Hydrothermal Carbonization Kinetics of Lignocellulosic Agro-Wastes: Experimental Data and Modeling

Olive trimmings (OT) were used as feedstock for an in-depth experimental study on the reaction kinetics controlling hydrothermal carbonization (HTC). OT were hydrothermally carbonized for a residence time τ of up to 8 h at temperatures between 180 and 250 °C to systematically investigate the chemical and energy properties changes of hydrochars during HTC. Additional experiments at 120 and 150 °C at τ = 0 h were carried out to analyze the heat-up transient phase required to reach the HTC set-point temperature. Furthermore, an original HTC reaction kinetics model was developed. The HTC reaction pathway was described through a lumped model, in which biomass is converted into solid (distinguished between primary and secondary char), liquid, and gaseous products. The kinetics model, written in MATLABTM, was used in best fitting routines with HTC experimental data obtained using OT and two other agro-wastes previously tested: grape marc and Opuntia Ficus Indica. The HTC kinetics model effectively predicts carbon distribution among HTC products versus time with the thermal transient phase included; it represents an effective tool for R&D in the HTC field. Importantly, both modeling and experimental data suggest that already during the heat-up phase, biomass greatly carbonizes, in particular at the highest temperature tested of 250 °C.

[1]  Weicheng Fan,et al.  Kinetic Compensation Effect In The Thermal Decomposition Of Biomass In Air Atmosphere , 2003 .

[2]  S. Román,et al.  Generation of biofuel from hydrothermal carbonization of cellulose. Kinetics modelling. , 2016 .

[3]  Zhengang Liu,et al.  Hydrothermal Carbonization of Waste Biomass for Energy Generation , 2012 .

[4]  L. Fiori,et al.  Hydrothermal carbonization of off-specification compost: a byproduct of the organic municipal solid waste treatment. , 2015, Bioresource technology.

[5]  T. S. Lira,et al.  Pyrolysis of brewer’s spent grain: Kinetic study and products identification , 2018, Industrial Crops and Products.

[6]  T. Matsuto,et al.  Recovery of solid fuel from municipal solid waste by hydrothermal treatment using subcritical water. , 2012, Waste management.

[7]  Aleksandar M. Orlović,et al.  Determination of kinetic parameters for complex transesterification reaction by standard optimisation methods , 2014 .

[8]  Andrea Kruse,et al.  Hydrothermal Carbonization Brewer’s Spent Grains with the Focus on Improving the Degradation of the Feedstock , 2018, Energies.

[9]  M. Titirici Hydrothermal Carbons: Synthesis, Characterization, and Applications , 2012 .

[10]  A. Corma,et al.  The hydrothermal carbonization (HTC) plant as a decentral biorefinery for wet biomass , 2015 .

[11]  S. Cordiner,et al.  Spent coffee enhanced biomethane potential via an integrated hydrothermal carbonization-anaerobic digestion process. , 2018, Bioresource technology.

[12]  Maria-Magdalena Titirici,et al.  Sustainable Carbon Materials from Hydrothermal Processes , 2013 .

[13]  S. Román,et al.  Conversion of tomato-peel waste into solid fuel by hydrothermal carbonization: Influence of the processing variables. , 2016, Waste management.

[14]  L. Fiori,et al.  One stage olive mill waste streams valorisation via hydrothermal carbonisation. , 2018, Waste management.

[15]  X. Zhuang,et al.  Insights into the evolution of chemical structures in lignocellulose and non-lignocellulose biowastes during hydrothermal carbonization (HTC) , 2019, Fuel.

[16]  Jillian L. Goldfarb,et al.  Hydrothermal carbonization of Opuntia ficus-indica cladodes: Role of process parameters on hydrochar properties. , 2018, Bioresource technology.

[17]  Nicole D Berge,et al.  Hydrothermal carbonization of municipal waste streams. , 2011, Environmental science & technology.

[18]  W. V. Swaaij,et al.  Hydrothermal Conversion Of Biomass. II. Conversion Of Wood, Pyrolysis Oil, And Glucose In Hot Compressed Water , 2010 .

[19]  Luca Fiori,et al.  From olive waste to solid biofuel through hydrothermal carbonisation: The role of temperature and solid load on secondary char formation and hydrochar energy properties , 2017 .

[20]  Luca Fiori,et al.  Hydrothermal Carbonization of Waste Biomass: Process Design, Modeling, Energy Efficiency and Cost Analysis , 2017 .

[21]  K. Yoshikawa,et al.  Ash behavior during hydrothermal treatment for solid fuel applications. Part 1: Overview of different feedstock , 2016 .

[22]  A. Schumpe,et al.  Kinetics of hydrothermal carbonization (HTC) of soft rush , 2015 .

[23]  L. Fiori,et al.  Kinetic and Thermal Modeling of Hydrothermal Carbonization Applied to Grape Marc , 2015 .

[24]  E. Yel,et al.  Self-catalyzing pyrolysis of olive pomace , 2018, Journal of Analytical and Applied Pyrolysis.

[25]  J. Yanik,et al.  Characterization of products from hydrothermal carbonization of orange pomace including anaerobic digestibility of process liquor. , 2015, Bioresource technology.

[26]  H. Spliethoff,et al.  Impact of HTC reaction conditions on the hydrochar properties and CO2 gasification properties of spent grains , 2017 .

