Biofuel Research Journal

Biofuel Research Journal

Stirred and non-stirred lignin solvolysis with formic acid in aqueous and ethanolic solvent systems at different levels of loading in a 5-L reactor

Document Type : Research Paper

Authors
Solmaz Ghoreishi 1
Tanja Barth 1
Hailegebrel Derribsa 2
1 Department of Chemistry, University of Bergen, Norway, Allégaten 41, N-5007 Bergen, Norway.
2 Mjøsvegen 6J, 2380 Brumunddal, Norway.
10.18331/BRJ2019.6.1.5
Abstract
Lignin polymer is biologically and chemically stable and requires highly vigorous conditions for de-polymerization, and subsequent stabilization of the monomeric conversion products to prevent re-polymerization and char production. The Lignin-to-Liquid (LtL) process is a solvolytic conversion of lignin with formic acid. Formic acid has been shown to both catalyze the de-polymerization and supply hydrogen that stabilizes the de-polymerization products. In this paper, lignin from Eucalyptus wood was used as the feedstock, and the LtL-process was performed in both aqueous and ethanolic solvent systems. The experimental variables were different levels of loading in the reactor, stirred and non-stirred conditions, and different reaction temperatures. The bio-oil consisted mostly of phenolic compounds, and the bio-oil yields differed with type of the solvent used, level of loading in the reactor, stirring condition, and operating temperature. More than 55 wt.% of the lignin was recovered as bio-oil at 320 °C at stirred conditions when the reactor was loaded at high level. Overall, the ethanolic solvent together with maximum level of loading in the reactor under stirred condition resulted in the highest bio-oil yield. Elemental balance data for bio-oil and char yields and the molecular composition of the bio-oils were also investigated using, respectively, elemental analysis and GC-MS. Finally, principal component analysis was used as well to systematically explore the relationship between the bio-oil and char yields and the reaction conditions.

Graphical Abstract

Stirred and non-stirred lignin solvolysis with formic acid in aqueous and ethanolic solvent systems at different levels of loading in a 5-L reactor

Highlights

  • Oil yields increased and char yields decreased with a high loading in the reactor at stirred condition.
  • In comparison with water-based system, ethanol-based system tended to give higher oil yields.
  • Oil yields decreased, more or less, with increasing reaction temperature regardless of solvent type.
  • The bio-oils from ethanol-based experiments had the highest H/C and O/C ratios.
  • The bio-oil composition produced in each solvent system was quite stable and independent of other reaction conditions.

 

Keywords
Lignin de-polymerization
Stabilization
Lignin-to-Liquid
5-L Scale
Stirring
 

