Study of Ammonium Adsorption Mechanism in Hydrothermalized Pahae Natural Zeolites: Kinetic and Isotherm Adsorption, and Thermodynamics
DOI:
https://doi.org/10.48048/tis.2025.8993Keywords:
Adsorption, Hydrothermal, Ammonia, Zeolite, Adsorption, Hydrothermal, Ammonia, ZeoliteAbstract
This paper focuses on the effectiveness of hydrothermalized natural zeolite from Pahae, North Sumatera to remove ammonium ion and analysis the kinetics models of the zeolite adsorption ability, such as isothermic and kinetics adsorption; thermodynamics as well as desorption-regeneration studies. Our findings have demonstrated that natural zeolite shows good performance in terms of for ammonium removal up to 97 % depending on contact time, zeolite loading, initial ammonium concentration and pH. The adsorption kinetics is best estimated by the pseudo-second-order model, whereas the adsorption isotherm results indicated that Freundlich model provides the best fit for the equilibrium data. Furthermore, with regard to thermodynamic parameters, Gibbs free energy change (ΔG°), −19.52 kJ/mol at 25 °C, −20.45 kJ/mol at 35 °C and −22.91 kJ/mol at 45 °C, is negative due to the spontaneous nature of the adsorption process, whereas the enthalpy change (ΔH°), the energy of 30.96 kJ/mol is positive, suggesting endothermic adsorption process. The entropy change (ΔS°), 0.169 kJ/(mol/K) at 25 °C is also positive, indicating an increase of randomness at the solid-solution interface during adsorption. In addition, the desorption-regeneration studies demonstrated that desorption of ammonium on zeolite is sufficiently high using NaCl solutions.
HIGHLIGHTS
- Natural zeolite and hydrothermal-activated zeolite were used to remove ammonium.
- The hydrothermal-activated zeolite shows good performance for ammonium removal with up to 79 %.
- The performance depends on the contact time, zeolite loading, initial ammonium concentration and pH.
- The adsorption kinetics is best approximated by the pseudo-second-order model.
- Freundlich model provides the best fit for the adsorption isotherm result.
GRAPHICAL ABSTRACT
Downloads
References
S Rakesh, P Ramesh, R Murugaragavan, S Avudainayagam and S Karthikeyan. Characterization and treatment of grey water: A review. International Journal of Chemical Studies 2020; 8(1), 34-40.
K Delhiraja and L Philip. Characterization of segregated greywater from Indian households: Part A-physico-chemical and microbial parameters. Environmental Monitoring and Assessment 2020; 192, 428.
C Noutsopoulos, A Andreadakis, N Kouris, D Charchousi, P Mendrinou, A Galani, I Mantziara and E Koumaki. Greywater characterization and loadings - physicochemical treatment to promote onsite reuse. Journal of Environmental Management 2018; 216, 337-346.
AAS Al-Gheethi, EA Noman, RMSR Mohamed, JD Bala and AH Mohd Kassim. Qualitative characterization of household greywater in developing countries: A comprehensive review. In: R Radin Mohamed, A Al-Gheethi and AM Kassim (Eds). Management of Greywater in Developing Countries. Water Science and Technology Library, Springer, Cham, 2019.
VK Gupta, H Sadegh, M Yari, RS Ghoshekandi, B Maazinejad and M Chahardori. Removal of ammonium ions from wastewater: A short review in development of efficient methods. Global Journal of Environmental Science and Management 2015; 1(2), 149-158.
JC Prajapati, HS Syed and J Chauhan. Removal of ammonia from wastewater by ion exchange technology. Internationnal Journal Innovative Research in Tecnology 2014; 1(9), 6-11.
J Huang, NR Kankanamge, C Chow, DT Welsh, T Li and PR Teasdale. Removing ammonium from water and wastewater using cost-effective adsorbents: A review. Journal of Environmental Sciences 2018; 63, 174-197.
V Kokol, V Vivod, S Arnus, U Cernigoj, b Galicic, KO Vazner, B Neral and A mihelic. Zeolite integrated nanocellulose films for removal of loose anionic reactive dye by adsorption vs. Filtration mode during textile laundering. Fibers and Polymers 2018; 19, 1556-1566.
