Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds
Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane c...
- Autores:
-
Frantz Lütke, Sabrina
Dotto, Guilherme Luiz
Silva Oliveira, Marcos Leandro
Silva Oliveira, Luis Felipe
Ben Amara, Fakhreddine
Knani, Salah
Alruwaili, Amani
Jemli, Sonia
- 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:11323/13318
- Acceso en línea:
- https://hdl.handle.net/11323/13318
https://repositorio.cuc.edu.co/
- Palabra clave:
- Adsorption
Bioadsorbent
Mechanisms
Produced water
Statistical physics
- Rights
- embargoedAccess
- License
- Atribución 4.0 Internacional (CC BY 4.0)
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Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| title |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| spellingShingle |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds Adsorption Bioadsorbent Mechanisms Produced water Statistical physics |
| title_short |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| title_full |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| title_fullStr |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| title_full_unstemmed |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| title_sort |
Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds |
| dc.creator.fl_str_mv |
Frantz Lütke, Sabrina Dotto, Guilherme Luiz Silva Oliveira, Marcos Leandro Silva Oliveira, Luis Felipe Ben Amara, Fakhreddine Knani, Salah Alruwaili, Amani Jemli, Sonia |
| dc.contributor.author.none.fl_str_mv |
Frantz Lütke, Sabrina Dotto, Guilherme Luiz Silva Oliveira, Marcos Leandro Silva Oliveira, Luis Felipe Ben Amara, Fakhreddine Knani, Salah Alruwaili, Amani Jemli, Sonia |
| dc.subject.proposal.eng.fl_str_mv |
Adsorption Bioadsorbent Mechanisms Produced water Statistical physics |
| topic |
Adsorption Bioadsorbent Mechanisms Produced water Statistical physics |
| description |
Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min−1 mg−1), while the equilibrium data fitted the Sips model ( = 140.55 mg g−1). The process’s thermodynamics indicated that the target NA’s adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( ). The number of molecules adsorbed per site ) was highly influenced by the temperature as decreased with increasing temperature and increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C6H11COO−(aq.) and C6H11COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m2 g−1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied. |
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2024 |
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2024-09-12T19:43:25Z |
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2024-09-12T19:43:25Z 2025-06-17 |
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2024-06-17 |
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Artículo de revista |
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Vieira, Y., Fuhr, A.C.F.P., Lütke, S.F. et al. Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds. Environ Sci Pollut Res 31, 42889–42901 (2024). https://doi.org/10.1007/s11356-024-33977-5 |
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0944-1344 |
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https://hdl.handle.net/11323/13318 |
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10.1007/s11356-024-33977-5 |
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1614-7499 |
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Corporación Universidad de la Costa |
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REDICUC - Repositorio CUC |
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https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Vieira, Y., Fuhr, A.C.F.P., Lütke, S.F. et al. Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds. Environ Sci Pollut Res 31, 42889–42901 (2024). https://doi.org/10.1007/s11356-024-33977-5 0944-1344 10.1007/s11356-024-33977-5 1614-7499 Corporación Universidad de la Costa REDICUC - Repositorio CUC |
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https://hdl.handle.net/11323/13318 https://repositorio.cuc.edu.co/ |
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eng |
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eng |
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Environmental Science and Pollution Research |
