Abbas, M.M.

Dahmen, N.

Funke, A.

English

Abbas, M. M.

KITopen

KIT – University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association Upgrading of Fast Pyrolysis Byproducts  for Material Use with High Value Funke, A.; Abbas, M. M.; Dahmen, N. Institut of Catalysis Research and Technology Motivation and Aims  Fast pyrolysis is a thermochemical conversion process for the production of liquid substances from solid organic fuels, be it a blend for energetic use (liquid fuel) or more specific chemical substances for material use. However, complete liquefaction of the biomass cannot be achieved and there is always a solid byproduct, i.e. char. The amount of this byproduct increases inevitably when feedstocks with high ash content are used (see Figure 1).  In this study, activation of fast pyrolysis char was investigated. One focus was on suitable ways to deal with the high ash content of the char (~40 %) which results from using wheat straw as feed material. The aim is to produce a marketable pulverized activated carbon (PAC). After the use for adsorption, spent material can still be used within the bioliq® concept for the production of chemicals and/or drop-in fuels. Experimental Section and Results  The experimental procedure of activation started with a demineralization yielding a demineralized char. With this demineralized char, chemical activation at 700 °C (method described in Figure 3) and steam activation at 750 °C were conducted.   Steam activation produced an activated carbon with much higher ash content due to the carbon burn off, which results in an enrichment of minerals. In consequence, the BET surface area of the steam activated carbon is comparably low (Figure 2). Activation with KOH leads to a near complete removal of inorganic compounds and a suspiciously high BET surface area. Iodine number (ASTM D 4607) has been determined for the chemically activated carbon to be 2400 mg g-1. It is concluded that the fast pyrolysis char has been activated successfully [2].  39.8 19.6 38 0.7 4 24 550 2900 0500100015002000250030003500051015202530354045Char Demin. char Steam Act. KOH Act.BET surface area (m² g-1) Ash content (%) Figure 1: Fast pyrolysis product distribution with varying ash content of the feedstocks [1] Figure 2: Ash content and BET surface area of char, demineralized char, steam activated carbon, and chemically activated carbon Notably, demineralization decreased the ash content only by about 50 % whereas chemical activation lead to a near complete removal of ash. Screening tests were performed to simplify the chemcial activation method (see Figure 3) and it was found that the activation and washing step is sufficient to achieve a near complete removal of ash components.  Further reserach will be conducted to optimize the activation procedure in order to achieve an economically viable solution. Furthermore, process integration will be investigated to assess possible synergies when the activation step is conducted on site of the pyrolysis plant.    Use of residues       Decentralized                       ‚Direct‘ char use              Gasification        &     Synthesis    (e. g. wheat straw)       fast pyrolysis                of oil and char                            Cascaded char use Demineralization (1N H2SO4:HCl 1:1 solution for 24 h at room temperature) Impregnation (2:1 wt./wt. KOH:char in H2O at 60 °C) Activation (4:1 wt./wt.KOH:char, 50 L h-1) Washing (1N HCl and rinsing with H2O) Activation (4:1 wt./wt. KOH:char, 50 L h-1) Washing (1N HCl and rinsing with H2O) X X Figure 3: Full and simplified method for chemical activation   Biosyncrude (oil & char mixture)  Oil  Activated Carbon (AC)   Adsorption application Spent AC     Drop-in fuels  Chemicals Contact:  axel.funke@kit.edu    +49 721 608 22391  www.bioliq.de  [1] Tröger, N., D. Richter, et al. J Anal Appl Pyr 100 (2013) p 158-165. [2] Funke, A., A. Niebel, et al. Bioresour Technol, submitted 