MV Obuzdina, EA Rush and VE Gozbenko. Mathematical description of the process of adsorption of metal ions by modified zeolites in adsorbers with a fixed adsorbent layer. IOP Conference Series: Earth and Environmental Science 2021; 666, 022047.
SF Sim, SY Ling, L Nyanti, N Gerunsin, YE Wong and LP Kho. Assessment of heavy metals in water, sediment, and fishes of a large tropical hydroelectric dam in sarawak, Malaysia. Journal of Chemistry 2016; 2016, 8923183.
FD Fouchecour, V Larzilliere, T Bouchez and R Moscoviz. Systematic and quantitative analysis of two decades of anodic wastewater treatment in bioelectrochemical reactors. Water Research 2022; 214, 118142.
G Kashi, S Younesi, A Heidary, Z Akbarishahabi, B Kavianpour and RR Kalantary. Carwash wastewater treatment using the chemical processes. Water Science & Technology 2021; 84(1), 16-26.
BH Shabalin, KK Yaroshenko and NB Mitsiuk. Composition of chemical elements and ion exchange complex of acid- and alkali-modified natural zeolites from the sokyrnytsky deposit. Mineralogical Journal 2023; 45(2), 116-123.
A Chaudhary and A Singh. Zeolites: The aluminosilicate framework with promising scenarios. Recent Advances in Petrochemical Science 2017; 2(5), 555598.
N Asano, S Asahina, J Lu, J Xu, Y Shen, Z Qin and S Mintova. Advanced scanning electron microscopy techniques for structural characterization of zeolites. Inorganic Chemistry Frontiers 2022; 9(16), 4225-4231.
PB Ho, C Foo, W Lin, SCE Tsang and PD Nellist. Spatial Differentiation of aluminium siting by the single-atom adsorption sites in zeolite by electron microscopy Microscopy and Microanalysis 2020; 28, 2156-2158.
J Canellas, A Soares and B Jefferson. Removing ammonia from wastewater using natural and synthetic zeolites: A batch experiment. ChemRxiv, Washington DC, 2019.
D Munkhjargal, J Oyuntsetseg, R Ulambayar and J Ganbaatar. The investigation of the effect of relevant parameters of Mongolian natural zeolites for ammonium ion removal from aqueous solution. Zastita Materijala 2016; 57(4), 571-576.
J Canellas, A Soares and B Jefferson. A comparison of natural and synthetic zeolites in continuous column-based experiments for removing ammonia from wastewater. ChemRxiv, Washington DC, 2019.
K Ham, BS Kim and Y Choi. Enhanced ammonium removal efficiency by ion exchange process of synthetic zeolite after Na+ and heat pretreatment. Water Science and Technology 2018; 78(6), 1417-1425.
Q Zhang, B Lin, J Hong and CT Chang. Removal of ammonium and heavy metals by cost-effective zeolite synthesized from waste quartz sand and calcium fluoride sludge. Water Science & Technology 2017; 75(3), 587-597.
S Guida, C Potter, B Jefferson and A Soares. Preparation and evaluation of zeolites for ammonium removal from municipal wastewater through ion exchange process. Scientific Reports 2020; 10, 12426.
DTN Wijesinghe, KB Dassanayake, SG Sommer, GY Jayasinghe, PJ Scales and D Chen. Ammonium removal from high-strength aqueous solutions by Australian zeolite. Journal of Environmental Science and Health, Part A Toxic/Hazardous Substances and Environmental Engineering 2016; 51, 614-625.
S Mosanefi, N Alavi, A Eslami, M Saadani and A Ghavami. Ammonium removal from landfill fresh leachate using zeolite as adsorbent. Journal of Material Cycles and Waste Management 2021; 23, 1383-1393.
PV Viotti, WM Moreira, H Straioto, R Bergamasco, MHNO Scaliante and MF Vieira. The “chimie douce” process towards the modification of natural zeolites for removing drugs and pesticides from water. Journal of Chemical Technology & Biotechnology 2022; 97(8), 2149-2162.
Y Watanabe, H Yamada, J Tanaka and Y Moriyoshi. Hydrothermal modification of natural zeolites to improve uptake of ammonium ions. Journal of Chemical Technology & Biotechnology 2005; 80(4), 376-380.
G Feng, P Cheng, W Yan, M Boronat, X Li, J Su, J Wang, Y Li, A Corma, R Xu and J Yu. Accelerated crystallization of zeolites via hydroxyl free radicals. Science 2016; 351(6278), 1188-1191.
