-based geopolymer cement composite[J]. Journal of Chemical Technology & Biotechnology, 2021, 96(5): 1358-1369.
[51] LAN T, GUO S W, LI X L, et al. Mixed precursor geopolymer synthesis for removal of Pb(II) and Cd(II)[J]. Materials Letters, 2020, 274: 127977.
[52] EL ALOUANI M, ALEHYEN S, EL ACHOURI M, et al. Removal of cationic dye-methylene blue-from aque ous solution by adsorption on fly ash-based geopolymer[J]. Journal of Materials and Environmental Sciences, 2018, 9(1): 32-46.
[53] HUA P Y, SELLAOUI L, FRANCO D, et al. Adsorption of acid green and procion red on a magnetic geopolymer based adsorbent: experiments, characterization and theoretical treatment[J]. Chemical Engineering Journal, 2020, 383: 123113.
[54] BARBOSA T R, FOLETTO E L, DOTTO G L, et al. Preparation of mesoporous geopolymer using metakaolin and rice husk ash as synthesis precursors and its use as potential adsorbent to remove organic dye from aqueous solutions[J]. Ceramics International, 2018, 44(1): 416-423.
[55] 雷嘉芊. 粉煤灰基地质聚合物复合阳极材料的制备及电化学性能研究[D]. 西安: 西安建筑科技大学, 2021.
LEI J Q. Preparation and electrochemical properties of fly ash-based geopolymer composite anode materials[D]. Xi'an: Xi'an University of Architecture and Technology, 2021 (in Chinese).
[56] 窦怀远. 地质聚合物基锂分子筛的制备与表征[D]. 南宁: 广西大学, 2023.
DOU H Y. Preparation and characterization of geopolymer-based lithium molecular sieves[D]. Nanning: Guangxi University, 2023 (in Chinese).
[57] 王飞凡. 矿渣基地聚物微球的制备及其应用性能[D]. 南宁: 广西大学, 2023.
WANG F F. Preparation and application properties of slag-based polymer microspheres[D]. Nanning: Guangxi University, 2023 (in Chinese).
[58] 孟倩. 地质聚合物光阳极材料的制备及光电催化性能[D]. 西安: 西安建筑科技大学, 2023.
MENG Q. Preparation and photocatalytic properties of geopolymer photoanode materials[D]. Xi'an: Xi'an University of Architecture and Technology, 2023 (in Chinese).
[59] KAYA-ÖZKIPER K, UZUN A, SOYER-UZUN S. Red mud- and metakaolin-based geopolymers for adsorption and photocatalytic degradation of methylene blue: towards self-cleaning construction materials[J]. Journal of Cleaner Production, 2021, 288: 125120.
[60] SANG M M, ZHAO H Z, LI Y, et al. The adsorption properties of steel slag-based porous geopolymer for Cu²⁺ removal[J]. Minerals Engineering, 2023, 201: 108225.
[61] CARVALHEIRAS J A, NOVAIS R M, LABRINCHA J A A. Metakaolin/red mud-derived geopolymer monoliths: novel bulk-type sorbents for lead removal from wastewaters[J]. Applied Clay Science, 2023, 232: 106770.
[62] AL-ZBOON K, AL-HARAHSHEH M S, HANI F B. Fly ash-based geopolymer for Pb removal from aqueous solution[J]. Journal of Hazardous Materials, 2011, 188(1/2/3): 414-421.
[63] YU Z F, SONG W F, LI J Y, et al. Improved simultaneous adsorption of Cu(II) and Cr(VI) of organic modified metakaolin-based geopolymer[J]. Arabian Journal of Chemistry, 2020, 13(3): 4811-4823.
[64] 陆艳, 罗中秋, 周新涛, 等. 铜渣铁基类沸石地质聚合物吸附Pb²⁺、Cu²⁺、Zn²⁺性能及机理[J]. 精细化工, 2023, 40(12): 2739-2751.
LU Y, LUO Z Q, ZHOU X T, et al. Properties and mechanism of adsorption of Pb²⁺, Cu²⁺ and Zn²⁺ by copper slag iron-based zeolite geopolymers[J]. Fine Chemicals, 2023, 40 (12): 2739-2751 (in Chinese).
[65] ONUTAI S, KOBAYASHI T, THAVORNITI P, et al. Porous fly ash-based geopolymer composite fiber as an adsorbent for removal of heavy metal ions from wastewater[J]. Materials Letters, 2019, 236: 30-33.
[66] LIU Y, ZHAO S H, QIU X M, et al. Clinoptilolite based zeolite-geopolymer hybrid foams: potential application as low-cost sorbents for heavy metals[J]. Journal of Environmental Management, 2023, 330: 117167.
[67] 屈湃. 粉煤灰基地质聚合物陶粒的制备及吸附性能研究[D]. 太原: 太原理工大学, 2022.
QU P. Preparation and adsorption properties of fly ash-based geopolymer ceramsite[D]. Taiyuan: Taiyuan University of Technology, 2022 (in Chinese).
[68] 宋学锋, 王楠. 原位合成LDHs@地聚物复合材料的矿物组成及其除磷效果[J]. 材料导报, 2024, 38(8): 111-116.
SONG X F, WANG N. Mineral composition and phosphorus removal effect of in-situ synthesis of LDHs@geopolymer composites [J]. Material Reports, 2024, 38(8): 111-116 (in Chinese).
[69] 魏静, 郑小刚, 张国维, 等. 官厅水库、密云水库上游流域地表水氮磷含量现状[J]. 环境工程, 2020, 38(9): 101-105+144.
WEI J, ZHENG X G, ZHANG G W, et al. Current status of nitrogen and phosphorus content in surface water in the upper reaches of Guanting Reservoir and Miyun Reservoir[J]. Environmental Engineering, 2020, 38(9): 101-105+144 (in Chinese).
[70] 丁浩. 自支撑粉煤灰基多孔吸附材料的制备及其脱氮除磷效果[D]. 西安: 西安建筑科技大学, 2021.
DING H. Preparation of self-supporting fly ash-based porous adsorption material and its nitrogen and phosphorus removal effect[D]. Xi'an: Xi'an University of Architecture and Technology, 2021 (in Chinese).
[71] 魏逸明. 自支撑钢渣基多孔吸附材料的制备及其脱氮除磷效果研究[D]. 西安: 西安建筑科技大学, 2021.
WEI Y M. Preparation of self-supporting steel slag-based porous adsorption material and its nitrogen and phosphorus removal effect[D]. Xi'an: Xi'an University of Architecture and Technology, 2021 (in Chinese).
[72] SALAM M A, MOKHTAR M, ALBUKHARI S M, et al. Synthesis of zeolite/geopolymer composite for enhanced sequestration of phosphate (PO^3-₄) and ammonium (NH⁺₄) ions; equilibrium properties and realistic study[J]. Journal of Environmental Management, 2021, 300: 113723.
[73] LUUKKONEN T, VĔŽNÍKOVÁ K, TOLONEN E T, et al. Removal of ammonium from municipal wastewater with powdered and granulated metakaolin geopolymer[J]. Environmental Technology, 2018, 39(4): 414-423.
[74] SANGUANPAK S, WANNAGON A, SAENGAM C, et al. Porous metakaolin-based geopolymer granules for removal of ammonium in aqueous solution and anaerobically pretreated piggery wastewater[J]. Journal of Cleaner Production, 2021, 297: 126643.
[75] MEDRI V, PAPA E, LANDI E, et al. Ammonium removal and recovery from municipal wastewater by ion exchange using a metakaolin K-based geopolymer[J]. Water Research, 2022, 225: 119203.