Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite
ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its prop...
- Autores:
-
Dotto, Guilherme Luiz
Pinto, Diana
Silva Oliveira, Luis Felipe
Grimm, Alejandro
Rizwan Khan, Mohammad
Ahmad, Naushad
de Brum, Irineu A.S.
Mikkola, Jyri-Pekka
Simoes dos Reis, Glaydson
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2024
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13308
- Acceso en línea:
- https://hdl.handle.net/11323/13308
https://repositorio.cuc.edu.co/
- Palabra clave:
- Microporous zeolite
Adsorption of rare earth elements
Ion-exchange mechanism
- Rights
- openAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
id |
RCUC2_cef92c2d2498689468b99449aed8a38f |
---|---|
oai_identifier_str |
oai:repositorio.cuc.edu.co:11323/13308 |
network_acronym_str |
RCUC2 |
network_name_str |
REDICUC - Repositorio CUC |
repository_id_str |
|
dc.title.eng.fl_str_mv |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
title |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
spellingShingle |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite Microporous zeolite Adsorption of rare earth elements Ion-exchange mechanism |
title_short |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
title_full |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
title_fullStr |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
title_full_unstemmed |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
title_sort |
Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite |
dc.creator.fl_str_mv |
Dotto, Guilherme Luiz Pinto, Diana Silva Oliveira, Luis Felipe Grimm, Alejandro Rizwan Khan, Mohammad Ahmad, Naushad de Brum, Irineu A.S. Mikkola, Jyri-Pekka Simoes dos Reis, Glaydson |
dc.contributor.author.none.fl_str_mv |
Dotto, Guilherme Luiz Pinto, Diana Silva Oliveira, Luis Felipe Grimm, Alejandro Rizwan Khan, Mohammad Ahmad, Naushad de Brum, Irineu A.S. Mikkola, Jyri-Pekka Simoes dos Reis, Glaydson |
dc.subject.proposal.eng.fl_str_mv |
Microporous zeolite Adsorption of rare earth elements Ion-exchange mechanism |
topic |
Microporous zeolite Adsorption of rare earth elements Ion-exchange mechanism |
description |
ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the as-prepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce3+, La3+, and Nd3+ were 99.42 mg g−1, 96.43 mg g−1, 118.10 mg g−1, respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce3+, La3+, and Nd3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples. |
publishDate |
2024 |
dc.date.accessioned.none.fl_str_mv |
2024-09-12T14:16:01Z |
dc.date.available.none.fl_str_mv |
2024-09-12T14:16:01Z |
dc.date.issued.none.fl_str_mv |
2024-10-05 |
dc.type.spa.fl_str_mv |
Artículo de revista |
dc.type.coar.spa.fl_str_mv |
http://purl.org/coar/resource_type/c_2df8fbb1 |
dc.type.content.spa.fl_str_mv |
Text |
dc.type.driver.spa.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.redcol.spa.fl_str_mv |
http://purl.org/redcol/resource_type/ART |
dc.type.version.spa.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.coarversion.spa.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
format |
http://purl.org/coar/resource_type/c_2df8fbb1 |
status_str |
publishedVersion |
dc.identifier.citation.spa.fl_str_mv |
Guilherme Luiz Dotto, Diana Pinto, Luis Felipe Oliveira Silva, Alejandro Grimm, Mohammad Rizwan Khan, Naushad Ahmad, Irineu A.S. de Brum, Jyri-Pekka Mikkola, Glaydson S. dos Reis, Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Volume 698, 2024, 134549, ISSN 0927-7757, https://doi.org/10.1016/j.colsurfa.2024.134549. |
dc.identifier.issn.spa.fl_str_mv |
0927-7757 |
dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/13308 |
dc.identifier.eissn.spa.fl_str_mv |
1873-4359 |
dc.identifier.instname.spa.fl_str_mv |
Corporación Universidad de la Costa |
dc.identifier.reponame.spa.fl_str_mv |
REDICUC - Repositorio CUC |
dc.identifier.repourl.spa.fl_str_mv |
https://repositorio.cuc.edu.co/ |
identifier_str_mv |
