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Adsorption of short chain carboxylic acids from aqueous solution by swellable organically modified silica materials

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Abstract

The adsorption of C2–C6 short chain carboxylic acids was measured for swellable organically modified silicas (SOMS), hydrophobic polysilsesquioxane based materials prepared via the sol–gel process. Adsorption was measured for SOMS materials that were either hydrophobic or incorporated variable amounts of quaternary amine groups to serve as ion exchange sites. Batch equilibrium experiments were performed for carboxylic acids and alcohols to standard hydrophobic SOMS. Results show that SOMS has partition coefficients for short chain alcohols that are approximately 3× greater than liquid–liquid extraction into octanol, and 10× greater for the extraction of short chain carboxylic acids. Affinity for valeric acid was similar to commercially available Amberlite XAD-4 resins, however the organosilica derived sorbent had a 3× higher total adsorption capacity which was attributed to the ability of the pores to expand. Column experiments using SOMS were used to measure breakthrough curves for valeric acid across a wide range of concentrations. The isotherm for dynamic adsorption was linear indicating that capacity to adsorb valeric acid was controlled by equilibrium and not limited by set pore volume capacity. Addition of quaternary amine sites to SOMS improved adsorption affinity of valeric acid at low concentrations, but those modifications reduced the swelling of the matrix and lowered capacity at higher concentrations. Overall, SOMS was found to be poorly suited to extract organic acids at concentrations < 10 mM, but has high capacity for adsorption at higher concentrations (up to 700 mg/g). Adsorbed valeric acid could be recovered by solvent rinse.

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References

  • Agirre, I., Arias, P.L., Castricum, H.L., Creatore, M., Johan, E., Paradis, G.G., Ngamou, P.H., van Veen, H.M., Vente, J.F.: Hybrid organosilica membranes and processes: status and outlook. Sep. Purif. Technol. 121, 2–12 (2014)

    Article  CAS  Google Scholar 

  • Aiken, G.R., Thurman, E.M., Malcolm, R.L., Walton, H.F.: Comparison of XAD macroporous resins for the concentration of fulvic acid from aqueous solution. Anal. Chem. 51, 1799–1803 (1979)

    Article  CAS  Google Scholar 

  • Aiken, G., McKnight, D.M., Thorn, K.A., Thurman, E.M.: Isolation of hydrophilic organic acids from water using nonionic macroporous resins. Org. Geochem. 18, 567–573 (1992)

    Article  CAS  Google Scholar 

  • Alkaya, E., Kaptan, S., Ozkan, L., Uludag-Demirer, S., Demirer, G.N.: Recovery of acids from anaerobic acidification broth by liquid–liquid extraction. Chemosphere 77, 1137–1142 (2009)

    Article  CAS  Google Scholar 

  • Barrett, E.P., Joyner, L.G., Halenda, P.P.: The determination of pore volume and area distributions in porous substances. I. Computations from nitrogen isotherms. J. Am. Chem. Soc. 73, 373–380 (1951)

    Article  CAS  Google Scholar 

  • Brunauer, S., Emmett, P.H., Teller, E.: Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 60, 309–319 (1938)

    Article  CAS  Google Scholar 

  • Burkett, C.M., Underwood, L.A., Volzer, R.S., Baughman, J.A., Edmiston, P.L.: Organic–inorganic hybrid materials that rapidly swell in non-polar liquids: nanoscale morphology and swelling mechanism. Chem. Mater. 20, 1312–1321 (2008)

    Article  CAS  Google Scholar 

  • Burleigh, M.C., Markowitz, M.A., Spector, M.S., Gaber, B.P.: Amine-functionalized periodic mesoporous organosilicas. Chem. Mater. 13, 4760–4766 (2001)

    Article  CAS  Google Scholar 

  • Burleigh, M.C., Jayasundera, S., Thomas, C.W., Spector, M.S., Markowitz, M.A., Gaber, B.P.: A versatile synthetic approach to periodic mesoporous organosilicas. Colloid. Polym. Sci. 282, 728–733 (2004)