MJ Stephenson, MP Attfield, SM Holmes and RAW Dryfe. Electrochemically controlled ion exchange: Proton ion exchange with sodium zeolite X and A. Journal of Solid State Electrochemistry 2015; 19, 1985-1992.
J Qiu, D Liu, S Jiang, G Chen, Y Wang, G Li, G Yao, P Wu, X Zhu, G Wang and X Lyu. Effect of crystal chemistry properties on the distribution characteristics of H2O and Na+ in Na-montmorillonite interlayer space: Molecular dynamics simulation study. Minerals 2020; 10(2), 162.
E Sundhararasu, H Runtti, T Kangas, J Pesonen, U Lassi and S Tuomikoski. Column adsorption studies for the removal of ammonium using Na-Zeolite-Based geopolymers. Resources 2022; 11(12), 119.
N Imchuen, Y Lubphoo, JM Chyan, S Padungthon and CH Liao. Using cation exchange resin for ammonium removal as part of sequential process for nitrate reduction by nanoiron. Sustainable Environment Research 2016; 26(4), 156-160.
C Li, Y Yu, Q Zhang, H Zhong and S Wang. Removal of ammonium from aqueous solutions using zeolite synthesized from electrolytic manganese residue. International Journal of Chemical Engineering 2020; 2020(1), 8818455.
A Kotoulas, D Agathou, IE Triantaphyllidou, TI Tatoulis, CS Akratos, AG tekerlekopoulou and DV Vayenas. Zeolite as a potential medium for ammonium recovery and second cheese whey treatment. Water 2019; 11(1), 136.
H Chen, Y Lin, B Chen, I Yoshiyuki, SY Liou and R Huang. A further investigation of NH4+ removal mechanisms by using natural and synthetic zeolites in different concentrations and temperatures. Minerals 2018; 8(11), 499.
C Zhou, Y An, W Zhang, D Yang, J Tang, J Ye and Z Zhou. Inhibitory effects of Ca2+ on ammonium exchange by zeolite in the long-term exchange and NaClO-NaCl regeneration process. Chemosphere 2021; 263, 128216.
F Mazloomi and M Jalali. Ammonium removal from aqueous solutions by natural Iranian zeolite in the presence of organic acids, cations and anions. Journal of Environmental Chemical Engineering 2016; 4(2), 1664-1673.
R Malekian, J Abedi-Koupai, SS Eslamian, SF Mousavi, KC Abbaspour and M Afyuni. Ion-exchange process for ammonium removal and release using natural Iranian zeolite. Applied Clay Science 2011; 51(3), 323-329.
C Hackett and KD Hammond. Simulating the effect of the quadrupole moment on the adsorption of nitrogen in siliceous zeolites. Microporous and Mesoporous Materials 2018; 263, 231-235.
V Sabadash, J Gumnitsky and S Omelyanova. Simulation of ion exchange interaction kinetics in the clinoptylolite - ammonium ion system. Environmental Problems 2021; 6(4), 233-237.
VJ Inglezakis and MM Fyrillas. Experimental study of zeolitic diffusion by use of a concentration-dependent surface diffusion model. Heliyon 2019; 5(7), e02143.
S Essid, F Ayari, R Bulanek, J Vaculik, E Asedegbega-Nieto, M Mhamdi, G Delahay and A Ghorbel. Solid–state ion exchange of CoCl2·6H2O into NH4+–Beta zeolite: Pathway analysis. Microporous and Mesoporous Materials 2018; 264, 218-229.
AJ O’Malley, M Sarwar, J Armstrong, CRA Catlow, IP Silverwood, APE York and I Hitchcock. Comparing ammonia diffusion in NH3-SCR zeolite catalysts: A quasielastic neutron scattering and molecular dynamics simulation study. Physical Chemistry Chemical Physics 2018; 20(17), 11976-11986.
Susilawati, YA Sihombing, SU Rahayu, L Waldiansyah and YYB Sembiring. The effectiveness of pahae natural zeolite-cocoa shell activated charcoal nanofilter as a water adsorber in bioethanol purification. ACS Omega 2022; 7(43), 38417-38425.
Downloads
Published
Issue
Section
License
Copyright (c) 2024 Walailak University
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