On the cover


One of the main concerns for producing biofuels from lignin polymer is its recalcitrant nature against biological/chemical depolymerization. The lignin-to-liquid (LtL) process could be a viable route to overcome this challenge. During this process, lignin polymer is depolymerized in a high-temperature solvolytic aqueous environment in the presence of a hydrogen-donor catalyst such as formic acid. In this issue of Biofuel Research Journal, a group of Norwegian researchers shed light on the effects of different variables (i.e., feeding reactor loading, stirred and non-stirred conditions, and reaction temperature) on the performance of water/ethanolic solvolytic LtL-process with formic acid. They emphasize that the stirred condition with large feeding loadings and at high temperatures would be more promising for lignin-oriented biofuel production at large scale. Cover art by BiofuelResJ.
[1] Azadi, P., Inderwildi, O.R., Farnood, R., King, D.A., 2013. Liquid fuels, hydrogen and chemicals from lignin: a critical review. Renew. Sust. Energy Rev. 21, 506-523.
[2] Bengoechea, M.O., Hertzberg, A., Miletić, N., Arias, P.L., Barth, T., 2015. Simultaneous catalytic de-polymerization and hydrodeoxygenation of lignin in water/formic acid media with Rh/Al2O3, Ru/Al2O3 and Pd/Al2O3 as bifunctional catalysts. J. Anal. Appl. Pyrolysis. 113, 713-722.
[3] Bu, Q., Lei, H., Zacher, A.H., Wang, L., Ren, S., Liang, J., Wei, Y., Liu, Y., Tang, J., Zhang, Q., Ruan, R., 2012. A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis. Bioresour. Technol. 124, 470-477.
[4] Carlson, R., Carlson, J.E., 2005. Design and optimization in organic synthesis. Elsevier, Amsterdam, The Netherlands. 24.
[5] Cherubini, F., 2010. The biorefinery concept: using biomass instead of oil for producing energy and chemicals. Energy Convers. Manage. 51(7), 1412-1421.
[6] Cherubini, F., Jungmeier, G., 2010. LCA of a biorefinery concept producing bioethanol, bioenergy, and chemicals from switchgrass. Int. J. Life Cycle Assess. 15(1), 53-66.
[7] Creutzig, F., Ravindranath, N.H., Berndes, G., Bolwig, S., Bright, R., Cherubini, F., Chum, H., Corbera, E., Delucchi, M., Faaji, A., Fargione, J., Haberl, H., Heath, G., Lucon, O., Pelvin, R., Popp, A., Robledo-Abad, C., Rose, S., Smith, P., Stormmans, A., Suh, S., Masera, O., 2015. Bioenergy and climate change mitigation: an assessment. GCB Bioenergy. 7(5), 916-944.
[8] Gasson, J.R., Kleinert, M., Barth, T., Forchheim, D., Sahin, E., Kruse, A., Eide, I., 2010. Lignin solvolysis: upscaling of the Lignin-to-Liquid conversion process towards technical applicability. The 18th European Biomass Conference and Exhibition, Lyon, France. 3-12.
[9] Gasson, J.R., Forchheim, D., Sutter, T., Hornung, U., Kruse, A., Barth, T., 2012. Modeling the lignin degradation kinetics in an ethanol/formic acid solvolysis approach. part 1. kinetic model development. Ind. Eng. Chem. Res. 51(32), 10595-10606.
[10] Gerber, L., Gassner, M., Maréchal, F., 2011. Systematic integration of LCA in process systems design: application to combined fuel and electricity production from lignocellulosic biomass. Comput. Chem. Eng. 35(7), 1265-1280.
[11] Gerssen-Gondelach, S.J., Saygin, D., Wicke, B., Patel, M.K., Faaij, A.P.C., 2014. Competing uses of biomass: assessment and comparison of the performance of bio-based heat, power, fuels and materials. Renew. Sust. Energy Rev. 40, 964-998.
[12] Holmelid, B., Kleinert, M., Barth, T., 2012. Reactivity and reaction pathways in thermochemical treatment of selected lignin-like model compounds under hydrogen rich conditions. J. Anal. Appl. Pyrolysis. 98, 37-44.
[13] Kim, J.Y., Oh, S., Hwang, H., Cho, T.S., Choi, I.G., Choi, J.W., 2013. Effects of various reaction parameters on solvolytical depolymerization of lignin in sub- and supercritical ethanol. Chemosphere. 93(9), 1755-1764.
[14] Kleinert, M., Barth, T., 2008. Towards a lignincellulosic biorefinery: direct one-step conversion of lignin to hydrogen-enriched biofuel. Energy Fuels. 22(2), 1371-1379.
[15] Kleinert, M., Gasson, J.R., Barth, T., 2009. Optimizing solvolysis conditions for integrated depolymerisation and hydrodeoxygenation of lignin to produce liquid biofuel. J. Anal. Appl. Pyrolysis. 85(1-2), 108-117.
[16] Kristianto, I., Limarta, S.O., Lee, H., Ha, J.M., Suh, D.J., Jae, J., 2017. Effective depolymerization of concentrated acid hydrolysis lignin using a carbon-supported ruthenium catalyst in ethanol/formic acid media. Bioresour. Technol. 234, 424-431.
[17] Liguori, L., Barth, T., 2011. Palladium-Nafion SAC-13 catalysed depolymerisation of lignin to phenols in formic acid and water. J. Anal. Appl. Pyrolysis. 92(2), 477-484.
[18] Liu, W.J., Jiang, H., Yu, H.Q., 2015. Thermochemical conversion of lignin to functional materials: a review and future directions. Green Chem. 17(11), 4888-4907.
[19] Løhre, C., Barth, T., Kleinert, M., 2016. The effect of solvent and input material pretreatment on product yield and composition of bio-oils from lignin solvolysis. J. Anal. Appl. Pyrolysis. 119, 208-216.
[20] Løhre, C., Kleinert, M., Barth, T., 2017. Organosolv extraction of softwood combined with lignin-to-liquid solvolysis as a semi-continuous percolation reactor. Biomass Bioenergy. 99, 147-155.
[21] Mood, S.H., Golfeshan, A.H., Tabatabaei, M., Jouzani, G.S., Najafi, G.H., Gholami, M., Ardjmand, M., 2013. Lignocellulosic biomass to bioethanol, a comprehensive review with a focus on pretreatment. Renew. Sust. Energy Rev. 27, 77-93.
[22] Nigam, P.S., Singh, A., 2011. Production of liquid biofuels from renewable resources. Prog. Energy Combust. Sci. 37(1), 52-68.
[23] Oregui-Bengoechea, M., Gandarias, I., Arias, P.L., Barth, T., 2017. Unravelling the role of formic acid and the type of solvent in the catalytic conversion of lignin: a holistic approach. ChemSusChem. 10(4), 754-766.
[24] Singh, A., Pant, D., Korres, N.E., Nizami, A.S., Prasad, S., Murphy, J.D., 2010. Key issues in life cycle assessment of ethanol production from lignocellulosic biomass: challenges and perspectives. Bioresour. Technol. 101(13), 5003-5012.
[25] Singh, R., Prakash, A., Dhiman, S.K., Balagurumurthy, B., Arora, A.K., Puri, S.K., Bhaskar, T., 2014. Hydrothermal conversion of lignin to substituted phenols and aromatic ethers. Bioresour. Technol. 165, 319-322.
[26] Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., 2008. Determination of ash in biomass, laboratory analytical procedure (LAP), Golden, CO, USA. NREL/TP-510-42622.
[27] Tanaka, K., Berntsen, T., Fuglestvedt, J.S, Rypdal, K., 2012. Climate effects of emission standards: the case for gasoline and diesel cars. Environ. Sci. Technol. 46(9), 5205-5213.
[28] Zhang, X., Tu, M., Paice, M.G., 2011. Routes to potential bioproducts from lignocellulosic biomass lignin and hemicelluloses. BioEnergy Res. 4(4), 246-257.
Biofuel Research Journal
Volume 6, Issue 1 - Serial Number 1
Winter 2019
Pages 937-946