Abstract
Pretreatment is one of the key steps for the utilization of lignocellulosic biomasses via biorefinery. Green liquor (GL) pretreatment has been considered as an effective approach to improve the subsequent enzymatic saccharification. For the better understanding of the structural changes of lignin in GL pretreatment, milled wood lignin (MWL) samples isolated from untreated and GL-pretreated poplar by the Björkman method were characterized by means of gel permeation chromatography (GPC), alkaline nitrobenzene oxidation (NBO), Fourier transform-infrared (FT-IR) spectroscopy, and quantitative 13C and 2D heteronuclear single quantum coherence nuclear magnetic resonance (HSQC NMR). The results indicate that the average molecular weight of MWLs decreased after GL pretreatment. Surprisingly, more guaiacyl-propane units are extracted under mild alkaline conditions than syringyl-propane units, which results in a higher condensation degree and higher S/G ratios of MWLs isolated from GL-pretreated poplars. The amount of β–O–4 structures decreased, while the β–β and β-5 structures increased after GL pretreatment. The structure of esterified p-hydroxybenzoic acid was detected in poplar MWL sample and it degraded obviously after GL pretreatment.
Funding source: National Natural Science Foundation of China
Award Identifier / Grant number: 31370571
Award Identifier / Grant number: 31400514
Funding statement: This work was supported by the National Key Technology Research and Development Program of China (grant number 2015BAD15B09); the National Natural Science Foundation of China (grant numbers 31370571, 31400514); the Specialized Research Fund for the Doctoral Program of Higher Education, China (grant number 20133204110006); and the Priority Academic Program Development of Jiangsu Higher Education Institutions, China. The authors also would like to thank Dr. Jialong Wen of Institute of Biomass Chemistry and Technology, Beijing Forestry University for the NMR analysis.
Acknowledgments
This work was supported by the National Key Technology Research and Development Program of China (grant number 2015BAD15B09); the National Natural Science Foundation of China (grant numbers 31370571, 31400514); the Specialized Research Fund for the Doctoral Program of Higher Education, China (grant number 20133204110006); and the Priority Academic Program Development of Jiangsu Higher Education Institutions, China. The authors also would like to thank Dr. Jialong Wen of Institute of Biomass Chemistry and Technology, Beijing Forestry University for the NMR analysis.
References
Argyropoulos, D.S., Sadeghifar, H., Cui, C., Sen, S. (2014) Synthesis and characterization of poly(arylene ether sulfone) kraft lignin heat stable copolymers. ACS Sustain. Chem. Eng. 2:264–271.10.1021/sc4002998Suche in Google Scholar
Björkman, A. (1956) Studies on the finely divided wood. Part I. Extraction of lignin with neutral solvents. Svensk Paperstid. 59:477–485.Suche in Google Scholar
Blumentritt, M., Gardner, D.J., Cole, B.J.W., Shaler, S.M. (2016) Influence of hot-water extraction on ultrastructure and distribution of glucomannans and xylans in poplar xylem as detected by gold immunolabeling. Holzforschung 70:243–252.10.1515/hf-2015-0030Suche in Google Scholar
Capanema, E.A., Balakshin, M.Y., Kadla, J.F. (2005) Quantitative characterization of a hardwood milled wood lignin by nuclear magnetic resonance spectroscopy. J. Agric. Food Chem. 53:9639–9649.10.1021/jf0515330Suche in Google Scholar