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Amrhar O, El Gana L, Mobarak M (2021) Calculation of adsorption isotherms by statistical physics models: a review. Environ Chem Lett 19:4519–4547. https://doi.org/10.1007/s10311-021-01279-8 Arrigo R, Jagdale P, Bartoli M et al (2019) Structure–property relationships in polyethylene-based composites filled with biochar derived from waste coffee grounds. Polymers 11:1336. https://doi.org/10.3390/polym11081336 Ballesteros LF, Teixeira JA, Mussatto SI (2014) Chemical, functional, and structural properties of spent coffee grounds and coffee silverskin. Food Bioprocess Technol 7:3493–3503. https://doi.org/10.1007/s11947-014-1349-z Bijla L, Aissa R, Laknifli A et al (2022) Spent coffee grounds: a sustainable approach toward novel perspectives of valorization. J Food Biochem 46:e14190. https://doi.org/10.1111/jfbc.14190 Brient JA, Wessner PJ, Doyle MN (2000) Kirk‐Othmer encyclopedia of chemical technology. John Wiley & Sons, Hoboken. Naphthenic acids Brown LD, Ulrich AC (2015) Oil sands naphthenic acids: a review of properties, measurement, and treatment. Chemosphere 127:276–290. https://doi.org/10.1016/j.chemosphere.2015.02.003 Campos NF, Barbosa CM, Rodríguez-Díaz JM, Duarte MM (2018) Removal of naphthenic acids using activated charcoal: kinetic and equilibrium studies. Adsorpt Sci Technol 36:1405–1421. https://doi.org/10.1177/0263617418773844 Campos NF, Sales DCS, Rodríguez-Díaz JM et al (2022) Adsorption of naphthenic acids on peanut shell activated carbon: batch and fixed-bed column study of the process. Chem Eng Res Des 188:633–644. https://doi.org/10.1016/j.cherd.2022.10.023 Ceretta MB, Vieira Y, Wolski EA et al (2020) Biological degradation coupled to photocatalysis by ZnO/polypyrrole composite for the treatment of real textile wastewater. J Water Process Eng 35:101230. https://doi.org/10.1016/j.jwpe.2020.101230 Craig AP, Franca AS, Oliveira LS (2012) Evaluation of the potential of FTIR and chemometrics for separation between defective and non-defective coffees. Food Chem 132:1368–1374. https://doi.org/10.1016/j.foodchem.2011.11.121 Cruz-Lopes L, Domingos I, Ferreira J, Esteves B (2017) A new way of using spent coffee ground. Journal of International Scientific Publications v. 5:85–93 Fuhr ACFP, Vieira Y, Oliveira MLS et al (2023) A detailed study on the selection of borderline features for accurate mechanism description of the adsorption of different pesticide molecules under different temperature ranges. J Mol Liq 390:123107. https://doi.org/10.1016/j.molliq.2023.123107 Gkika DA, Mitropoulos AC, Kyzas GZ (2022) Why reuse spent adsorbents? The latest challenges and limitations. Sci Total Environ 822:153612. https://doi.org/10.1016/j.scitotenv.2022.153612 Hendges LT, Costa TC, Temochko B et al (2021) Adsorption and desorption of water-soluble naphthenic acid in simulated offshore oilfield produced water. Process Saf Environ Prot 145:262–272. https://doi.org/10.1016/j.psep.2020.08.018 Jemli S, Pinto D, Kanhounnon WG et al (2023) Green β-cyclodextrin nanosponges for the efficient adsorption of light rare earth elements: cerium and lanthanum. Chem Eng J 466:143108. https://doi.org/10.1016/j.cej.2023.143108 Jemli S, Vieira Y, Dotto GL et al (2024) Neodymium adsorption from aqueous solution by β-cyclodextrin nanosponges and a polymer valorized from potato peels waste: experiments and conventional and statistical physics interpretations. Environ Sci Pollut Res 31:19974–19985. https://doi.org/10.1007/s11356-024-32473-0 Jutakridsada P, Prajaksud C, Kuboonya-Aruk L et al (2016) Adsorption characteristics of activated carbon prepared from spent ground coffee. Clean Techn Environ Policy 18:639–645. https://doi.org/10.1007/s10098-015-1083-x Keleşoğlu S, Volden S, Kes M, Sjöblom J (2012) Adsorption of naphthenic acids onto mineral surfaces studied by quartz crystal microbalance with dissipation monitoring (QCM-D). Energy Fuels 26:5060–5068. https://doi.org/10.1021/ef300612z Klemz AC, Damas MSP, González SYG et al (2020) The use of oilfield gaseous byproducts as extractants of recalcitrant naphthenic acids from synthetic produced water. Sep Purif Technol 248:117123. https://doi.org/10.1016/j.seppur.2020.117123 Knag AC, Sebire M, Mayer I et al (2013) In vivo endocrine effects of naphthenic acids