    Article  CAS  Google Scholar 

  • Castricum, H.L., Paradis, G.G., Mittelmeijer-Hazeleger, M.C., Kreiter, R., Vente, J.F., Ten Elshof, J.E.: Tailoring the separation behavior of hybrid organosilica membranes by adjusting the structure of the organic bridging group. Adv. Funct. Mater. 21, 2319–2329 (2011)

    Article  CAS  Google Scholar 

  • Chanda, M., O’Driscoll, K.F., Rempel, G.L.: Sorption of phenolics and carboxylic acids on polybenzimidazole. React. Polym. Ion Exch. Sorbents 4, 39–48 (1985)

    Article  CAS  Google Scholar 

  • Colominas, C., Teixidó, J., Cemelí, J., Luque, F.J., Orozco, M.: Dimerization of carboxylic acids: reliability of theoretical calculations and the effect of solvent. J. Phys. Chem. B. 102, 2269–2276 (1998)

    Article  CAS  Google Scholar 

  • Da’na, E.: Adsorption of heavy metals on functionalized-mesoporous silica: a review. Microporous Mesoporous Mater. 247, 145–157 (2017)

    Article  Google Scholar 

  • Davis, M.E.: Ordered porous materials for emerging applications. Nature. 417, 813–821 (2002)

    Article  CAS  Google Scholar 

  • Edmiston, P.L., Underwood, L.A.: Absorption of dissolved organic species from water using organically modified silica that swells. Sep. Purif. Technol. 66, 532–540 (2009)

    Article  CAS  Google Scholar 

  • Edmiston, P.L., West, L.J., Chin, A., Mellor, N., Barth, D.: Adsorption of gas phase organic compounds by swellable organically modified silica. Ind. Eng. Chem. Res. 55, 12068–12079 (2016)

    Article  CAS  Google Scholar 

  • El-Sayed, Y., Bandosz, T.J.: Adsorption of valeric acid from aqueous solution onto activated carbons: role of surface basic sites. J. Colloid Interface Sci. 273, 64–72 (2004)

    Article  CAS  Google Scholar 

  • Finizio, A., Vighi, M., Sandroni, D.: Determination of n-octanol/water partition coefficient (Kow) of pesticide critical review and comparison of methods. Chemosphere. 34, 131–161 (1997)

    Article  CAS  Google Scholar 

  • Gluszcz, P., Jamroz, T., Sencio, B., Ledakowicz, S.: Equilibrium and dynamic investigations of organic acids adsorption onto ion-exchange resins. Bioprocess Biosyst. Eng. 26, 185–190 (2004)

    Article  CAS  Google Scholar 

  • Gustafson, R.L., Albright, R.L., Heisler, J., Lirio, J.A., Reid, O.T. Jr.: Adsorption of organic species by high surface area styrene-divinylbenzene copolymers. Ind. Eng. Chem. Prod. Res. Dev. 7, 107–115 (1968)

    Article  CAS  Google Scholar 

  • Hu, L.C., Shea, K.J.: Organo–silica hybrid functional nanomaterials: how do organic bridging groups and silsesquioxane moieties work hand-in-hand? Chem. Soc. Rev. 40, 688–695 (2011)

    Article  CAS  Google Scholar 

  • Ingale, M.N., Mahajani, V.V.: Recovery of carboxylic acids, C2–C6, from an aqueous waste stream using tributylphosphate (TBP): effect of presence of inorganic acids and their sodium salts. Sep. Technol. 6, 1–7 (1996)

    Article  CAS  Google Scholar 

  • Jayasundera, S., Burleigh, M.C., Zeinali, M., Spector, M.S., Miller, J.B., Yan, W., Dai, S., Markowitz, M.A.: Organosilica copolymers for the adsorption and separation of multiple pollutants. J. Phys. Chem. B. 109, 9198–9201 (2005)

