Merz, Daniela

Saatzer, Tilman

Stapf, Dieter

Zeller, Michael

English

KITopen

www.kit.eduKIT – The Research University in the Helmholtz Association©ShutterstockShu terstockThermogravimetric studies and kinetic modeling of the pyrolysis of polyurethane plastics Michael Zeller, Tilman Saatzer, Daniela Merz, Dieter StapfPYRO Ghent 05/2022Michael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Introduction[1][2][3][4][5]https://plasticseurope.org/knowledge-hub/plastics-the-facts-2020/Michael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Polyurethane Chemistry[6][8][7]Foaming agentsCross LinkersFlame RetardantsStabilizersFillers …[6] Von Chem Sim 2001 - Eigenes Werk, Gemeinfrei, https://commons.wikimedia.org/w/index.php?curid=78819735[7] Von Yikrazuul - Eigenes Werk, Gemeinfrei, https://commons.wikimedia.org/w/index.php?curid=5046205[8] Von Jü - Eigenes Werk, Gemeinfrei, https://commons.wikimedia.org/w/index.php?curid=81399249[9] Von Jü - Eigenes Werk, CC BY-SA 4.0, https://commons.wikimedia.org/w/index.php?curid=36661045[10] Von Jü - Eigenes Werk, Gemeinfrei, https://commons.wikimedia.org/w/index.php?curid=42160752[11] Von Roland.chem - Eigenes Werk, CC0, https://commons.wikimedia.org/w/index.php?curid=36670935TDIMDIIPDIIsocyanates[9][10]Polyols[11]PolyurethanesMichael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Characteristics of Polyurethane DegradationKumagai, Shogo; Motokucho, Suguru; Yabuki, Ryosuke; Anzai, Airi; Kameda, Tomohito; Watanabe, Atsushi et al. (2017): Effects of hard- and soft-segment composition on pyrolysis characteristics of MDI, BD, and PTMG-based polyurethane elastomers. In: Journal of Analytical and Applied Pyrolysis 126, S. 337–345. DOI: 10.1016/j.jaap.2017.05.012.abMichael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Material Selection - Model PolyurethanesFlexible Foam Rigid FoamThermoplasticPURCast ElastomerFlame RetardedTPUMDI/PMDI + EO&PO-Polyether-olsFoaming agent: WaterMDI + PolyTHFMichael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry0 200 400 600 800020406080100Mass in %Temperature in °C Rigid Foam Flexible Foam Cast Elastomer Flame retardant TPU TPU19.5.2022Thermogravimetry – Kinetic Modelingm0=10 mg, 10 K/min, Atmosphere: N2𝑤𝑐𝑎𝑙 = 1 − 𝛼1𝑣1∞ − 𝛼2𝑣2∞Fit Parameters𝑑 Τ𝑣2 𝑣2∞𝑑𝑇=𝑑𝛼2𝑑𝑇=𝑘0,2𝛽𝑒𝑥𝑝−𝐸A,2𝑅𝑇𝛼1 − 𝛼2𝑛2𝑑 Τ𝑣1 𝑣1∞𝑑𝑇=𝑑𝛼1𝑑𝑇=𝑘0,1𝛽𝑒𝑥𝑝−𝐸A,1𝑅𝑇1 − 𝛼1𝑛1from Garrido et al. 2016 (https://doi.org/10.1016/j.enconman.2016.04.048)Michael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Kinetic Modeling – work in progress0 200 400 600 800020406080100Mass in %Temperature in °C Experiment ModelRigid Foamβ= 5 K/minv1∞ v2∞ EA,1 EA,2 k0,1 k0,2 n1 n2- - kJ/mol kJ/mol 1/s 1/s - -0,65 0,21 175 238 9,37*1012 6,41*1014 2,05 2,37Exp. Volatile products from primarydegradation:MDI (56 wt.% in PUR)Glycerine (4 wt.% in PUR)Sorbitol (7 wt.% in PUR)≈ v1∞0 200 400 600 800-1,5-1,0-0,50,0Mass change rate in %/°CTemperature in °C Experiment ModelRigid Foamβ= 5 K/minMichael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Kinetic Modeling – work in progress0 200 400 600 800020406080100Mass in %Temperature in °C Experiment ModelCast Elastomer β= 5 K/min0 200 400 600 800-2,0-1,5-1,0-0,50,0Mass change rate in %/KTemperature in °C Experiment ModelCast Elastomer β= 5 K/minv1∞ v2∞ EA,1 EA,2 k0,1 k0,2 n1 n2- - kJ/mol kJ/mol 1/s 1/s - -0,21 0,76 178 223 9,23*1012 6,24*1014 1,22 1,16Exp. Volatile products from primarydegradation:MDI (20 wt.% in PUR)1,4-BDO (2 wt.% in PUR)≈ v1∞Michael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry19.5.2022Kinetic Modeling – work in progress0 200 400 600 800020406080100Mass in %Temperature in °C Experiment ModelFlexible Foamβ= 5 K/min0 200 400 600 800-2,5-2,0-1,5-1,0-0,50,0Mass change rate in %/KTemperature in °C Experiment ModelFlexible Foamβ= 5 K/minExp. Volatile products from primarydegradation:MDI (29 wt.% in PUR)Glycerine (2 wt.% in PUR) ≠ v1∞v1∞ v2∞ EA,1 EA,2 k0,1 k0,2 n1 n2- - kJ/mol kJ/mol 1/s 1/s - -0,10 0,83 171 203 4,92*1013 1,26*1014 2,86 1,50Michael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry0 100 200 300 400020406080100Mass in %Time in min 350°C 450°CSlow isothermal mass loss→ slow degradation reactions→ little volatiles generation→ N-Release?19.5.2022Preperative TGA – work in progressT Element Balance°C % Feedstock C% Feedstock H% Feedstock N350 37 27 55450 19 9 25TG-FTIR, Py-GC-MSResidual mass @ 900°C = 15,6%Rigid Foamβ= 5 K/min, 4h isothermal timeMichael Zeller | PYRO 2022 Ghent Institute for Technical ChemistryTwo-step mechanism confirmed for broad range of PURsKinetic Model can reproduce overall mass loss and peak temperatures wellCurrent & Future workExpansion of model dataset with isothermal experimentsProduct evolutionTG-FTIRPy-GC-MS → higher heating ratesInfluence of secondary reactions in lab scale pyrolysis19.5.2022Conclusions & OutlookMichael Zeller | PYRO 2022 Ghent Institute for Technical Chemistry[1] https://www.effizienzhaus-online.de/polyurethan-pur (accessed 30.4.21)[2] https://galusaustralis.com/2019/11/53556/polyurethane-shoe-sole-market-rising-trends-demands-and-growing-business-opportunities-2019/ (accessed 30.4.21)[3] https://www.caparol.de/produkte/bautenlacke-lasuren/capalac-aqua/weiss-und-buntlacke/capalac-aqua-2k-pu-lack (accessed 30.4.21)[4] https://www.bm-online.de/wissen/bauelemente/pu-schaum-so-gehts/ (accessed 30.4.21)[5] https://huber-schaumstoffe.de/index.php/pur-schaum/ (accessed 30.4.21)19.5.2022Image Sources

Thermogravimetric studies and kinetic modeling of the pyrolysis of polyurethane plastics

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Thermogravimetric studies and kinetic modeling of the pyrolysis of polyurethane plastics

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