Capanema, E.A., Balakshin, M.Y., Kadla, J.F., Chang, H.-M. (2007) On isolation of milled wood lignin from eucalyptus wood. O Papel N5:74–79.Suche in Google Scholar
Chen, C.-L. (1992) Nitrobenzene and cupric oxide oxidations. In: Methods in Lignin Chemistry. Eds. Lin, D.S.Y., Dence, C.W., Springer-Verlag, Berlin. pp. 301–321.10.1007/978-3-642-74065-7_21Suche in Google Scholar
del Río, J.C., Rencoret, J., Marques, G., Li, J.-B., Gellerstedt, G., Jiménez-Barbero, J., Martínez, Á.T., Gutiérrez, A. (2009) Structural characterization of the lignin from jute (Corchorus capsularis) fibers. J. Agric. Food Chem. 57:10271–10281.10.1021/jf900815xSuche in Google Scholar
Díaz, M.J., Huijgen, W.J.J., van der Laan, R.R., Reith, J.H., Cara, C., Castro, E. (2011) Organosolv pretreatment of olive tree biomass for fermentable sugars. Holzforschung 65:177–183.10.1515/hf.2011.030Suche in Google Scholar
Faix, O. (1991) Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 45:21–28.10.1515/hfsg.1991.45.s1.21Suche in Google Scholar
Fang, S., Xu, X., Lu, S., Tang, L. (1999) Growth dynamics and biomass production in short-rotation poplar plantations: 6-year results for three clones at four spacings. Biomass Bioenerg. 17:415–425.10.1016/S0961-9534(99)00060-4Suche in Google Scholar
Gellerstedt, G., Lindfors, E.L. (1984) Structural changes in lignin during kraft pulping. Holzforschung 38:151–158.10.1515/hfsg.1984.38.3.151Suche in Google Scholar
Gellerstedt, G., Gustafsson, K., Labidi, A., Pla, F. (1992) Alkaline delignification of hardwoods in a flow-through reactor working at a low residence time – part IV. Characterization of lignins by oxidative degradation and Aminolysis. Holzforschung 46:199–204.10.1515/hfsg.1992.46.3.199Suche in Google Scholar
Govender, M., Bush,T., Spark, A., Bose, S.K., Francis, R.C. (2009) An accurate and non-labor intensive method for the determination of syringyl to guaiacyl ratio in lignin. Bioresource Technol. 100:5834–5839.10.1016/j.biortech.2009.06.009Suche in Google Scholar PubMed
Gu, F., Yang, L., Jin, Y., Han, Q., Chang, H.-M., Jameel, H., Phillips, R. (2012) Green liquor pretreatment for improving enzymatic hydrolysis of corn stover. Bioresource Technol. 124:299–305.10.1016/j.biortech.2012.08.054Suche in Google Scholar PubMed
Gu, F., Wang, W., Jing, L., Jin, Y. (2013) Effects of green liquor pretreatment on the chemical composition and enzymatic digestibility of rice straw. Bioresource Technol. 149:375–382.10.1016/j.biortech.2013.09.064Suche in Google Scholar PubMed
Gu, F., Posoknistakul, P., Shimizu, S., Yokoyama, T., Jin, Y., Matsumoto, Y. (2014) Synergistic contribution of hydrosulfide and carbonate anions to the β–O–4 bond cleavage of lignin model compounds in a green liquor pretreatment for enzymatic hydrolysis of lignocellulosic materials. J. Wood Sci. 60:346–352.10.1007/s10086-014-1411-5Suche in Google Scholar
Hallac, B.B., Pu, Y., Ragauskas, A.J. (2010) Chemical transformations of Buddleja davidii lignin during ethanol organosolv pretreatment. Energy Fuels 24:2723–2732.10.1021/ef901556uSuche in Google Scholar
Ilharco, L.M., Brito de Barros, R. (2000) Aggregation of pseudoisocyanine iodide in cellulose acetate films: structural characterization by FTIR. Langmuir 16:9331–9337.10.1021/la000579eSuche in Google Scholar
Jiang, B., Wang, W., Gu, F., Cao, T., Jin, Y. (2016) Comparison of the substrate enzymatic digestibility and lignin structure of wheat straw stems and leaves pretreated by green liquor. Bioresource Technol. 199:181–187.10.1016/j.biortech.2015.08.104Suche in Google Scholar PubMed