Guilherme Luiz Dotto, Diana Pinto, Luis Felipe Oliveira Silva, Alejandro Grimm, Mohammad Rizwan Khan, Naushad Ahmad, Irineu A.S. de Brum, Jyri-Pekka Mikkola, Glaydson S. dos Reis, Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Volume 698, 2024, 134549, ISSN 0927-7757, https://doi.org/10.1016/j.colsurfa.2024.134549. 0927-7757 1873-4359 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
url |
https://hdl.handle.net/11323/13308 https://repositorio.cuc.edu.co/ |
dc.language.iso.spa.fl_str_mv |
eng |
language |
eng |
dc.relation.ispartofjournal.spa.fl_str_mv |
Colloids and Surfaces A: Physicochemical and Engineering Aspects |
dc.relation.references.spa.fl_str_mv |
[1] V. Fernandez, Rare-earth elements market: a historical and financial perspective, Resour. Policy 53 (2017) 26–45, https://doi.org/10.1016/j. resourpol.2017.05.010. [2] M.A. de Boer, K. Lammertsma, Scarcity of rare earth elements, ChemSusChem 6 (2013) 2045–2055. [3] T.Z. Humsa, R.K. Srivastava, Impact of rare earth mining and processing on soil and water environment at Chavara, Kollam, Kerala: a case study, Procedia Earth Planet. Sci. 11 (2015) 566–581, https://doi.org/10.1016/j.proeps.2015.06.059. [4] J. Li, K. Peng, P. Wang, N. Zhang, K. Feng, D. Guan, J. Meng, W. Wei, Q. Yang, Critical Rare-Earth Elements Mismatch Global WindPower Ambitions, One Earth 3 (2020) 116–125. [5] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, analysis, recycling, and environmental impact, Geosci. Front. 10 (2019) 1285–1303. [6] J. Kulczycka, Z. Kowalski, M. Smol, H. Wirth, Evaluation of the recovery of rare earth elements (REE) from phosphogypsum waste case study of the WIZOW chemical plant (Poland), J. Clean. Prod. 113 (2016) 345–354. [7] V.N. Rychkov, E.V. Kirillov, S.V. Kirillov, V.S. Semenishchev, G.M. Bunkov, M. S. Botalov, D.V. Smyshlyaev, A.S. Malyshev, Recovery of rare earth elements from phosphogypsum, J. Clean. Prod. 196 (2018) 674–681. [8] R.K. Jyothi, T. Thenepalli, J.W. Ahn, P.K. Parhi, K.W. Chung, J.Y. Lee, Review of rare earth elements recovery from secondary resources for clean energy technologies: grand opportunities to create wealth from waste, J. Clean. Prod. 267 (2020) 122048, https://doi.org/10.1016/j.jclepro.2020.122048. [9] Abhilash, P. Meshram, S. Sarkar, T. Venugopalan, Exploring blast furnace slag as a secondary resource for extraction of rare earth elements, Miner. Metall. Process. 34 (2017) 178–182, https://doi.org/10.19150/mmp.7857. [10] S. Panda, R.B. Costa, S.S. Shah, S. Mishra, D. Bevilaqua, A. Akcil, Biotechnological trends and market impact on the recovery of rare earth elements from bauxite residue (red mud)–a review, Resour., Conserv. Recycl. 171 (2021) 105645, https:// doi.org/10.1016/j.resconrec.2021.105645. [11] S. Peelman, Z.H. Sun, J. Sietsma, Y. Yang, Leaching of rare earth elements: review of past and present technologies, Rare Earths Ind. (2016) 319–334, https://doi. org/10.1016/B978-0-12-802328-0.00021-8. [12] Z. Hammache, S. Bensaadi, Y. Berbar, N. Audebrand, A. Szymczyk, M. Amara, Recovery of rare earth elements from electronic waste by diffusion dialysis, Sep. Purif. Technol. 254 (2021) 117641, https://doi.org/10.1016/j. seppur.2020.117641. [13] S.F. Lütke, M.L.S. Oliveira, S.R. Waechter, L.F.O. Silva, T.R.S. Cadaval Jr., F. A. Duarte, G.L. Dotto, Leaching of rare earth elements from phosphogypsum, Chemosphere 301 (2022) 134661. [14] R.F. Pinheiro, A. Grimm, M.L.S. Oliveira, J. Vieillard, L.F.O. Silva, I.A.S. De Brum, E.C. Lima, M. Naushad, L. Sellaoui, G.L. Dotto, G.S. dos Reis, Adsorptive behavior of the rare earth elements Ce and La on a soybean pod derived activated carbon: application in synthetic solutions, real leachate and mechanistic insights by statistical physics modeling, Chem. Eng. J. 471 (2023) 144484. [15] G.L. Dotto, J. Vieillard, D. Pinto, S.F. Lütke, L.F.O. Silva, G.S. dos Reis, E.C. Lima, D.S.P. Franco, Selective adsorption of gadolinium from real leachate using a natural bentonite clay, J. Environ. Chem. Eng. 11 (2023) 109748. [16] G.S. dos Reis, V. Srivastava, M.F.A. Taleb, et al., Adsorption of rare earth elements on a magnetic geopolymer derived from rice husk: studies in batch, column, and application in real phosphogypsum leachate sample, Environ. Sci. Pollut. Res. (2024), https://doi.org/10.1007/s11356-024-31925-x. [17] Walawalkar, K.Nichol Connie, Gisele Azimi, Process investigation