Hydrothermal carbonization of biomass

1. Institute for Technology of Nuclear and Other Mineral Raw Materials, Belgrade, Serbia Hydrothermal carbonization of biomass Dr Marija Mihajlović “Development of technologies and products based on mineral raw materials and waste biomass with the aim of protecting resources for the safe food production “ Project TR31003 financed bythe Serbian Ministry of Education, Science and Technological Development

2. Our project team has continuity in development of new materials: based on natural and modified aluminosilicates (zeolite, bentonite, diatomite)and raw industrial and agricultural waste biomass (lignocelulosic) • Biosorbents (heavy metals, mycotoxins, dyes)*,**,***,**** • Fertilizers **** • Feed supplements Peach stone * Apricot stone Corn silk ** Corn cob Grape pomace Eurasian water-milfoil*** (Myriophylumspicatum) Miscanthus × giganteus Paulownia elongata • *Lopičić Z. Stojanović M. Marković S. Milojković J., Mihajlović M., Kaluđerović Radoičić T., Kijevčanin M. Effects of different mechanical treatments on structural changes of lignocellulosic waste biomass and subsequent Cu(II) removal kinetics, Arabian Journal of Chemistry, 2016, In Press • ***Petrović M., Šoštаrić T., Stojаnović M., Milojković J., Mihаjlović M., Stаnojević M., Stаnković s., Removаl of Pb2+ ions by rаw Corn silk (Zeа Mаys L. ) аs а novel biosorbent, - Journаl of the Tаiwаn Institute of Chemicаl Engineers, • ****Milojković J.V., Mihаjlović M.L., Stojаnović M.D., Lopičić Z.R., Petrović M.S., Šoštаrić T.D., Ristić M.Đ.: Pb(II) removаl from аqueous solution by Myriophyllum spicаtum аnd its compost: equilibrium, kinetic аnd thermodynаmic study, - Journаl of Chemicаl Technology & Biotechnology, 2014, 89(5), pp. 662–670 • ***** Mihаjlović M., Perišić N., Pezo L., Stojаnović M., Milojković J., Lopičić Z., Petrović M.Utilizаtion of Phosphаte Rock from Lisinа for Direct Applicаtion: Releаse of Plаnt Nutrients in the Exchаnge-Fertilizer Mixtures, Journаl of Agriculturаl аnd Food Chemistry, 2014, 62(41), pp 9965–9973.

3. Hydrothermal carbonization-HTC (Wet pyrolysis) • Process proposed in the early 20thCentury *, as a simulation of the natural formation of coal + Biomassand biowaste • The precursors are readily available, cheap, and renewable • Process is “green” , simple and efficient • Wet biomass load • Usage of unconventional biomasses • No CH4or CO2 release into the atmosphere Temperature 180-250 °C Autogenic pressure <10 bar Subcritical condition of water HTC • Phenolic compounds • Organic acids (levulinic, acetic, formic, maleic acid, etc) • HMF etc. Process water • Energy-dense solid (18-36 MJ/kg)** • Abundant withpolar oxygen-containing surface functional groups (-OH, -COOH, C=O) • Tunanble surface chemistry Hydrochar *F. Bergius (1931) Chemical reactions under high pressure. Nobel Foundation (Lecture Note), p. 1–33. **M. Mihajlović*, J. Petrović1, M.Stojanović, J.Milojković, Z.Lopičić1, M.Koprivica, Č. Lačnjevac, (2016) Hydrochars, perspective adsorbents of heavy metals: a review of the current state of studies. Zaštita Materijala, 3, In Press 2

4. HTC optimization Chracteristics of hydrochars depends primarily of: • Feedstock type • Temperature • Reaction time Important to know chemical structure of HTC products as a function of production conditions in order to understand its roles and utilize it benificially Fig.1. PLSR results of FT-NIR and FT-IR spectra , presented as correlation loadings plotfor GP and HCobtained at 180, 200 and 220 °C * Fig.2.HPLC-MS chromatograms of GP-PWsobtained at 180, 200 and 220 °C* * J. Petrović, N. Perišić, J. Dragišić Maksimović, V. Maksimović, M. Kragović, M. Stojanović, M. Laušević, M. Mihajlović (2016) Hydrothermal conversion of grape pomace: detailed characterization of obtained hydrochar and liquid phase, Journal of Analytical and Applied Pyrolysis, 118, 267–277.

5. Applications of hydrochars Current investigations • Adsorbents of heavy metals • Carbon sequestration • Soil conditioners • Carriers of microorgansms Figure 3. Effect of process parameters on Pb2+ adsorption onto GP-HC and GP- HCact: (a) pH, (b) adsorbent dosage, (c) contact time and (d) initial Pb2+ concentration* Fig. 4 . Effect of contact time on adsorption of copper by HC-GP (pH=5.0, sorbent dose 0.5 g L-1, initial metal concentration 1mM, T = 25°C)** • J.Petrović, M. Stojanović, J. Milojković, M. Petrović, T.Šoštarić, M. Laušević, M. Mihajlović (2016) Alkali modified hydrochar of grape pomace as a perspective adsorbent of Pb2+ from aqueous solution Journal of Environmental Management, 182,292-300 • ** J.Petrović, M. Stojanović, J. Milojković, M. Petrović, Z. Lopičić1, T.Šoštarić, M. Mihajlović (2016) Biosorption of Cu2+ from aqueous solution by hydrochar of grape pomace, Natural resources, green tecnology & sustainable development , Conference paper.

6. Future interests Usage of biomass-derivedcarbons to catalyze the production of chemicals or biofuelsintegrated into future biorefinery schemes offering the co-production of biofuels, platform chemicals and energy Applications of hydrochar in nanotechnology • Heterogeneous Catalysis • Catalyst Supports • Electrocatalysisin Fuel Cells • Photocatalysis Hydrochars and hybrids with a basic or acid character could play a specific role for various catalytic reactions when used as solid catalysts.

7. Thanks for your attention ! Hvala na pažnji Institute for technology of nuclear and other mineral raw materials 86 Franchet d’Esperey St., 11000 Belgrade, Serbia +381 11 3691-722, +381 11 3691-581 m.mihajlovic@itnms.ac.rs