[27]  M. Reza,et al.  Effect of hydrothermal carbonization temperature on pH, dissociation constants, and acidic functional groups on hydrochar from cellulose and wood , 2019, Journal of Analytical and Applied Pyrolysis.

[28]  I. Gökalp,et al.  Hydrothermal carbonization of dried olive pomace: Energy potential and process performances , 2017 .

[29]  Marco Baratieri,et al.  Agro-industrial waste to solid biofuel through hydrothermal carbonization. , 2016, Waste management.

[30]  Andres Fullana,et al.  Upgrading of moist agro-industrial wastes by hydrothermal carbonization☆ , 2015 .

[31]  Animesh Dutta,et al.  A comparative review of biochar and hydrochar in terms of production, physico-chemical properties and applications , 2015 .

[32]  A. Funke,et al.  Hydrothermal carbonization of biomass: A summary and discussion of chemical mechanisms for process engineering , 2010 .

[33]  Elias Christoforou,et al.  A review of olive mill solid wastes to energy utilization techniques. , 2016, Waste management.

[34]  C. Fühner,et al.  Process conditions of pyrolysis and hydrothermal carbonization affect the potential of sewage sludge for soil carbon sequestration and amelioration , 2017 .

[35]  Beata Urych Determination of Kinetic Parameters of Coal Pyrolysis to Simulate the Process of Underground Coal Gasification (UCG) , 2014 .

[36]  A. Kruse,et al.  Char and Coke Formation as Unwanted Side Reaction of the Hydrothermal Biomass Gasification , 2008 .

[37]  Jillian L. Goldfarb,et al.  Does hydrothermal carbonization as a biomass pretreatment reduce fuel segregation of coal-biomass blends during oxidation? , 2019, Energy Conversion and Management.

[38]  L. Fiori,et al.  A Novel Reaction Kinetics Model for Estimating the Carbon Content into Hydrothermal Carbonization Products , 2018 .

[39]  Jillian L. Goldfarb,et al.  Impact of hydrothermal carbonization conditions on the formation of hydrochars and secondary chars from the organic fraction of municipal solid waste , 2018, Fuel.

[40]  L. Fiori,et al.  Spatially resolved spectral determination of polysaccharides in hydrothermally carbonized biomass , 2018 .

[41]  Antonio Messineo,et al.  Sustainable Production of Bio-Combustibles from Pyrolysis of Agro-Industrial Wastes , 2014 .

[42]  M. Muhler,et al.  Oxidation characteristics of a cellulose-derived hydrochar in thermogravimetric and laminar flow burner experiments , 2016 .

[43]  Luca Fiori,et al.  Upgrading of Olive Tree Trimmings Residue as Biofuel by Hydrothermal Carbonization and Torrefaction: a Comparative Study , 2016 .

[44]  Haiquan Su,et al.  Morphology evolution, formation mechanism and adsorption properties of hydrochars prepared by hydrothermal carbonization of corn stalk , 2016 .

[45]  Maria-Magdalena Titirici,et al.  Hydrothermal conversion of biomass to fuels and energetic materials. , 2013, Current opinion in chemical biology.

[46]  Domenico Panno,et al.  Upgrade of citrus waste as a biofuel via slow pyrolysis , 2015 .

[47]  Marco Baratieri,et al.  Hydrothermal Carbonization of Biomass : Design of a Batch Reactor and Preliminary Experimental Results , 2014 .

[48]  H Wedwitschka,et al.  Hydrothermal carbonization of olive mill wastewater. , 2013, Bioresource technology.

[49]  M. J. Barajas,et al.  Comparative kinetic study of the pyrolysis of mandarin and pineapple peel , 2016 .

[50]  S. Cordiner,et al.  Biomass fast pyrolysis in a shaftless screw reactor: A 1-D numerical model , 2018, Energy.

[51]  A. Celzard,et al.  Modelling the reactions of cellulose, hemicellulose and lignin submitted to hydrothermal treatment , 2018, Industrial Crops and Products.

[52]  A. Kruse,et al.  Elimination of micropollutants by activated carbon produced from fibers taken from wastewater screenings using hydrothermal carbonization. , 2018, Journal of environmental management.

[53]  N. Berge,et al.  Hydrothermal carbonization of biomass residuals: a comparative review of the chemistry, processes and applications of wet and dry pyrolysis , 2011 .

[54]  A. Kruse,et al.  Evaluation of Arrhenius-type overall kinetic equations for hydrothermal carbonization , 2017 .

[55]  Xiaowei Lu,et al.  Thermal conversion of municipal solid waste via hydrothermal carbonization: comparison of carbonization products to products from current waste management techniques. , 2012, Waste management.

[56]  S. Hoekman,et al.  Reaction kinetics of hydrothermal carbonization of loblolly pine. , 2013, Bioresource technology.

[57]  Liang Li,et al.  Hydrothermal Carbonization: Modeling, Final Properties Design and Applications: A Review , 2018 .

[58]  S. Ucar,et al.  Comparative evaluation of dry and wet carbonization of agro industrial wastes for the production of soil improver , 2018 .

[59]  Luca Fiori,et al.  Modeling of the devolatilization kinetics during pyrolysis of grape residues. , 2012, Bioresource technology.

[60]  A. Kruse,et al.  Hydrothermale Karbonisierung: 2. Kinetik der Biertreber-Umwandlung , 2012 .