in fish. Chemosphere 93:2356–2364. https://doi.org/10.1016/j.chemosphere.2013.08.033 Kovalcik A, Obruca S, Marova I (2018) Valorization of spent coffee grounds: a review. Food Bioprod Process 110:104–119. https://doi.org/10.1016/j.fbp.2018.05.002 Leclair LA, Pohler L, Wiseman SB et al (2015) In vitro assessment of endocrine disrupting potential of naphthenic acid fractions derived from oil sands-influenced water. Environ Sci Technol 49:5743–5752. https://doi.org/10.1021/acs.est.5b00077 Li Z, Sellaoui L, Gueddida S et al (2020) Adsorption of methylene blue on silica nanoparticles: modelling analysis of the adsorption mechanism via a double layer model. J Mol Liq 319:114348. https://doi.org/10.1016/j.molliq.2020.114348 Lima EC, Hosseini-Bandegharaei A, Moreno-Piraján JC, Anastopoulos I (2019) A critical review of the estimation of the thermodynamic parameters on adsorption equilibria. Wrong use of equilibrium constant in the Van’t Hoof equation for calculation of thermodynamic parameters of adsorption. J Mol Liq 273:425–434. https://doi.org/10.1016/j.molliq.2018.10.048 Loughery JR, Marentette JR, Frank RA et al (2019) Transcriptome profiling in larval fathead minnow exposed to commercial naphthenic acids and extracts from fresh and aged oil sands process-affected water. Environ Sci Technol 53:10435–10444. https://doi.org/10.1021/acs.est.9b01493 Marquardt DW (1963) An Algorithm for least-squares estimation of nonlinear parameters. J Soc Ind Appl Math 11:431–441. https://doi.org/10.1137/0111030 Mezura-Montes E, Coello Coello CA (2011) Constraint-handling in nature-inspired numerical optimization: past, present and future. Swarm Evol Comput 1:173–194. https://doi.org/10.1016/j.swevo.2011.10.001 Migliorin LS, Franco DSP, Knani S et al (2022) Application of mesoporous zeolite Socony Mobil-5 (ZSM-5) as an adsorbent material for the removal of naphthenic acid present in oil-produced water. Microporous Mesoporous Mater 344:112216. https://doi.org/10.1016/j.micromeso.2022.112216 Mohamed MH, Wilson LD, Headley JV, Peru KM (2011) Sequestration of naphthenic acids from aqueous solution using β-cyclodextrin-based polyurethanes. Phys Chem Chem Phys 13:1112–1122. https://doi.org/10.1039/C0CP00421A Nguyen V-T, Vo T-D-H, Nguyen T-B et al (2022) Adsorption of norfloxacin from aqueous solution on biochar derived from spent coffee ground: master variables and response surface method optimized adsorption process. Chemosphere 288:132577. https://doi.org/10.1016/j.chemosphere.2021.132577 Niasar HS, Li H, Kasanneni TVR et al (2016) Surface amination of activated carbon and petroleum coke for the removal of naphthenic acids and treatment of oil sands process-affected water (OSPW). Chem Eng J 293:189–199. https://doi.org/10.1016/j.cej.2016.02.062 Niasar HS, Das S, Xu C (Charles), Ray MB (2019) Continuous column adsorption of naphthenic acids from synthetic and real oil sands process-affected water (OSPW) using carbon-based adsorbents. Chemosphere 214:511–518https://doi.org/10.1016/j.chemosphere.2018.09.078 Pinzón-Espinosa A, Kanda R (2020) Naphthenic acids are key contributors to toxicity of heavy oil refining effluents. Sci Total Environ 729:138119. https://doi.org/10.1016/j.scitotenv.2020.138119 Poli R, Kennedy J, Blackwell T (2007) Particle Swarm Optimization. Swarm Intell 1:33–57. https://doi.org/10.1007/s11721-007-0002-0 Radelyuk I, Tussupova K, Klemeš JJ, Persson KM (2021) Oil refinery and water pollution in the context of sustainable development: developing and developed countries. J Clean Prod 302:126987. https://doi.org/10.1016/j.jclepro.2021.126987 Robinson CE, Elvidge CK, Frank RA et al (2023) Naphthenic acid fraction compounds reduce the reproductive success of wood frogs (Rana sylvatica) by affecting offspring viability. Environ Pollut 316:120455. https://doi.org/10.1016/j.envpol.2022.120455 Scott AC, Zubot W, Davis CW, Brogly J (2020) Bioaccumulation potential of naphthenic acids and other ionizable dissolved organics in oil sands process water (OSPW) – a review. Sci Total Environ 712:134558. https://doi.org/10.1016/j.scitotenv.2019.134558 Sellaoui L, Silva LFO, Badawi M et al (2021a) Adsorption of ketoprofen and 2- nitrophenol on activated carbon prepared from winery wastes: a combined experimental and theoretical study. J Mol Liq 