Jin, Y., Jameel, H., Chang, H.-M., Phillips, R. (2010) Green liquor pretreatment of mixed hardwood for ethanol production in a repurposed kraft pulp mill. J. Wood Chem. Technol. 30:86–104.10.1080/02773810903578360Suche in Google Scholar
Kirsch, C., Zetzl, C., Smirnova, I. (2011) Development of an integrated thermal and enzymatic hydrolysis for lignocellulosic biomass in fixed-bed reactors. Holzforschung 65:483–489.10.1515/hf.2011.061Suche in Google Scholar
Lapierre, C., Lallemand, J.Y., Monties, B. (1982) Evidence of poplar lignin heterogeneity by combination of 13C and 1H NMR spectroscopy. Holzforschung 36:275–282.10.1515/hfsg.1982.36.6.275Suche in Google Scholar
Lapierre, C., Monties, B., Guittet, E., Lallemand, J. (1984) Photosynthetically 13C-labelled poplar lignins: -13C NMR experiments. Holzforschung 38:333–342.10.1515/hfsg.1984.38.6.333Suche in Google Scholar
Li, X., Weng, J.-K., Chapple, C. (2008) Improvement of biomass through lignin modification. Plant J. 54:569–581.10.1111/j.1365-313X.2008.03457.xSuche in Google Scholar PubMed
Lu, F.-C., Ralph, J., Morreel, K., Messens, E., Boerjan, W. (2004) Preparation and relevance of a cross-coupling product between sinapyl alcohol and sinapyl p-hydroxybenzoate. Org. Biomol. Chem. 2:2888–2890.10.1039/b411428kSuche in Google Scholar PubMed
Lundquist, K. (1992) Proton (1H) NMR spectroscopy. In: Methods in Lignin Chemistry. Eds. Lin, D.S.Y., Dence, C.W., Springer-Verlag, Berlin. pp. 242–249.10.1007/978-3-642-74065-7_17Suche in Google Scholar
Martín, C., Puls, J., Schreiber, A., Saake, B. (2013) Optimization of sulfuric acid-assisted glycerol pretreatment of sugarcane bagasse. Holzforschung 67:523–530.10.1515/hf-2012-0179Suche in Google Scholar
Meng, X., Geng, W., Ren, H., Jin, Y., Chang, H.-M., Jameel, H. (2014) Enhancement of enzymatic saccharification of poplar by green liquor pretreatment. Bioresources 9:3236–3247.10.15376/biores.9.2.3236-3247Suche in Google Scholar
Min, D., Li, Q., Jameel, H., Chiang, V., Chang, H.-M. (2011) Comparison of pretreatment protocols for cellulase-mediated saccharification of wood derived from transgenic low-xylan lines of cottonwood (P. trichocarpa). Biomass Bioenerg. 35:3514–3521.10.1016/j.biombioe.2011.04.034Suche in Google Scholar
Muzamal, M., Jedvert, K., Theliander, H., Rasmuson, A. (2015) Structural changes in spruce wood during different steps of steam explosion pretreatment. Holzforschung 69:61–66.10.1515/hf-2013-0234Suche in Google Scholar
Morreel, K., Ralph, J., Kim, H., Lu, F.-C., Goeminne, G., Ralph, S., Messens, E., Boerjan, W. (2004) Profiling of oligolignols reveals monolignol coupling conditions in lignifying poplar xylem. Plant Physiol. 136:3537–3549.10.1104/pp.104.049304Suche in Google Scholar PubMed PubMed Central
Park, S.J., Um, B.H. (2014) Optimization study on acid hydrolysis of hardwood-derived hemicellulosic extract for alcohol fermentation using response surface methodology. Holzforschung 69:135–141.10.1515/hf-2014-0064Suche in Google Scholar
Pinto, P.C., Evtugiun, D.V., Neto, C.P., Silvestre, A.J.D., Amado, F.M.L. (2002) Behaviour of Eucalyptus grandis lignin during kraft pulping. II. Analysis by NMR, ESI/MS, and GPC. J. Wood Chem. Technol. 22:109–125.10.1081/WCT-120013356Suche in Google Scholar