Upgrading of fast pyrolysis byproducts for material use with high value

Engineering Conferences International

Engineering Conferences InternationalECI Digital ArchivesBiorefinery I: Chemicals and Materials FromThermo-Chemical Biomass Conversion and RelatedProcessesProceedings2015Upgrading of Fast Pyrolysis Byproducts forMaterial Use with High ValueA. FunkeInstitute of Catalysis Research and Technology (IKFT)M.M. AbbasInstitute of Catalysis Research and Technology (IKFT)N. DahmenInstitute of Catalysis Research and Technology (IKFT)Follow this and additional works at: http://dc.engconfintl.org/biorefinery_IPart of the Chemical Engineering CommonsThis Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion inBiorefinery I: Chemicals and Materials From Thermo-Chemical Biomass Conversion and Related Processes by an authorized administrator of ECIDigital Archives. For more information, please contact franco@bepress.com.Recommended CitationA. Funke, M.M. Abbas, and N. Dahmen, "Upgrading of Fast Pyrolysis Byproducts for Material Use with High Value" in "Biorefinery I:Chemicals and Materials From Thermo-Chemical Biomass Conversion and Related Processes", Nicolas Abatzoglou, Université deSherbrooke, Canada Sascha Kersten, University of Twente, The Netherlands Dietrich Meier, Thünen Institute of Wood Research,Germany Eds, ECI Symposium Series, (2015). http://dc.engconfintl.org/biorefinery_I/8KIT – University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz AssociationINSTITUTE OF CATALYSIS RESEARCH AND TECHNOLOGY (IKFT)www.kit.eduUpgrading of Fast Pyrolysis Byproducts for Material Use with High ValueA. Funke; M. M. Abbas, N. DahmenInstitute of catalysis research and technology (IKFT)2OutlineRationale of using char from fast pyrolysisExample bioliqActivation and demineralization of fast pyrolysis charbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015Institute of catalysis research and technology (IKFT)3Fast pyrolysis bio-oilModerate temperature and high heating rate (wood):60-70 % liquid organics<10 % charChar represents byproduct oflow quantityCurrent useOxidation to provide processheatSurplus heat & power asoptional productsbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015gaseousliquidsolidLow heatingrateHigh heatingrateLiquid productsGaseous productsSolid productsTemperatureYieldAdapted from: Hofbauer, H., M. Kaltschmitt, et al. (2009). Energie aus Biomasse -Grundlagen, Techniken, Verfahren. Springer Verlag, Berlin Heidelberg.Institute of catalysis research and technology (IKFT)4Ash-containing feedstockAsh increases the yield of (organic) solidsSolids contain significant fraction of carbonUse of char becomes more attractivebiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.201524 8 44 3 17 40 % 10 % 20 % 30 % 40 % 50 % 60 % 70 % 80 % 90 % 100 %Fraction of carbon input (wt. %)Solids Solids/OC OC/without solids Aqueous condensate Gas DeficitFast pyrolysis of wheat straw – product distributionTröger, N., D. Richter, et al. 2013, J Anal Appl Pyr100:158-165.Institute of catalysis research and technology (IKFT)5bioliq® concept for 2nd generation biofuelVolumetric energy densification in decentralized unitsEconomic production of drop-in fuels andchemicals in industrial scalebiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015 Energy density: 2 GJ/m3 25 GJ/m3 36 GJ/m3Institute of catalysis research and technology (IKFT)6Pilot plant and research platformbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015TRL 6 bioliq® pilot plantTRL 5 Process development unit (PYTHON)TRL 4 Labscale fast pyrolysisCommercial applicationBasic researchInstitute of catalysis research and technology (IKFT)7Cascaded approachRevenue must compensate the valueaddition from producing biofuelPositive impacts on gasifier designNo water gas shift requiredNo solids, less ashbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015 Adsorption application DisposalFast pyrolysis bio-oilChar/ activated carbononly compensate carbonlosses due to activat on (burn off)Negligible effects on gas fier designInstitute of catalysis research and technology (IKFT)8SteamActivationChemical (KOH)ActivationActivation proceduresbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015Demineralization(1N H2SO4:HCl 1:1 solution for 24 h at room temperature)Impregnation(2:1 wt./wt. KOH:char in H2O at 60 °C)Activation @ 700 °C(1 h @ 700 °C, N2 50 L h-1, 4:1 wt./wt.KOH:char)Washing(1N HCl and rinsing with H2O)Pelletizing(fast pyrolysis tar as binder)Activation(1 h @ 750 °C, steam 4.5 L h-1)Char from 5 mm wheat straw(fast pyrolysis at 500 °C, augerreactor with heat carrier)Institute of catalysis research and technology (IKFT)9Results of different activation methodsbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.201539.819.6380.74 2455029000500100015002000250030003500051015202530354045Char Demin. char Steam Act. KOH Act.BET surface area (m² g-1)Ash content (%)Institute of catalysis research and technology (IKFT)10Characterization of activated carbonSteam activation: mesoporesChemical activation: microporesbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015Institute of catalysis research and technology (IKFT)11Simplifying activation methodbiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015Demineralization(1N H2SO4:HCl 1:1 solution for 24 h at room temperature)Impregnation(2:1 wt./wt. KOH:char in H2O at 60 °C)Activation @ 700 °C(1 h @ 700 °C, N2 50 L h-1, 4:1 wt./wt.KOH:char)Washing(1N HCl and rinsing with H2O)Char from 5 mm wheat straw(fast pyrolysis at 500 °C, augerreactor with heat carrier)Ash reduction to 20 % Ash content 40 % Ash reduction to 15 % Ash reduction to <1 % Institute of catalysis research and technology (IKFT)12Activation burn offCarbon losses due to activation are <40 %biorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015100 %40 %40 %Ash60 %Carbon40 %CarbonMass loss due to activation Mass loss due to activationconsidering ash contentInstitute of catalysis research and technology (IKFT)13SummaryFast pyrolysis char is a significant byproduct if feedstocks with high ash content are usedIt was shown that combined activation and demineralization of fast pyrolysis char is possiblebiorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015Institute of catalysis research and technology (IKFT)14Thank you for your attention!And many thanks to:Willy HabichtThomas OttoElisabeth SchröderPatrick WenkeDr.-Ing. Axel FunkeKarlsruhe Institute of Technology (KIT)Institute of Catalysis Research and Technology (IKFT)Phone: +49 721 608-22391Email: axel.funke@kit.eduWeb: http://www.kit.edu/biorefinery I, 27.09.-02.10.2015 Chania/ Greece - Fast Pyrolysis Char03.11.2015

Upgrading of Fast Pyrolysis Byproducts for Material Use with High Value

https://publikationen.bibliothek.kit.edu/220102213/3816908

Upgrading of Fast Pyrolysis Byproducts for Material Use with High Value

Abstract

Similar works

Full text

Available Versions

KITopen

Engineering Conferences International