333:115906. https://doi.org/10.1016/j.molliq.2021.115906 Sellaoui L, Yazidi A, Taamalli S et al (2021b) Adsorption of 3-aminophenol and resorcinol on avocado seed activated carbon: mathematical modelling, thermodynamic study and description of adsorbent performance. J Mol Liq 342:116952. https://doi.org/10.1016/j.molliq.2021.116952 Shamsudin MS, Azha SF, Sellaoui L et al (2020) Fabrication and characterization of a thin coated adsorbent for antibiotic and analgesic adsorption: experimental investigation and statistical physical modelling. Chem Eng J 401:126007. https://doi.org/10.1016/j.cej.2020.126007 Singh R, Naik DV, Dutta RK, Kanaujia PK (2020) Biochars for the removal of naphthenic acids from water: a prospective approach towards remediation of petroleum refinery wastewater. J Clean Prod 266:121986. https://doi.org/10.1016/j.jclepro.2020.121986 Steigerwald JM, Peng S, Ray JR (2023) Novel perfluorooctanesulfonate-imprinted polymer immobilized on spent coffee grounds biochar for selective removal of perfluoroalkyl acids in synthetic wastewater. ACS EST Eng 3:520–532. https://doi.org/10.1021/acsestengg.2c00336 Susilayati M, Marwoto P, Priatmoko S (2022) Characterization of spent coffee grounds in the community as supporting materials for renewable energy. Jppipa, pendidikan Ipa, Fisika, Biologi, Kimia 8:918–924. https://doi.org/10.29303/jppipa.v8i2.1227 Taleb F, Ammar M, ben Mosbah M et al (2020) Chemical modification of lignin derived from spent coffee grounds for methylene blue adsorption. Sci Rep 10:11048 Vieira Y, dos Santos JMN, Georgin J et al (2022a) An overview of forest residues as promising low-cost adsorbents. Gondwana Res 110:393–420. https://doi.org/10.1016/j.gr.2021.06.018 Vieira Y, Schnorr C, Piazzi AC et al (2022b) An advanced combination of density functional theory simulations and statistical physics modeling in the unveiling and prediction of adsorption mechanisms of 2,4-D pesticide to activated carbon. J Mol Liq 361:119639. https://doi.org/10.1016/j.molliq.2022.119639 Vieira Y, Silveira JP, Dotto GL et al (2022c) Mechanistic insights and steric interpretations through statistical physics modelling and density functional theory calculations for the adsorption of the pesticides atrazine and diuron by Hovenia dulcis biochar. J Mol Liq 367:120418. https://doi.org/10.1016/j.molliq.2022.120418 Wang X, Kasperski KL (2010) Analysis of naphthenic acids in aqueous solution using HPLC-MS/MS. Anal Methods 2:1715–1722. https://doi.org/10.1039/C0AY00204F Wang N, Lim L-T (2012) Fourier transform infrared and physicochemical analyses of roasted coffee. J Agric Food Chem 60:5446–5453. https://doi.org/10.1021/jf300348e Wu C, De Visscher A, Gates ID (2019) On naphthenic acids removal from crude oil and oil sands process-affected water. Fuel 253:1229–1246. https://doi.org/10.1016/j.fuel.2019.05.091 Yu L, Han M, He F (2017) A review of treating oily wastewater. Arab J Chem 10:S1913–S1922. https://doi.org/10.1016/j.arabjc.2013.07.020 Zhang X, Zhang Y, Ngo HH et al (2020) Characterization and sulfonamide antibiotics adsorption capacity of spent coffee grounds based biochar and hydrochar. Sci Total Environ 716:137015. https://doi.org/10.1016/j.scitotenv.2020.137015 |
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Atribución 4.0 Internacional (CC BY 4.0)© 2024 Springer Naturehttps://creativecommons.org/licenses/by/4.0/info:eu-repo/semantics/embargoedAccesshttp://purl.org/coar/access_right/c_f1cfFrantz Lütke, SabrinaDotto, Guilherme LuizSilva Oliveira, Marcos LeandroSilva Oliveira, Luis FelipeBen Amara, FakhreddineKnani, SalahAlruwaili, Amani Jemli, Sonia2024-09-12T19:43:25Z2025-06-172024-09-12T19:43:25Z2024-06-17Vieira, Y., Fuhr, A.C.F.P., Lütke, S.F. et al. Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds. Environ Sci Pollut Res 31, 42889–42901 (2024). https://doi.org/10.1007/s11356-024-33977-50944-1344https://hdl.handle.net/11323/1331810.1007/s11356-024-33977-51614-7499Corporación Universidad de la CostaREDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/Naphthenic acids (NA) are organic compounds commonly found in crude oil and produced water, known for their recalcitrance and toxicity. This study introduces a new adsorbent, a polymer derived from spent coffee grounds (SCGs), through a straightforward cross-linking method for removing cyclohexane carboxylic acid as representative NA. The adsorption kinetics followed a pseudo-second-order model for the data (0.007 g min−1 mg−1), while the equilibrium data fitted the Sips model ( = 140.55 mg g−1). The process’s thermodynamics indicated that the target NA’s adsorption was spontaneous and exothermic. The localized sterical and energetic aspects were investigated through statistical physical modeling, which corroborated that the adsorption occurred indeed in monolayer, as suggested by the Sips model, but revealed the contribution of two energies per site ( ). The number of molecules adsorbed per site ) was highly influenced by the temperature as decreased with increasing temperature and increased. These results were experimentally demonstrated within the pH range between 4 and 6, where both C6H11COO−(aq.) and C6H11COOH(aq.) species coexisted and were adsorbed by different energy sites. The polymer produced was naturally porous and amorphous, with a low surface area of 20 to 30 m2 g−1 that presented more energetically accessible sites than other adsorbents with much higher surface areas. Thus, this study shows that the relation between surface area and high adsorption efficiency depends on the compatibility between the energetic states of the receptor sites, the speciation of the adsorbate molecules, and the temperature range studied.7 páginasapplication/pdfengSpringerGermanyhttps://link.springer.com/article/10.1007/s11356-024-33977-5Adsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee groundsArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/drafthttp://purl.org/coar/version/c_b1a7d7d4d402bcceEnvironmental Science and Pollution ResearchAmrhar O, El Gana L, Mobarak M (2021) Calculation of adsorption isotherms by statistical physics models: a review. Environ Chem Lett 19:4519–4547. https://doi.org/10.1007/s10311-021-01279-8Arrigo R, Jagdale P, Bartoli M et al (2019) Structure–property relationships in polyethylene-based composites filled with biochar derived from waste coffee grounds. Polymers 11:1336. https://doi.org/10.3390/polym11081336Ballesteros LF, Teixeira JA, Mussatto SI (2014) Chemical, functional, and structural properties of spent coffee grounds and coffee silverskin. Food Bioprocess Technol 7:3493–3503. https://doi.org/10.1007/s11947-014-1349-zBijla L, Aissa R, Laknifli A et al (2022) Spent coffee grounds: a sustainable approach toward novel perspectives of valorization. J Food Biochem 46:e14190. https://doi.org/10.1111/jfbc.14190Brient JA, Wessner PJ, Doyle MN (2000) Kirk‐Othmer encyclopedia of chemical technology. John Wiley & Sons, Hoboken. Naphthenic acidsBrown LD, Ulrich AC (2015) Oil sands naphthenic acids: a review of properties, measurement, and treatment. 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Sci Total Environ 716:137015. https://doi.org/10.1016/j.scitotenv.2020.13701542901428893031AdsorptionBioadsorbentMechanismsProduced waterStatistical physicsPublicationORIGINALAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdfAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdfArtículoapplication/pdf222678https://repositorio.cuc.edu.co/bitstreams/f7e2bed9-a061-48f8-8d5a-789fb284741f/download0afb57939ce5a4248ea7038080ac3b59MD51LICENSElicense.txtlicense.txttext/plain; charset=utf-814828https://repositorio.cuc.edu.co/bitstreams/3af5f9e6-f663-4050-aa9b-727805f3956e/download2f9959eaf5b71fae44bbf9ec84150c7aMD52TEXTAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdf.txtAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdf.txtExtracted texttext/plain15256https://repositorio.cuc.edu.co/bitstreams/844cd815-ea44-4143-b7a0-3cc80124b5a8/download7c9b04be20e47c98d851e1c83b225246MD53THUMBNAILAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdf.jpgAdsorptive features of cyclohexane carboxylic naphthenic acid on a novel cross-linked polymer developed from spent coffee grounds.pdf.jpgGenerated Thumbnailimage/jpeg14723https://repositorio.cuc.edu.co/bitstreams/669bae13-5d4b-4c7d-b966-55f35ced7df5/downloadb11e985dc2ed6ec9f658cd7ef4a9cbd7MD5411323/13318oai:repositorio.cuc.edu.co:11323/133182024-09-17 14:19:45.187https://creativecommons.org/licenses/by/4.0/© 2024 Springer Natureopen.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa 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ada en las Obras Colectivas.