Rahikainen, J., Mikander, S., Marjamaa, K., Tamminen, T., Lappas, A., Viikari, L., Kruus, K. (2011) Inhibition of enzymatic hydrolysis by residual lignins from softwood – study of enzyme binding and inactivation on lignin-rich surface. Biotechnol. Bioeng. 108: 2823–2834.10.1002/bit.23242Suche in Google Scholar PubMed
Rencoret, J., Marques, G., Gutiérrez, A., Nieto, L., Jiménez-Barbero, J., Martínez, Á.T., Del Río, J.C. (2009) Isolation and structural characterization of the milled-wood lignin from Paulownia fortunei wood. Ind. Crops Prod. 30:137–143.10.1016/j.indcrop.2009.03.004Suche in Google Scholar
Rencoret, J., Del Río, J.C., Gutiérrez, A., Martínez, Á.T., Li, S., Parkås, J., Lundquist, K. (2011) Origin of the acetylated structures present in white birch (Betula pendula Roth) milled wood lignin. Wood Sci. Technol. 46:459–471.10.1007/s00226-011-0417-zSuche in Google Scholar
Santos, R.B., Capanema, E.A., Balakshin, M.Y., Chang, H.-M. Jameel, H. (2012) Lignin structural variation in hardwood species. J. Agric. Food Chem. 60:4923–4930.10.1021/jf301276aSuche in Google Scholar PubMed
Schütt, F., Puls, J., Saake, B. (2011) Optimization of steam pretreatment conditions for enzymatic hydrolysis of poplar wood. Holzforschung 65:453–459.10.1515/hf.2011.066Suche in Google Scholar
Schütt, F., Haas, N.P., Dehne, L., Koch, G., Janzon, R., Saake, B. (2013) Steam pretreatment for enzymatic hydrolysis of poplar wood: comparison of optimal conditions with and without SO2 impregnation. Holzforschung 67:9–17.10.1515/hf-2012-0076Suche in Google Scholar
Sette, M., Wechselberger, R., Crestini, C. (2011) Elucidation of lignin structure by quantitative 2D NMR. Chem. -Eur. J. 17:9529–9535.10.1002/chem.201003045Suche in Google Scholar PubMed
Shi, Z., Cai, Z., Wang, S., Zhong, Q., Bozell, J.J. (2013) Short-time ultrasonication treatment in enzymatic hydrolysis of biomass. Holzforschung 67:891–897.10.1515/hf-2013-0024Suche in Google Scholar
Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., Crocker, D. (2008) Determination of structural carbohydrates and lignin in biomass. Laboratory Analytical Procedure, NREL Report No. TP–510–42618.Suche in Google Scholar
Sugimoto, T., Magara, K., Hosoya, S., Oosawa, S., Shimoda, T., Nishibori, K. (2009) Ozone pretreatment of lignocellulosic materials for ethanol production: Improvement of enzymatic susceptibility of softwood. Holzforschung 63:537–543.10.1515/HF.2009.091Suche in Google Scholar
Villaverde, J.J., Li, J., Ek, M., Ligero, P., de Vega, A. (2009) Native lignin structure of Miscanthus x giganteus and its changes during acetic and formic acid fractionation. J. Agric. Food Chem. 57:6262–6270.10.1021/jf900483tSuche in Google Scholar PubMed
Wen, J.-L., Sun, S.-L., Xue, B.-L., Sun, R.-C. (2013a) Quantitative structures and thermal properties of Birch lignins after ionic liquid pretreatment. J. Agric. Food Chem. 61:635–645.10.1021/jf3051939Suche in Google Scholar PubMed
Wen, J.-L., Sun, S.-L., Xue, B.-L., Sun, R.-C. (2013b) Unmasking the structural features and property of lignin from bamboo. Ind. Crops Prod. 42:1332–343.10.1016/j.indcrop.2012.05.041Suche in Google Scholar
Xu, F., Jiang, J.-X., Sun, R.C., Tang, J.-N., Sun, J.-X., Su, Y.-Q. (2008) Fractional isolation and structural characterization of mild ball-milled lignin in high yield and purity from Eucommia ulmoides Oliv. Wood Sci. Technol. 42:211–226.10.1007/s00226-007-0162-5Suche in Google Scholar
Yuan, T.-Q., Sun, S.-N., Xu, F., Sun, R.-C. (2011a) Isolation and physicochemical characterization of lignins from ultrasound irradiated fastgrowing poplar wood. Bioresources 6:414–433.10.15376/biores.6.1.414-433Suche in Google Scholar