    Article  CAS  Google Scholar 

  • Kaneko, Y., Abe, M., Ogino, K.: Adsorption characteristics of organic compounds dissolved in water on surface-improved activated carbon fibres. Colloids Surf. 37, 211–222 (1989)

    Article  Google Scholar 

  • Kapoor, M.P., Yang, Q., Inagaki, S.: Self-assembly of biphenylene-bridged hybrid mesoporous solid with molecular-scale periodicity in the pore walls. J. Am. Chem. Soc. 124, 15176–15177 (2002)

    Article  CAS  Google Scholar 

  • Kawabata, N., Yoshida, J.I., Tanigawa, Y.: Removal and recovery of organic pollutants from aquatic environment. 4. Separation of carboxylic acids from aqueous solution using crosslinked poly (4-vinylpyridine). Ind. Eng. Chem. Prod. Res. Dev. 20, 386–390 (1981a)

    Article  CAS  Google Scholar 

  • Kawabata, N., Higuchi, I., Yoshida, J.I.: Removal and recovery of organic pollutants from the aquatic environment. VII. Adsorption of phenol and carboxylic acids on crosslinked poly (4-vinylpyridine). Bull. Chem. Soc. Jpn. 54, 3253–3258 (1981b)

    Article  CAS  Google Scholar 

  • Keshav, A., Wasewar, K.L.: Back extraction of propionic acid from loaded organic phase. Chem. Eng. Sci. 65, 2751–2757 (2010)

    Article  CAS  Google Scholar 

  • Keshav, A., Wasewar, K.L., Chand, S.: Recovery of propionic acid from an aqueous stream by reactive extraction: effect of diluents. Desalination. 244, 12–23 (2009a)

    Article  CAS  Google Scholar 

  • Keshav, A., Chand, S., Wasewar, K.L.: Recovery of propionic acid from aqueous phase by reactive extraction using quarternary amine (Aliquat 336) in various diluents. Chem. Eng. J. 152, 95–102 (2009b)

    Article  CAS  Google Scholar 

  • Kon, K., Onodera, W., Shimizu, K.I.: Selective hydrogenation of levulinic acid to valeric acid and valeric biofuels by a Pt/HMFI catalyst. Catal. Sci. Technol. 4, 3227–3234 (2014)

    Article  CAS  Google Scholar 

  • Kunin, R.: Polymeric adsorbents for treatment of waste effluents. Polym. Eng. Sci. 17, 58–62 (1977)

    Article  CAS  Google Scholar 

  • Lange, J.P., Price, R., Ayoub, P.M., Louis, J., Petrus, L., Clarke, L., Gosselink, H.: Valeric biofuels: a platform of cellulosic transportation fuels. Angew. Chem. Int. Ed. 49, 4479–4483 (2010)

    Article  CAS  Google Scholar 

  • Lee, W.S., Chua, A.S.M., Yeoh, H.K., Ngoh, G.C.: A review of the production and applications of waste-derived volatile fatty acids. Chem. Eng. J. 235, 83–99 (2014)

    Article  CAS  Google Scholar 

  • Li, W., Zhao, D.: An overview of the synthesis of ordered mesoporous materials. Chem. Commun. 49, 943–946 (2013)

    Article  CAS  Google Scholar 

  • Li, Z., Qin, W., Dai, Y.: Liquid–liquid equilibria of acetic, propionic, butyric, and valeric acids with trioctylamine as extractant. J. Chem. Eng. Data 47, 843–848 (2002)

    Article  Google Scholar 

  • Li, Q., Li, W.L., Wang, D., Liu, B.B., Tang, H., Yang, M.H., Liu, Q.F., Xing, J.M., Su, Z.G.: pH neutralization while succinic acid adsorption onto anion-exchange resins. Appl. Biochem. Biotechnol. 160, 438–445 (2010)