b.	Distribuir copias o fonogramas de las Obras, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública, incluyéndolas como incorporadas en Obras Colectivas, según corresponda.

c.	Distribuir copias de las Obras Derivadas que se generen, exhibirlas públicamente, ejecutarlas públicamente y/o ponerlas a disposición pública.
Los derechos mencionados anteriormente pueden ser ejercidos en todos los medios y formatos, actualmente conocidos o que se inventen en el futuro. Los derechos antes mencionados incluyen el derecho a realizar dichas modificaciones en la medida que sean técnicamente necesarias para ejercer los derechos en otro medio o formatos, pero de otra manera usted no está autorizado para realizar obras derivadas. Todos los derechos no otorgados expresamente por el Licenciante quedan por este medio reservados, incluyendo pero sin limitarse a aquellos que se mencionan en las secciones 4(d) y 4(e).

4. Restricciones.
La licencia otorgada en la anterior Sección 3 está expresamente sujeta y limitada por las siguientes restricciones:

a.	Usted puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra sólo bajo las condiciones de esta Licencia, y Usted debe incluir una copia de esta licencia o del Identificador Universal de Recursos de la misma con cada copia de la Obra que distribuya, exhiba públicamente, ejecute públicamente o ponga a disposición pública. No es posible ofrecer o imponer ninguna condición sobre la Obra que altere o limite las condiciones de esta Licencia o el ejercicio de los derechos de los destinatarios otorgados en este documento. No es posible sublicenciar la Obra. Usted debe mantener intactos todos los avisos que hagan referencia a esta Licencia y a la cláusula de limitación de garantías. Usted no puede distribuir, exhibir públicamente, ejecutar públicamente, o poner a disposición pública la Obra con alguna medida tecnológica que controle el acceso o la utilización de ella de una forma que sea inconsistente con las condiciones de esta Licencia. Lo anterior se aplica a la Obra incorporada a una Obra Colectiva, pero esto no exige que la Obra Colectiva aparte de la obra misma quede sujeta a las condiciones de esta Licencia. Si Usted crea una Obra Colectiva, previo aviso de cualquier Licenciante debe, en la medida de lo posible, eliminar de la Obra Colectiva cualquier referencia a dicho Licenciante o al Autor Original, según lo solicitado por el Licenciante y conforme lo exige la cláusula 4(c).

