Abstract
Two commercial Ca2+ and NH4 + lignin derivatives were catalytically oxidised and photooxidised both aerobically and in presence of H2O2 (Fenton system), under green conditions (water solution, 20°C, 1 atm), to obtain fractions with reduced degrees of polymerisation. Analyses of the oxidised solutions were carried out using NMR, MS and UV spectrometry. The catalytic and photocatalytic systems used showed satisfactory conservation of the organic material, except for the Fenton system. Lignins showed some mineralisation when irradiated in the presence of H5[PMo10V2O40] × H2O (POM-1), K5[Ru(H2O)PW11O39] (POM-2), K4[SiW12O40]·8H2O (POM-3) and TiO2. When the POMs were used as thermal catalysts, POM-3 was almost inactive, while the reactivities of POM-1 and POM-2 under both thermal and photochemical conditions were comparable, revealing little effect of irradiation on the reaction mechanism. The best compromise appears to be the TiO2 photosystem, which shows low carbon consumption, good preservation of aromatic rings, and greatly reduced mineralisation. Alternatively, POM-1 can be used, and particularly under thermal conditions.
Similar content being viewed by others
References
Anastas, P.T., Warner, J.C.: Green chemistry. Theory and practice. Oxford University Press, New York (2000)
Detroy, R.W., Julian, G.S.T.: Biomass conversion: fermentation chemicals and fuels. Crit. Rev. Microbiol. 10, 203–228 (1982)
Dagley, S.: New perspectives in aromatic catabolism. In: Leisinger, T., Cook, A.M., Hütter, R., Nüesch, J. (eds.) Degradation of xenobiotics and recalcitrant compounds, pp. 181–186. Academic Press, Inc, New York (1981)
Adler, E.: Lignin chemistry—past, present and future. Wood Sci. Technol. 11, 169–218 (1977)
Reale, S., Di Tullio, A., Spreti, N., De Angelis, F.: Mass spectrometry in the biosynthetic and structural investigations of lignin’s. Mass Spectrom. Rev. 23, 87–126 (2004)
Reale, S., Attanasio, F., Spreti, N., De Angelis, F.: Lignin chemistry: biosynthetic study and structural characterisation of coniferyl alcohol oligomers formed in vitro in a micellar environment. Chem. Eur. J. 16, 6077–6087 (2010)
da Costa Sousa, L., Chundawat, S.P.S., Balan, V., Dale, B.E.: ‘Cradle-to-grave’ assessment of existing lignocellulose pretreatment technologies. Curr. Opin. Biotech 20, 339–347 (2009)
Eggleston, G.: Future sustainability of the sugar and sugar-ethanol industries, in ACS symposium series. Am. Chem. Soc. 1058, 1–19 (2010)
Ragauskas, A.J., Williams, C.K., Davison, B.H., Britovsek, G., Cairney, J., Eckert, C.A., Frederick Jr., W.J., Hallett, J.P., Leak, D.J., Liotta, C.L., Mielenz, J.R., Murphy, R., Templer, R., Tschaplinski, T.: The path forward for biofuels and biomaterials. Science 311, 484–489 (2006)
Sun, Y., Cheng, J.: Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresource Thechnol 83, 1–11 (2002)
Yang, B., Wyman, C.E.: Pretreatment: the key to unlocking low-cost cellulosic ethanol. Biofuel. Bioprod. Bior. 2, 26–40 (2008)
Phillips, M., Goss, M.J.: The hydrolysis of lignin with 12% hydrochloric acid. J. Am. Chem. Soc. 54, 3374–3377 (1932)
Goldstein, I.S.: Perspectives on production of phenols and phenolic acids from lignin and bark. Appl. Polym. Symp. 28, 259–267 (1975)