of the acid leaching of rare earth elements from phosphogypsum using HCl, HNO3, and H2SO4, Hydrometallurgy 166 (2016) 195–204, https://doi.org/10.1016/j. hydromet.2016.06.008. [18] A. Khaleque, M.M. Alam, M. Hoque, S. Mondal, J.B. Haider, B. Xu, M.A.H. Johir, A. K. Karmakar, J.L. Zhou, M.B. Ahmed, M.A. Moni, Zeolite synthesis from low-cost materials and environmental applications: a review, Environ. Adv. 2 (2020) 100019. [19] E. Perez-Botella, S. Valencia, F. Rey, Zeolites in adsorption processes: state of the art and future prospects, Chem. Rev. 122 (2022) 17647–17695. [20] D. Stamires, Y. L. lam, J. Gorne, R. Wasserman, J.C.M. Ferreira, J. da Silva, Nucleating gel, process for its preparation, and its use in the synthesis of MFI-type zeolite. Patent Cooperation Treaty (PCT), no. WO/2006/087337, 2006. Available from: < https://patentscope.wipo.int/search/en/detail.jsf? docId=WO2006087337> [21] G.S. dos Reis, C.E. Schnorr, G.L. Dotto, J. Vieillar, M.S. Netto, L.F.O. Silva, I.A.S. De Brum, M. Thyrel, E.C. Lima, U. Lassi, Wood waste–based functionalized natural hydrochar for the efective removal of Ce(III) ions from aqueous solution, Environ. Sci. Pollut. Res. 30 (2023) 64067–64077. [22] G.S. dos Reis, D. Pinto, E.C. Lima, S. Knani, A. Grimm, L.F.O. Silva, T.R. S. Cadaval Jr, G.L. Dotto, Lanthanum uptake from water using chitosan with different configurations, React. Funct. Polym. 180 (2022) 105395. [23] H. Jedli, M.M. Almoneef, M. Mbarek, A. Jbara, K. Slimi, Adsorption of CO2 onto zeolite ZSM-5: kinetic, equilibrium and thermodynamic studies, Fuel 321 (2022) 124097. [24] W. Panpa, S. Jinawath, Synthesis of ZSM-5 zeolite and silicalite from rice husk ash, Appl. Catal. B 90 (2009) 389–394. [25] S. Bosnar, V. Rac, D. Stosic, A. Travert, G. Postole, A. Auroux, S. Skapin, L. DamjanoviVasili, J. Bronic, X. Du, S. Markovic, V. Pavlovi, V. Rakic, Overcoming phase separation in dual templating: a homogeneous hierarchical ZSM-5 zeolite with flower-like morphology, synthesis and in-depth acidity study, Microporous Mesoporous Mater. 329 (2022) 111534. [26] L. Chu, G. Liu, Q. Xiao, Direct construction of hierarchical ZSM–5 microspheres aided by 3–glycidoxypropyltrimethoxysilane, Mater. Res. Bull. 60 (2014) 746–751. [27] P.S. Kumar, L. Korving, K.J. Keesman, Mark C.M. van Loosdrecht, G.-J. Witkamp, Effect of pore size distribution and particle size of porous metal oxides on phosphate adsorption capacity and kinetics, Chem. Eng. J. 358 (2019) 160–169. [28] Y. Wang, T. Du, X. Fang, H. Jia, Z. Qiu, Y. Song, Synthesis of CO2 -adsorbing ZSM-5 zeolite from rice husk ash via the colloidal pretreatment method, Mater. Chem. Phys. 232 (2019) 284–293. [29] J. Schnee, M. Quezada, O. Norosoa, F. Azzolina-Jury, ZSM-5 surface modification by plasma for catalytic activity improvement in the gas phase methanol-todimethylether reaction, Catal. Today 337 (2019) 195–200. [30] X. Feng, O. Onel, M. Council-Troche, A. Noble, R.H. Yoon, J.R. Morris, A study of rare earth ion-adsorption clays: the speciation of rare earth elements on kaolinite at basic pH, Appl. Clay Sci. 201 (2021) 105920. [31] G.S. dos Reis, J. Thivet, E. Laisn’e, V. Srivastava, A. Grimm, E.C. Lima, D. Bergna, T. Hu, M. Naushad, U. Lassi, Synthesis of novel mesoporous selenium-doped biochar with high-performance sodium diclofenac and reactive orange 16 dye removals, Chem. Eng. Sci. (2023) 119129, https://doi.org/10.1016/j. ces.2023.119129. [32] G.S. dos Reis, D. Bergna, A. Grimm, E.C. Lima, H. Hu, M. Naushad, U. Lassi, Preparation of highly porous nitrogen-doped biochar derived from birch tree wastes with superior dye removal performance, Colloids Surf. A 669 (2023) 131493, https://doi.org/10.1016/j.colsurfa.2023.131493. [33] A. Grimm, G.S. dos Reis, V.M. Dinh, S.H. Larsson, J.-P. Mikkola, E.C. Lima, S. Xiong, Hardwood spent mushroom substrate–based activated biochar as a sustainable bioresource for removal of emerging pollutants from wastewater, Biomass-.-. Convers. Biorefin. 