    Article  CAS  Google Scholar 

  • Mathews, D.M., Sheets, R.W.: Effect of surface adsorption on the determination by infrared spectroscopy of hydrogen bond energies in carboxylic acid dimers. J. Chem. Soc. A (1969). https://doi.org/10.1039/J19690002203

    Google Scholar 

  • Matsumoto, A., Misran, H., Tsutsumi, K.: Adsorption characteristics of organosilica based mesoporous materials. Langmuir. 20, 7139–7145 (2004)

    Article  CAS  Google Scholar 

  • Melde, B.J., Johnson, B.J., Dinderman, M.A., Deschamps, J.R.: Macroporous periodic mesoporous organosilicas with diethylbenzene bridging groups. Microporous Mesoporous Mater. 130, 180–188 (2010)

    Article  CAS  Google Scholar 

  • Mengmeng, C., Hong, C., Qingliang, Z., Shirley, S.N., Jie, R.: Optimal production of polyhydroxyalkanoates (PHA) in activated sludge fed by volatile fatty acids (VFAs) generated from alkaline excess sludge fermentation. Bioresour. Technol. 100, 1399–1405 (2009)

    Article  Google Scholar 

  • Mizoshita, N., Tani, T., Inagaki, S.: Syntheses, properties and applications of periodic mesoporous organosilicas prepared from bridged organosilane precursors. Chem. Soc. Rev. 40, 789–800 (2011)

    Article  CAS  Google Scholar 

  • Mostafa, N.A.: Production and recovery of volatile fatty acids from fermentation broth. ‎Energy Convers. Manage. 40, 1543–1553 (1999)

    Article  CAS  Google Scholar 

  • Niri, V.H., Bragg, L., Pawliszyn, J.: Fast analysis of volatile organic compounds and disinfection by-products in drinking water using solid-phase microextraction–gas chromatography/time-of-flight mass spectrometry. J. Chromatogr. A. 1201, 222–227 (2008)

    Article  CAS  Google Scholar 

  • Rodriguez, M., Viegas, R.M.C., Luque, S., Coelhoso, I.M., Crespo, J.P.S.G., Alvarez, J.R.: Removal of valeric acid from wastewaters by membrane contactors. J. Membr. Sci. 137, 45–53 (1997)

    Article  CAS  Google Scholar 

  • Rodriguez, M., Luque, S., Alvarez, J., Coca, J.: A comparative study of reverse osmosis and freeze concentration for the removal of valeric acid from wastewaters. Desalination. 127, 1–11 (2000)

    Article  CAS  Google Scholar 

  • Rodriguez, M., González-Muñoz, M.J., Luque, S., Alvarez, J.R., Coca, J.: Extractive ultrafiltration for the removal of carboxylic acids. J. Membr. Sci. 274, 209–218 (2006)

    Article  CAS  Google Scholar 

  • Rubio, B., Escudero, I., Ruiz, M.O., Cabezas, J.L., Alvarez, J.R., Coca, J.: Application of crossflow ultrafiltration to emulsion separation in the extraction of valeric acid with tri-n-butyl phosphate. Sep. Sci. Technol. 35, 811–823 (2000)

    Article  CAS  Google Scholar 

  • Ruiz, M.O., Cabezas, J.L., Escudero, I., Coca, J.: Valeric acid extraction with tri-n-butyl phosphate impregnated in a macroporous resin. I. Equilibrium and mass transfer rates. Sep. Sci. Technol. 39, 77–95 (2005)

    Article  Google Scholar 

  • Seo, Y.K., Park, S.B., Park, D.H.: Mesoporous hybrid organosilica containing urethane moieties. J. Solid State Chem. 179, 1285–1288 (2006)

    Article  CAS  Google Scholar 

  • Shea, K.J., Loy, D.A., Webster, O.: Arylsilsesquioxane gels and related materials. New hybrids of organic and inorganic networks. J. Am. Chem. Soc. 114, 6700–6710 (1992) (1992)