Collinson, S.R., Thielemans, W.: The catalytic oxidation of biomass to new materials focusing on starch, cellulose and lignin. Chem. Commun. 254, 1854–1870 (2010)
Li, J., Gellerstedt, G.: Improved lignin properties and reactivity by modifications in the auto hydrolysis process of aspen wood. Ind. Crops Prod. 27, 175–181 (2008)
Schultz, T.P., Chen, C.L., Goldstein, I.S.: Attempted depolymerization of HCl lignin by catalytic hydrogenolysis. Wood Chem. Technol. 2, 33–46 (1982)
Kakemoto, G., Sagara, H., Suzuki, N., Kachi, S.: Method of manufacturing phenols from lignin. US Patent, 4900873 (1990)
Sales, F.G., Maranhao, L.C.A., Lima Filho, N.M., Abreu, C.A.M.: Kinetic evaluation and modeling of lignin catalytic wet oxidation to selective production of aromatic aldehydes. Ind. Eng. Chem. Res. 45, 6627–6631 (2006)
Ko, J.J., Shimizu, Y., Ikeda, K., Kim, S.K., Park, C.H., Matsui, S.: Biodegradation of high molecular weight lignin under sulfate reducing conditions: lignin degradability and degradation by-products. Bioresour. Technol. 100, 1622–1627 (2009)
Arora, D.S., Sharma, R.K.: Ligninolytic fungal laccases and their biotechnological applications. Appl. Biochem. Biotechnol. 160, 1760–1788 (2010)
Zakzeski, J., Bruijnincx, P.C.A., Jongerius, A.L., Weckhuysen, B.M.: The catalytic valorization of lignin for the production of renewable chemicals. Chem. Rev. 110, 3552 (2010)
Gaspar, A.R., Gamelas, J.A.F., Evtuguin, D.V., Neto, C.P.: Alternatives for lignocellulosic pulp delignification using polyoxometalates and oxygen: a review. Green Chem. 9, 717–730 (2007)
Portjanskaja, E., Stepanova, K., Klauson, D., Preis, S.: The influence of titanium dioxide modifications on photocatalytic oxidation of lignin and humic acids. Catal. Today 144, 26–30 (2009)
Makhotkina, O.A., Preis, S.V., Parkhomchuk, E.V.: Water delignification by advanced oxidation processes: homogeneous and heterogeneous Fenton and H2O2 photo-assisted reactions. Appl. Catal. B Environ. 84, 821–826 (2008)
Weinstock, I.A., Atalla, R.H., Reiner, R.S., Moen, M.A., Hammel, K.E., Houtman, C.J., Hill, C.L., Harrup, M.K.: A new environmentally benign technology for transforming wood pulp into paper. Engineering polyoxometalate as catalysts for multiple processes. J. Mol. Catal. A Chem. 116, 59–84 (1997)
Kim, Y.S., Chang, H., Kadla, J.F.: Polyoxometalate (POM) oxidation of milled wood lignin (MWL). J. Wood Chem. Technol. 27, 225–241 (2007)
Yokoyama, T., Chang, H., Reiner, R.S., Atalla, R.H., Weinstock, I.A., Kadla, J.F.: Polyoxometalate oxidation of non-phenolic lignin subunits in water: effect of substrate structure on reaction kinetics. Holzforschung 58, 116–121 (2004)
Bujanovic, B., Reiner, R.S., Ralph, S.A., Atalla, R.H.: Polyoxometalate delignification of Birch Kraft pulp and effect on residual lignin. J. Wood Chem. Technol. 31, 121–141 (2011)
Gaspar, A.R., Evtuguin, D.V., Neto, C.P.: Polyoxometalate-catalyzed oxygen delignification of Kraft pulp: a pilot-plant experience. Ind. Eng. Chem. Res. 43, 7754–7761 (2004)
Sun, N., Jiang, X., Maxim, M.L., Metlen, A., Rogers, R.D.: Use of polyoxometalate catalysts in ionic liquids to enhance the dissolution and delignification of woody biomass. Chem. Sus. Chem. 4, 65–73 (2011)
Voitl, T., von Rohr, P.R.: Oxidation of lignin using aqueous polyoxometalates in the presence of alcohols. Chem. Sus. Chem. 1, 763–769 (2008)