14 (2022) 2293–2309, https://doi.org/10.1007/ s13399-022-02618-7. [34] R.C. Ferreira, O.M.C. Junior, K.Q. Carvalho, P.A. Arroyo, M.A.S.D. Barros, Efect of solution pH on the removal of paracetamol by activated carbon of dende coconut mesocarp, Chem. Biochem Eng. Q 29 (2015) 47–53. [35] A.R. Cestari, E.F.S. Vieira, G.S. Vieira, L.E. Almeida, The removal of anionic dyes from aqueous solutions in the presence of anionic surfactant using aminopropyl silica-a kinetic study, J. Hazard Mater. 138 (2006) 133–141. [36] B. Ji, W. Zhang, Adsorption of cerium (III) by zeolites synthesized from kaolinite after rare earth elements (REEs) recovery, Chemosphere 303 (2022) 134941. [37] Y. Cheng, T. Zhang, L. Zhang, Z. Ke, L. Kovarik, H. Dong, Resource recovery: Adsorption and biomineralization of cerium by Bacillus licheniformis, J. Hazard. Mat. 426 (2022) 127844. [38] Y.A. Akbas, S. Yusan, S. Sert, S. Aytas, Sorption of Ce(III) on magnetic/olive pomace nanocomposite: isotherm, kinetic and thermodynamic studies, Environ. Sci. Pollut. Res. 28 (2021) 56782–56794. [39] H. Yuhua, L. Xiaogang, S. Minxin, Q. Yuanyuan, L. Xiancai, Study on the adsorption of lanthanum ion imprinted on SBA-15/Y, J. Indian Chem. Soc. 99 (2022) 100425. [40] J. Gaete, L. Molina, F. Valenzuela, C. Basualto, Recovery of lanthanum, praseodymium and samarium by adsorption using magnetic nanoparticles functionalized with a phosphonic group, Hydrometallurgy 203 (2021) 105698. [41] E. Kusrinia, W. Wicaksono, C. Gunawan, N.Z.A. Daud, A. Usman, Kinetics, mechanism, and thermodynamics of lanthanum adsorption on pectin extracted from durian rind, J. Environ. Chem. Eng. 6 (2018) 6580–6588. [42] H. Javadian, M. Ruiz, M. Taghvai, A.M. Sastre, Novel magnetic nanocomposite of calcium alginate carrying poly (pyrimidine-thiophene-amide) as a novel green synthesized polyamide for adsorption study of neodymium, terbium, and dysprosium rare-earth ions, Colloids Surf. A 603 (2020) 125252. [43] M.M. Yusoff, N.R.N. Mostapa, M.S. Sarkar, T.K. Biswas, M.L. Rahman, S.E. Arshad, M.S. Sarjadi, A.D. Kulkarni, Synthesis of ion imprinted polymers for selective recognition and separation of rare earth metals, J. Rare Earth 35 (2017) 177–186. [44] Radwa M. Ashour, Ramy El-sayed, Ahmed F. Abdel-Magied, Ahmed A. Abdelkhalek, M.M. Ali, Kerstin Forsberg, A. Uheida, Mamoun Muhammed, Joydeep Dutta, Selective separation of rare earth ions from aqueous solution using functionalized magnetite nanoparticles: kinetic and thermodynamic studies, Chem. Eng. J. 327 (2017) 286–296. [45] G.S. dos Reis, G.L. Dotto, J. Vieillard, M.L.S. Oliveira, S.F. Lütke, L.F.O. Silva, E. C. Lima, N.P.G. Salau, U. Lassi, Uptake the rare earth elements Nd, Ce, and La by a commercial diatomite: kinetics, equilibrium, thermodynamic and adsorption mechanism, J. Mol. Liq. 389 (2023) 122862, https://doi.org/10.1016/j. molliq.2023.122862. [46] M. Medykowska, M. Wisniewska, K. Szewczuk-Karpisz, R. Panek, Interaction mechanism of heavy metal ions with the nanostructured zeolites surface – adsorption, electrokinetic and XPS studies, J. Mol. Liq. 357 (2022) 119144. [47] L.H. Dong, L.A. Hou, Z.S. Wang, P. Gu, G.Y. Chen, R.F. Jiang, A new function of spent activated carbon in BAC process: removing heavy metals by ion exchange mechanism, J. Hazard. Mater. 359 (2018) 76–84. [48] G.S. dos Reis, A. Grimm, D.A. Fungaro, T. Hu, I.A.S. de Brum, E.C. Lima, M. Naushad, G.L. Dotto, U. Lassi, Synthesis of sustainable mesoporous sulfur-doped biobased carbon with superior performance sodium diclofenac removal: Kinetic, equilibrium, thermodynamic and mechanism, Environ. Res. 251 (2024) 118595. [49] G.S. dos Reis, G.L. Dotto, J. Vieillard, M.L.S. Oliveira, S.F. Lutke, A. Grimm, L.F. O. Silva, E.C. Lima, M. Naushad, U. Lassi, Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate, J. Alloy. Compd. 960 (2023) 170530. |
dc.relation.citationendpage.spa.fl_str_mv |
10 |
dc.relation.citationstartpage.spa.fl_str_mv |
1 |
dc.relation.citationvolume.spa.fl_str_mv |
698 |
dc.rights.license.spa.fl_str_mv |
Atribución 4.0 Internacional (CC BY 4.0) |
dc.rights.uri.spa.fl_str_mv |
https://creativecommons.org/licenses/by/4.0/ |
dc.rights.accessrights.spa.fl_str_mv |
info:eu-repo/semantics/openAccess |
dc.rights.coar.spa.fl_str_mv |
http://purl.org/coar/access_right/c_abf2 |
rights_invalid_str_mv |
Atribución 4.0 Internacional (CC BY 4.0) https://creativecommons.org/licenses/by/4.0/ http://purl.org/coar/access_right/c_abf2 |