    Article  CAS  Google Scholar 

  • Takahashi, H., Ohba, K., Kikuchi, K.I.: Sorption of mono-carboxylic acids by an anion-exchange membrane. Biochem. Eng. J. 16, 311–315 (2003)

    Article  CAS  Google Scholar 

  • Tan, B., Rankin, S.E.: Effects of progressive changes in organoalkoxysilane structure on the gelation and pore structure of templated and non-templated sol–gel materials. J. Non-Cryst. Solids. 352, 5453–5462 (2006)

    Article  CAS  Google Scholar 

  • Thurman, E.M., Malcolm, R.L., Aiken, G.R.: Prediction of capacity factors for aqueous organic solutes adsorbed on a porous acrylic resin. Anal. Chem. 50, 775–779 (1978)

    Article  CAS  Google Scholar 

  • Van Der Voort, P., Esquivel, D., De Canck, E., Goethals, F., Van Driessche, I., Romero-Salguero, F.J.: Periodic mesoporous organosilicas: from simple to complex bridges; A comprehensive overview of functions, morphologies and applications. Chem. Soc. Rev. 42, 3913–3955 (2013)

    Article  Google Scholar 

  • Walcarius, A., Mercier, L.: Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants. J. Mater. Chem. 20, 4478–4511 (2010)

    Article  CAS  Google Scholar 

  • Wang, Z., Luo, Y., Yu, P.: Recovery of organic acids from waste salt solutions derived from the manufacture of cyclohexanone by electrodialysis. J. Membr. Sci. 280, 134–137 (2006)

    Article  CAS  Google Scholar 

  • Wright, J.D., Sommerdijk, N.A.: Sol-Gel Materials: Chemistry and Applications, vol. 4. CRC Press, Boca Rotan (2000)

    Google Scholar 

  • Wu, H.Y., Chen, C.T., Hung, I.M., Liao, C.H., Vetrivel, S., Kao, H.M.: Direct synthesis of cubic benzene-bridged mesoporous organosilica functionalized with mercaptopropyl groups as an effective adsorbent for mercury and silver ions. J. Phys. Chem. C. 114, 7021–7029 (2010)

    Article  CAS  Google Scholar 

  • Wu, H.Y., Shieh, F.K., Kao, H.M., Chen, Y.W., Deka, J.R., Liao, S.H., Wu, K.C.W.: Synthesis, bifunctionalization, and remarkable adsorption performance of benzene-bridged periodic mesoporous organosilicas functionalized with high loadings of carboxylic acids. Chem. Eur. J. 19, 6358–6367 (2013)

    Article  CAS  Google Scholar 

  • Xiong, B., Richard, T.L., Kumar, M.: Integrated acidogenic digestion, carboxylic acid separation by nanofiltration membranes for the lignocellulosic carboxylate platform. J. Membr. Sci. 489, 275–283 (2015)

    Article  CAS  Google Scholar 

  • Yu, L., Guo, Q., Hao, J., Jiang, W.: Recovery of acetic acid from dilute wastewater by means of bipolar membrane electrodialysis. Desalination. 129, 283–288 (2000)

    Article  CAS  Google Scholar 

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Theron and Dorothy Peterson Chemistry Research Fund, The College of Wooster. National Science Foundation Award 0930371.

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  1. Department of Chemistry, The College of Wooster, 943 College Mall, Wooster, OH, 44691, USA

    Paul L. Edmiston, Alyssa R. Gilbert, Zachary Harvey & Noël Mellor

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  1. Paul L. Edmiston
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Correspondence to Paul L. Edmiston.

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The process to prepare swellable organically modified described within has been patented by The College of Wooster.

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Edmiston, P.L., Gilbert, A.R., Harvey, Z. et al. Adsorption of short chain carboxylic acids from aqueous solution by swellable organically modified silica materials. Adsorption 24, 53–63 (2018). https://doi.org/10.1007/s10450-017-9923-0

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