Tsigdinos, G.A., Hallada, C.J.: Molybdovanadophosphoric acids and their salts. I. Investigation of methods of preparation and characterization. Inorg. Chem. 7, 437–441 (1968)
Bressan, M., Forti, L., Ghelfi, F., Morvillo, A.: Ruthenium(II)-catalyzed oxidation of alcohols by persulfate. J. Mol. Catal. 79, 85–93 (1993)
Pope, M.T., Varga Jr., G.M.: Heteropoly blues. I. Reduction stoichiometries and reduction potentials of some 12-tungstates. Inorg. Chem. 5, 1249–1254 (1966)
Brevard, C., Schimpf, R., Tourne, G., Tourne, C.M.: Tungsten-183 NMR: a complete and unequivocal assignment of the tungsten–tungsten connectivities in heteropolytungstates via two dimensional 183W NMR techniques. J. Am. Chem. Soc. 105, 7059–7063 (1983)
Evans, I.P., Spencer, A., Wilkinson, G.: Dichlorotetrakis(dimethyl sulphoxide)ruthenium(II) and its use as a source material for some new ruthenium(II) complexes. J. Chem. Soc. Dalton Trans. 204–209 (1973)
Chen, C., Zhao, W., Lei, P., Zhao, J., Serpone, N.: Photosensitized degradation of dyes in polyoxometalate solutions versus TiO2 dispersions under visible-light irradiation: mechanistic implications. Chem. Eur. J. 10, 1956–1965 (2004)
Pettersson, L., Andersson, I., Selling, A., Grate, J.H.: Multicomponent polyanions. 46. Characterization of the isomeric Keggin decamolybdodivanadophosphate ions in aqueous solution by 31P and 51V NMR. Inorg. Chem. 33, 982–993 (1994)
Cho, D.W., Parthasarathi, R., Pimentel, A.S., Maestas, G.D., Park, H.J., Yoon, U.C., Dunaway Mariano, D., Gnanakaran, S., Langan, P., Mariano, P.S.: Nature and kinetic analysis of carbon–carbon bond fragmentation reactions of cation radicals derived from SET-oxidation of lignin model compounds. J. Org. Chem. 75, 6549–6552 (2010)
Cho, D.W., Latham, J.A., Park, H.J., Yoon, U.C., Langan, P., Dunaway Mariano, D., Mariano, P.S.: Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon–carbon bond fragmentation reactions of tetrameric lignin model compounds. J. Org. Chem. 76, 2840–2852 (2011)
Tanaka, K., Calanag, R.C.R., Hisanaga, T.: Photocatalyzed degradation of lignin on TiO2. J. Mol. Catal. A Chem. 138, 287–294 (1999)
Spiccia, L., Deacon, G.B., Kepert, C.M.: Synthetic routes to homoleptic and heteroleptic ruthenium(II) complexes incorporating bidentate imine ligands. Coord. Chem. Rev. 248, 1329–1341 (2004)
Bressan, M., d’Alessandro, N., Liberatore, L., Morvillo, A.: Ruthenium catalyzed oxidative dehalogenation of organics. Coord. Chem. Rev. 185–186, 385–402 (1999)
Arslan-Alaton, I.: Homogenous photocatalytic degradation of a disperse dye and its dye bath analogue by silicadodecatungstic acid. Dyes Pigment 60, 167–176 (2004)
Acknowledgments
The authors are grateful to the “Consorzio di Ricerca per l’Innovazione Tecnologica, la Qualità e la Sicurezza degli Alimenti S.C.R.L”. (DM MIUR n. 28497/2006), and to the “G. D’Annunzio” University for financial support.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Tonucci, L., Coccia, F., Bressan, M. et al. Mild Photocatalysed and Catalysed Green Oxidation of Lignin: A Useful Pathway to Low-Molecular-Weight Derivatives. Waste Biomass Valor 3, 165–174 (2012). https://doi.org/10.1007/s12649-011-9102-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12649-011-9102-6