eu_rights_str_mv |
openAccess |
dc.format.extent.spa.fl_str_mv |
10 páginas |
dc.format.mimetype.spa.fl_str_mv |
application/pdf |
dc.publisher.spa.fl_str_mv |
Elsevier B.V. |
dc.publisher.place.spa.fl_str_mv |
Netherlands |
dc.source.spa.fl_str_mv |
https://www.sciencedirect.com/science/article/pii/S0927775724014134?pes=vor |
institution |
Corporación Universidad de la Costa |
bitstream.url.fl_str_mv |
https://repositorio.cuc.edu.co/bitstreams/7883df31-7d4a-4640-b62a-37cbe9627477/download https://repositorio.cuc.edu.co/bitstreams/d515d0ee-d1d0-4779-bf39-2912caacbc50/download https://repositorio.cuc.edu.co/bitstreams/d4a191a5-993b-4cfa-b31e-aac1b27ce8ae/download https://repositorio.cuc.edu.co/bitstreams/3fd701c3-293f-4a03-b842-e593c96cb64b/download |
bitstream.checksum.fl_str_mv |
24e62396f0360ffa3c13d510f0779167 2f9959eaf5b71fae44bbf9ec84150c7a e61a1c909766173f3d9d3b0afa5d989c eddab24ca1731c3cc0250d81a98e2613 |
bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 |
repository.name.fl_str_mv |
Repositorio de la Universidad de la Costa CUC |
repository.mail.fl_str_mv |
repdigital@cuc.edu.co |
_version_ |
1811760837280399360 |
spelling |
Atribución 4.0 Internacional (CC BY 4.0)© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).https://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Dotto, Guilherme LuizPinto, DianaSilva Oliveira, Luis FelipeGrimm, AlejandroRizwan Khan, MohammadAhmad, Naushadde Brum, Irineu A.S.Mikkola, Jyri-PekkaSimoes dos Reis, Glaydson2024-09-12T14:16:01Z2024-09-12T14:16:01Z2024-10-05Guilherme Luiz Dotto, Diana Pinto, Luis Felipe Oliveira Silva, Alejandro Grimm, Mohammad Rizwan Khan, Naushad Ahmad, Irineu A.S. de Brum, Jyri-Pekka Mikkola, Glaydson S. dos Reis, Adsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeolite, Colloids and Surfaces A: Physicochemical and Engineering Aspects, Volume 698, 2024, 134549, ISSN 0927-7757, https://doi.org/10.1016/j.colsurfa.2024.134549.0927-7757https://hdl.handle.net/11323/133081873-4359Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/ZSM-5 zeolite is a multifunctional material highly efficient for adsorbing ions. Our ZSM-5 was synthesized by employing a nucleating gel as a structure-directing agent, followed by homogenization and hydrothermal treatment. The as-prepared ZSM-5 was physicochemically characterized to assess its properties. Next, the as-prepared zeolite was employed as an adsorbent to remove rare earth elements, REEs from synthetic solutions and real phosphogypsum leachate under batch mode operation. As expected, the ZSM-5 adsorbent was discovered to be highly microporous with abundant surface functionalities, which could positively impact REE adsorption. The adsorption data indicated a high affinity between ZSM-5 and all three REEs with rapid kinetics and high adsorption capacities. The modeling study suggested that the adsorption kinetic data were well fitted by Avrami-fractional order, and Liu described the equilibrium data. The maximum adsorption capacity for Ce3+, La3+, and Nd3+ were 99.42 mg g−1, 96.43 mg g−1, 118.10 mg g−1, respectively. Further, the thermodynamic analysis revealed that the interaction between ZSM-5 and Ce3+, La3+, and Nd3+ was favorable, spontaneous, and endothermic. The efficiency of ZSM-5 adsorbent was also studied in recovering several REEs from leachate of phosphogypsum wastes, and the data results proved its potency to do so. The findings reported in this work support the idea that ZSM-5 can be successfully used as an adsorbent to recover REEs from synthetic and real samples.10 páginasapplication/pdfengElsevier B.V.Netherlandshttps://www.sciencedirect.com/science/article/pii/S0927775724014134?pes=vorAdsorption of rare earth elements (Ce3+, La3+, and Nd3+) and recovery from phosphogypsum leachate using a novel ZSM-5 zeoliteArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Colloids and Surfaces A: Physicochemical and Engineering Aspects[1] V. Fernandez, Rare-earth elements market: a historical and financial perspective, Resour. Policy 53 (2017) 26–45, https://doi.org/10.1016/j. resourpol.2017.05.010.[2] M.A. de Boer, K. Lammertsma, Scarcity of rare earth elements, ChemSusChem 6 (2013) 2045–2055.