Yuan, T.-Q., Sun, S.-N., Xu, F., Sun, R.-C. (2011b) Structural characterization of lignin from triploid of Populus tomentosa Carr. J. Agric. Food Chem. 59:6605–6615.10.1021/jf2003865Suche in Google Scholar PubMed
Zhou, H., Zhu, J.Y., Gleisner, R., Qiu, X., Horn, E., Negrón, J. (2016) Pilot-scale demonstration of SPORL for bioconversion of lodgepole pine to bioethanol and lignosulfonate. Holzforschung 70:21–30.10.1515/hf-2014-0332Suche in Google Scholar
©2017 Walter de Gruyter GmbH, Berlin/Boston
Artikel in diesem Heft
- Frontmatter
- Original Articles
- Effects of hot water extraction (HWE) of Douglas fir as a pre-process for the sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL)
- Structural characteristics of milled wood lignin (MWL) isolated from green liquor (GL) pretreated poplar (Populus deltoides)
- TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds
- Microstructure of chemically modified wood using X-ray computed tomography in relation to wetting properties
- The effects of thermal treatment on the nanomechanical behavior of bamboo (Phyllostachys pubescens Mazel ex H. de Lehaie) cell walls observed by nanoindentation, XRD, and wet chemistry
- Assessing specific gravity of young Eucalyptus plantation trees using a resistance drilling technique
- A novel device to measure gaseous permeability over a wide range of pressures: characterisation of slip flow for Norway spruce, European beech, and wood-based materials
- Stress relaxation of composites made of polypropylene and organo-montmorillonite modified wood flour during water immersion
- Sorption/desorption hysteresis revisited. Sorption properties of Pinus pinea L. analysed by the parallel exponential kinetics and Kelvin-Voigt models
- Effect of exogenous IAA on tension wood formation by facilitating polar auxin transport and cellulose biosynthesis in hybrid poplar (Populus deltoids × Populus nigra) wood
Artikel in diesem Heft
- Frontmatter
- Original Articles
- Effects of hot water extraction (HWE) of Douglas fir as a pre-process for the sulfite pretreatment to overcome recalcitrance of lignocellulose (SPORL)
- Structural characteristics of milled wood lignin (MWL) isolated from green liquor (GL) pretreated poplar (Populus deltoides)
- TEMPO-mediated electro-oxidation reactions of non-phenolic β-O-4-type lignin model compounds
- Microstructure of chemically modified wood using X-ray computed tomography in relation to wetting properties
- The effects of thermal treatment on the nanomechanical behavior of bamboo (Phyllostachys pubescens Mazel ex H. de Lehaie) cell walls observed by nanoindentation, XRD, and wet chemistry
- Assessing specific gravity of young Eucalyptus plantation trees using a resistance drilling technique
- A novel device to measure gaseous permeability over a wide range of pressures: characterisation of slip flow for Norway spruce, European beech, and wood-based materials
- Stress relaxation of composites made of polypropylene and organo-montmorillonite modified wood flour during water immersion
- Sorption/desorption hysteresis revisited. Sorption properties of Pinus pinea L. analysed by the parallel exponential kinetics and Kelvin-Voigt models
- Effect of exogenous IAA on tension wood formation by facilitating polar auxin transport and cellulose biosynthesis in hybrid poplar (Populus deltoids × Populus nigra) wood