b.	Usted no puede ejercer ninguno de los derechos que le han sido otorgados en la Sección 3 precedente de modo que estén principalmente destinados o directamente dirigidos a conseguir un provecho comercial o una compensación monetaria privada. El intercambio de la Obra por otras obras protegidas por derechos de autor, ya sea a través de un sistema para compartir archivos digitales (digital file-sharing) o de cualquier otra manera no será considerado como estar destinado principalmente o dirigido directamente a conseguir un provecho comercial o una compensación monetaria privada, siempre que no se realice un pago mediante una compensación monetaria en relación con el intercambio de obras protegidas por el derecho de autor.

c.	Si usted distribuye, exhibe públicamente, ejecuta públicamente o ejecuta públicamente en forma digital la Obra o cualquier Obra Derivada u Obra Colectiva, Usted debe mantener intacta toda la información de derecho de autor de la Obra y proporcionar, de forma razonable según el medio o manera que Usted esté utilizando: (i) el nombre del Autor Original si está provisto (o seudónimo, si fuere aplicable), y/o (ii) el nombre de la parte o las partes que el Autor Original y/o el Licenciante hubieren designado para la atribución (v.g., un instituto patrocinador, editorial, publicación) en la información de los derechos de autor del Licenciante, términos de servicios o de otras formas razonables; el título de la Obra si está provisto; en la medida de lo razonablemente factible y, si está provisto, el Identificador Uniforme de Recursos (Uniform Resource Identifier) que el Licenciante especifica para ser asociado con la Obra, salvo que tal URI no se refiera a la nota sobre los derechos de autor o a la información sobre el licenciamiento de la Obra; y en el caso de una Obra Derivada, atribuir el crédito identificando el uso de la Obra en la Obra Derivada (v.g., "Traducción Francesa de la Obra del Autor Original," o "Guión Cinematográfico basado en la Obra original del Autor Original"). Tal crédito puede ser implementado de cualquier forma razonable; en el caso, sin embargo, de Obras Derivadas u Obras Colectivas, tal crédito aparecerá, como mínimo, donde aparece el crédito de cualquier otro autor comparable y de una manera, al menos, tan destacada como el crédito de otro autor comparable.

d.	Para evitar toda confusión, el Licenciante aclara que, cuando la obra es una composición musical:

i.	Regalías por interpretación y ejecución bajo licencias generales. El Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública o la ejecución pública digital de la obra y de recolectar, sea individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, SAYCO), las regalías por la ejecución pública o por la ejecución pública digital de la obra (por ejemplo Webcast) licenciada bajo licencias generales, si la interpretación o ejecución de la obra está primordialmente orientada por o dirigida a la obtención de una ventaja comercial o una compensación monetaria privada.

ii.	Regalías por Fonogramas. El Licenciante se reserva el derecho exclusivo de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, los consagrados por la SAYCO), una agencia de derechos musicales o algún agente designado, las regalías por cualquier fonograma que Usted cree a partir de la obra (“versión cover”) y distribuya, en los términos del régimen de derechos de autor, si la creación o distribución de esa versión cover está primordialmente destinada o dirigida a obtener una ventaja comercial o una compensación monetaria privada.

e.	Gestión de Derechos de Autor sobre Interpretaciones y Ejecuciones Digitales (WebCasting). Para evitar toda confusión, el Licenciante aclara que, cuando la obra sea un fonograma, el Licenciante se reserva el derecho exclusivo de autorizar la ejecución pública digital de la obra (por ejemplo, webcast) y de recolectar, individualmente o a través de una sociedad de gestión colectiva de derechos de autor y derechos conexos (por ejemplo, ACINPRO), las regalías por la ejecución pública digital de la obra (por ejemplo, webcast), sujeta a las disposiciones aplicables del régimen de Derecho de Autor, si esta ejecución pública digital está primordialmente dirigida a obtener una ventaja comercial o una compensación monetaria privada.

5. Representaciones, Garantías y Limitaciones de Responsabilidad.
A MENOS QUE LAS PARTES LO ACORDARAN DE OTRA FORMA POR ESCRITO, EL LICENCIANTE OFRECE LA OBRA (EN EL ESTADO EN EL QUE SE ENCUENTRA) “TAL CUAL”, SIN BRINDAR GARANTÍAS DE CLASE ALGUNA RESPECTO DE LA OBRA, YA SEA EXPRESA, IMPLÍCITA, LEGAL O CUALQUIERA OTRA, INCLUYENDO, SIN LIMITARSE A ELLAS, GARANTÍAS DE TITULARIDAD, COMERCIABILIDAD, ADAPTABILIDAD O ADECUACIÓN A PROPÓSITO DETERMINADO, AUSENCIA DE INFRACCIÓN, DE AUSENCIA DE DEFECTOS LATENTES O DE OTRO TIPO, O LA PRESENCIA O AUSENCIA DE ERRORES, SEAN O NO DESCUBRIBLES (PUEDAN O NO SER ESTOS DESCUBIERTOS). ALGUNAS JURISDICCIONES NO PERMITEN LA EXCLUSIÓN DE GARANTÍAS IMPLÍCITAS, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.