[3] T.Z. Humsa, R.K. Srivastava, Impact of rare earth mining and processing on soil and water environment at Chavara, Kollam, Kerala: a case study, Procedia Earth Planet. Sci. 11 (2015) 566–581, https://doi.org/10.1016/j.proeps.2015.06.059.[4] J. Li, K. Peng, P. Wang, N. Zhang, K. Feng, D. Guan, J. Meng, W. Wei, Q. Yang, Critical Rare-Earth Elements Mismatch Global WindPower Ambitions, One Earth 3 (2020) 116–125.[5] V. Balaram, Rare earth elements: a review of applications, occurrence, exploration, analysis, recycling, and environmental impact, Geosci. Front. 10 (2019) 1285–1303.[6] J. Kulczycka, Z. Kowalski, M. Smol, H. Wirth, Evaluation of the recovery of rare earth elements (REE) from phosphogypsum waste case study of the WIZOW chemical plant (Poland), J. Clean. Prod. 113 (2016) 345–354.[7] V.N. Rychkov, E.V. Kirillov, S.V. Kirillov, V.S. Semenishchev, G.M. Bunkov, M. S. Botalov, D.V. Smyshlyaev, A.S. Malyshev, Recovery of rare earth elements from phosphogypsum, J. Clean. Prod. 196 (2018) 674–681.[8] R.K. Jyothi, T. Thenepalli, J.W. Ahn, P.K. Parhi, K.W. Chung, J.Y. Lee, Review of rare earth elements recovery from secondary resources for clean energy technologies: grand opportunities to create wealth from waste, J. Clean. Prod. 267 (2020) 122048, https://doi.org/10.1016/j.jclepro.2020.122048.[9] Abhilash, P. Meshram, S. Sarkar, T. Venugopalan, Exploring blast furnace slag as a secondary resource for extraction of rare earth elements, Miner. Metall. Process. 34 (2017) 178–182, https://doi.org/10.19150/mmp.7857.[10] S. Panda, R.B. Costa, S.S. Shah, S. Mishra, D. Bevilaqua, A. Akcil, Biotechnological trends and market impact on the recovery of rare earth elements from bauxite residue (red mud)–a review, Resour., Conserv. Recycl. 171 (2021) 105645, https:// doi.org/10.1016/j.resconrec.2021.105645.[11] S. Peelman, Z.H. Sun, J. Sietsma, Y. Yang, Leaching of rare earth elements: review of past and present technologies, Rare Earths Ind. (2016) 319–334, https://doi. org/10.1016/B978-0-12-802328-0.00021-8.[12] Z. Hammache, S. Bensaadi, Y. Berbar, N. Audebrand, A. Szymczyk, M. Amara, Recovery of rare earth elements from electronic waste by diffusion dialysis, Sep. Purif. Technol. 254 (2021) 117641, https://doi.org/10.1016/j. seppur.2020.117641.[13] S.F. Lütke, M.L.S. Oliveira, S.R. Waechter, L.F.O. Silva, T.R.S. Cadaval Jr., F. A. Duarte, G.L. Dotto, Leaching of rare earth elements from phosphogypsum, Chemosphere 301 (2022) 134661.[14] R.F. Pinheiro, A. Grimm, M.L.S. Oliveira, J. Vieillard, L.F.O. Silva, I.A.S. De Brum, E.C. Lima, M. Naushad, L. Sellaoui, G.L. Dotto, G.S. dos Reis, Adsorptive behavior of the rare earth elements Ce and La on a soybean pod derived activated carbon: application in synthetic solutions, real leachate and mechanistic insights by statistical physics modeling, Chem. Eng. J. 471 (2023) 144484.[15] G.L. Dotto, J. Vieillard, D. Pinto, S.F. Lütke, L.F.O. Silva, G.S. dos Reis, E.C. Lima, D.S.P. Franco, Selective adsorption of gadolinium from real leachate using a natural bentonite clay, J. Environ. Chem. Eng. 11 (2023) 109748.[16] G.S. dos Reis, V. Srivastava, M.F.A. Taleb, et al., Adsorption of rare earth elements on a magnetic geopolymer derived from rice husk: studies in batch, column, and application in real phosphogypsum leachate sample, Environ. Sci. Pollut. Res. (2024), https://doi.org/10.1007/s11356-024-31925-x.[17] Walawalkar, K.Nichol Connie, Gisele Azimi, Process investigation of the acid leaching of rare earth elements from phosphogypsum using HCl, HNO3, and H2SO4, Hydrometallurgy 166 (2016) 195–204, https://doi.org/10.1016/j. hydromet.2016.06.008.[18] A. Khaleque, M.M. Alam, M. Hoque, S. Mondal, J.B. Haider, B. Xu, M.A.H. Johir, A. K. Karmakar, J.L. Zhou, M.B. Ahmed, M.A. Moni, Zeolite synthesis from low-cost materials and environmental applications: a review, Environ. Adv. 2 (2020) 100019.[19] E. Perez-Botella, S. Valencia, F. Rey, Zeolites in adsorption processes: state of the art and future prospects, Chem. Rev. 122 (2022) 17647–17695.[20] D. Stamires, Y. L. lam, J. Gorne, R. Wasserman, J.C.M. Ferreira, J. da Silva, Nucleating gel, process for its preparation, and its use in the synthesis of MFI-type zeolite. Patent Cooperation Treaty (PCT), no. WO/2006/087337, 2006. Available from: < https://patentscope.wipo.int/search/en/detail.jsf? docId=WO2006087337>[21] G.S. dos Reis, C.E. Schnorr, G.L. Dotto, J. Vieillar, M.S. Netto, L.F.O. Silva, I.A.S. De Brum, M. Thyrel, E.C. Lima, U. Lassi, Wood waste–based functionalized natural hydrochar for the efective removal of Ce(III) ions from aqueous solution, Environ. Sci. Pollut. Res. 30 (2023) 64067–64077.[22] G.S. dos Reis, D. Pinto, E.C. Lima, S. Knani, A. Grimm, L.F.O. Silva, T.R. S. Cadaval Jr, G.L. Dotto, Lanthanum uptake from water using chitosan with different configurations, React. Funct. Polym. 180 (2022) 105395.[23] H. Jedli, M.M. Almoneef, M. Mbarek, A. Jbara, K. Slimi, Adsorption of CO2 onto zeolite ZSM-5: kinetic, equilibrium and thermodynamic studies, Fuel 321 (2022) 124097.[24] W. Panpa, S. Jinawath, Synthesis of ZSM-5 zeolite and silicalite from rice husk ash, Appl. Catal. B 90 (2009) 389–394.[25] S. Bosnar, V. Rac, D. Stosic, A. Travert, G. Postole, A. Auroux, S. Skapin, L. DamjanoviVasili, J. Bronic, X. Du, S. Markovic, V. Pavlovi, V. Rakic, Overcoming phase separation in dual templating: a homogeneous hierarchical ZSM-5 zeolite with flower-like morphology, synthesis and in-depth acidity study, Microporous Mesoporous Mater. 329 (2022) 111534.[26] L. Chu, G. Liu, Q. Xiao, Direct construction of hierarchical ZSM–5 microspheres aided by 3–glycidoxypropyltrimethoxysilane, Mater. Res. Bull. 60 (2014) 746–751.[27] P.S. Kumar, L. Korving, K.J. Keesman, Mark C.M. van Loosdrecht, G.-J. Witkamp, Effect of pore size distribution and particle size of porous metal oxides on phosphate adsorption capacity and kinetics, Chem. Eng. J. 358 (2019) 160–169.[28] Y. Wang, T. Du, X. Fang, H. Jia, Z. Qiu, Y. Song, Synthesis of CO2 -adsorbing ZSM-5 zeolite from rice husk ash via the colloidal pretreatment method, Mater. Chem. Phys. 232 (2019) 284–293.[29] J. Schnee, M. Quezada, O. Norosoa, F. Azzolina-Jury, ZSM-5 surface modification by plasma for catalytic activity improvement in the gas phase methanol-todimethylether reaction, Catal. Today 337 (2019) 195–200.[30] X. Feng, O. Onel, M. Council-Troche, A. Noble, R.H. Yoon, J.R. Morris, A study of rare earth ion-adsorption clays: the speciation of rare earth elements on kaolinite at basic pH, Appl. Clay Sci. 201 (2021) 105920.[31] G.S. dos Reis, J. Thivet, E. Laisn’e, V. Srivastava, A. Grimm, E.C. Lima, D. Bergna, T. Hu, M. Naushad, U. Lassi, Synthesis of novel mesoporous selenium-doped biochar with high-performance sodium diclofenac and reactive orange 16 dye removals, Chem. Eng. Sci. (2023) 119129, https://doi.org/10.1016/j. ces.2023.119129.[32] G.S. dos Reis, D. Bergna, A. Grimm, E.C. Lima, H. Hu, M. Naushad, U. Lassi, Preparation of highly porous nitrogen-doped biochar derived from birch tree wastes with superior dye removal performance, Colloids Surf. A 669 (2023) 131493, https://doi.org/10.1016/j.colsurfa.2023.131493.[33] A. Grimm, G.S. dos Reis, V.M. Dinh, S.H. Larsson, J.-P. Mikkola, E.C. Lima, S. Xiong, Hardwood spent mushroom substrate–based activated biochar as a sustainable bioresource for removal of emerging pollutants from wastewater, Biomass-.-. Convers. Biorefin. 14 (2022) 2293–2309, https://doi.org/10.1007/ s13399-022-02618-7.[34] R.C. Ferreira, O.M.C. Junior, K.Q. Carvalho, P.A. Arroyo, M.A.S.D. Barros, Efect of solution pH on the removal of paracetamol by activated carbon of dende coconut mesocarp, Chem. Biochem Eng. Q 29 (2015) 47–53.[35] A.R. Cestari, E.F.S. Vieira, G.S. Vieira, L.E. Almeida, The removal of anionic dyes from aqueous solutions in the presence of anionic surfactant using aminopropyl silica-a kinetic study, J. Hazard Mater. 138 (2006) 133–141.[36] B. Ji, W. Zhang, Adsorption of cerium (III) by zeolites synthesized from kaolinite after rare earth elements (REEs) recovery, Chemosphere 303 (2022) 134941.[37] Y. Cheng, T. Zhang, L. Zhang, Z. Ke, L. Kovarik, H. Dong, Resource recovery: Adsorption and biomineralization of cerium by Bacillus licheniformis, J. Hazard. Mat. 426 (2022) 127844.