6. Limitación de responsabilidad.
A MENOS QUE LO EXIJA EXPRESAMENTE LA LEY APLICABLE, EL LICENCIANTE NO SERÁ RESPONSABLE ANTE USTED POR DAÑO ALGUNO, SEA POR RESPONSABILIDAD EXTRACONTRACTUAL, PRECONTRACTUAL O CONTRACTUAL, OBJETIVA O SUBJETIVA, SE TRATE DE DAÑOS MORALES O PATRIMONIALES, DIRECTOS O INDIRECTOS, PREVISTOS O IMPREVISTOS PRODUCIDOS POR EL USO DE ESTA LICENCIA O DE LA OBRA, AUN CUANDO EL LICENCIANTE HAYA SIDO ADVERTIDO DE LA POSIBILIDAD DE DICHOS DAÑOS. ALGUNAS LEYES NO PERMITEN LA EXCLUSIÓN DE CIERTA RESPONSABILIDAD, EN CUYO CASO ESTA EXCLUSIÓN PUEDE NO APLICARSE A USTED.

7. Término.

a.	Esta Licencia y los derechos otorgados en virtud de ella terminarán automáticamente si Usted infringe alguna condición establecida en ella. Sin embargo, los individuos o entidades que han recibido Obras Derivadas o Colectivas de Usted de conformidad con esta Licencia, no verán terminadas sus licencias, siempre que estos individuos o entidades sigan cumpliendo íntegramente las condiciones de estas licencias. Las Secciones 1, 2, 5, 6, 7, y 8 subsistirán a cualquier terminación de esta Licencia.

b.	Sujeta a las condiciones y términos anteriores, la licencia otorgada aquí es perpetua (durante el período de vigencia de los derechos de autor de la obra). No obstante lo anterior, el Licenciante se reserva el derecho a publicar y/o estrenar la Obra bajo condiciones de licencia diferentes o a dejar de distribuirla en los términos de esta Licencia en cualquier momento; en el entendido, sin embargo, que esa elección no servirá para revocar esta licencia o que deba ser otorgada , bajo los términos de esta licencia), y esta licencia continuará en pleno vigor y efecto a menos que sea terminada como se expresa atrás. La Licencia revocada continuará siendo plenamente vigente y efectiva si no se le da término en las condiciones indicadas anteriormente.

8. Varios.

a.	Cada vez que Usted distribuya o ponga a disposición pública la Obra o una Obra Colectiva, el Licenciante ofrecerá al destinatario una licencia en los mismos términos y condiciones que la licencia otorgada a Usted bajo esta Licencia.

b.	Si alguna disposición de esta Licencia resulta invalidada o no exigible, según la legislación vigente, esto no afectará ni la validez ni la aplicabilidad del resto de condiciones de esta Licencia y, sin acción adicional por parte de los sujetos de este acuerdo, aquélla se entenderá reformada lo mínimo necesario para hacer que dicha disposición sea válida y exigible.

c.	Ningún término o disposición de esta Licencia se estimará renunciada y ninguna violación de ella será consentida a menos que esa renuncia o consentimiento sea otorgado por escrito y firmado por la parte que renuncie o consienta.

d.	Esta Licencia refleja el acuerdo pleno entre las partes respecto a la Obra aquí licenciada. No hay arreglos, acuerdos o declaraciones respecto a la Obra que no estén especificados en este documento. El Licenciante no se verá limitado por ninguna disposición adicional que pueda surgir en alguna comunicación emanada de Usted. Esta Licencia no puede ser modificada sin el consentimiento mutuo por escrito del Licenciante y Usted.
 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