[38] Y.A. Akbas, S. Yusan, S. Sert, S. Aytas, Sorption of Ce(III) on magnetic/olive pomace nanocomposite: isotherm, kinetic and thermodynamic studies, Environ. Sci. Pollut. Res. 28 (2021) 56782–56794.[39] H. Yuhua, L. Xiaogang, S. Minxin, Q. Yuanyuan, L. Xiancai, Study on the adsorption of lanthanum ion imprinted on SBA-15/Y, J. Indian Chem. Soc. 99 (2022) 100425.[40] J. Gaete, L. Molina, F. Valenzuela, C. Basualto, Recovery of lanthanum, praseodymium and samarium by adsorption using magnetic nanoparticles functionalized with a phosphonic group, Hydrometallurgy 203 (2021) 105698.[41] E. Kusrinia, W. Wicaksono, C. Gunawan, N.Z.A. Daud, A. Usman, Kinetics, mechanism, and thermodynamics of lanthanum adsorption on pectin extracted from durian rind, J. Environ. Chem. Eng. 6 (2018) 6580–6588.[42] H. Javadian, M. Ruiz, M. Taghvai, A.M. Sastre, Novel magnetic nanocomposite of calcium alginate carrying poly (pyrimidine-thiophene-amide) as a novel green synthesized polyamide for adsorption study of neodymium, terbium, and dysprosium rare-earth ions, Colloids Surf. A 603 (2020) 125252.[43] M.M. Yusoff, N.R.N. Mostapa, M.S. Sarkar, T.K. Biswas, M.L. Rahman, S.E. Arshad, M.S. Sarjadi, A.D. Kulkarni, Synthesis of ion imprinted polymers for selective recognition and separation of rare earth metals, J. Rare Earth 35 (2017) 177–186.[44] Radwa M. Ashour, Ramy El-sayed, Ahmed F. Abdel-Magied, Ahmed A. Abdelkhalek, M.M. Ali, Kerstin Forsberg, A. Uheida, Mamoun Muhammed, Joydeep Dutta, Selective separation of rare earth ions from aqueous solution using functionalized magnetite nanoparticles: kinetic and thermodynamic studies, Chem. Eng. J. 327 (2017) 286–296.[45] G.S. dos Reis, G.L. Dotto, J. Vieillard, M.L.S. Oliveira, S.F. Lütke, L.F.O. Silva, E. C. Lima, N.P.G. Salau, U. Lassi, Uptake the rare earth elements Nd, Ce, and La by a commercial diatomite: kinetics, equilibrium, thermodynamic and adsorption mechanism, J. Mol. Liq. 389 (2023) 122862, https://doi.org/10.1016/j. molliq.2023.122862.[46] M. Medykowska, M. Wisniewska, K. Szewczuk-Karpisz, R. Panek, Interaction mechanism of heavy metal ions with the nanostructured zeolites surface – adsorption, electrokinetic and XPS studies, J. Mol. Liq. 357 (2022) 119144.[47] L.H. Dong, L.A. Hou, Z.S. Wang, P. Gu, G.Y. Chen, R.F. Jiang, A new function of spent activated carbon in BAC process: removing heavy metals by ion exchange mechanism, J. Hazard. Mater. 359 (2018) 76–84.[48] G.S. dos Reis, A. Grimm, D.A. Fungaro, T. Hu, I.A.S. de Brum, E.C. Lima, M. Naushad, G.L. Dotto, U. Lassi, Synthesis of sustainable mesoporous sulfur-doped biobased carbon with superior performance sodium diclofenac removal: Kinetic, equilibrium, thermodynamic and mechanism, Environ. Res. 251 (2024) 118595.[49] G.S. dos Reis, G.L. Dotto, J. Vieillard, M.L.S. Oliveira, S.F. Lutke, A. Grimm, L.F. O. Silva, E.C. Lima, M. Naushad, U. Lassi, Nickel-aluminium layered double hydroxide as an efficient adsorbent to selectively recover praseodymium and samarium from phosphogypsum leachate, J. Alloy. Compd. 960 (2023) 170530.101698Microporous zeoliteAdsorption of rare earth elementsIon-exchange mechanismPublicationORIGINALAdsorption of rare earth elements.pdfAdsorption of rare earth elements.pdfArtículoapplication/pdf2569392https://repositorio.cuc.edu.co/bitstreams/7883df31-7d4a-4640-b62a-37cbe9627477/download24e62396f0360ffa3c13d510f0779167MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/d515d0ee-d1d0-4779-bf39-2912caacbc50/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTAdsorption of rare earth elements.pdf.txtAdsorption of rare earth elements.pdf.txtExtracted texttext/plain49017https://repositorio.cuc.edu.co/bitstreams/d4a191a5-993b-4cfa-b31e-aac1b27ce8ae/downloade61a1c909766173f3d9d3b0afa5d989cMD53THUMBNAILAdsorption of rare earth elements.pdf.jpgAdsorption of rare earth elements.pdf.jpgGenerated Thumbnailimage/jpeg13245https://repositorio.cuc.edu.co/bitstreams/3fd701c3-293f-4a03-b842-e593c96cb64b/downloadeddab24ca1731c3cc0250d81a98e2613MD5411323/13308oai:repositorio.cuc.edu.co:11323/133082024-09-17 14:08:20.324https://creativecommons.org/licenses/by/4.0/© 2024 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.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 |