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Contents 1. INTRODUCTION ................................................................................................................. 11 2. THEORETICAL BACKGROUNDS .................................................................................... 12 2.1 Pyrolysis ........................................................................................................................ 12 2.1.1 Various possible methods of use of plastic polymers....................................... 14 2.2 Thermal analysis ........................................................................................................... 17 2.2.1 Thermogravimetric analysis.............................................................................. 19 2.3 Kinetics .......................................................................................................................... 24 2.3.1 Isothermal vs. non-isothermal kinetics and other issues................................. 28 2.4 Polymers ........................................................................................................................ 37 2.4.0 Studied polymers................................................................................................ 48 2.4.1 Lignin .................................................................................................................. 48 2.4.2 Cellulose.............................................................................................................. 60 2.4.3 EVA ..................................................................................................................... 62 2.4.4 PS ........................................................................................................................ 64 2.4.5 PVC ..................................................................................................................... 69 3. EXPERIMENTAL PART – STUDY OF THE KINETICS OF THE THERMAL DEGRADATION OF POLYMERS.......................................................................................... 72 3.1 Materials and experimental apparatuses..................................................................... 72 3.2 PART A – Kinetic study of the thermal degradation of polymers – isoconversional method (model-free method) ........................................................... 75 3.2.1 TGA data treatment ........................................................................................... 75 3.2.2 Kinetic model in literature ................................................................................ 81 3.2.2.1 Lignin ......................................................................................................... 81 3.2.2.2 Cellulose..................................................................................................... 83 3.2.2.3 Ethylene vinyl acetate............................................................................... 85 3.2.2.4 Polystyrene................................................................................................ 89 3.2.2.5 Polyvinyl chloride..................................................................................... 92 3.2.3 Analysis of experimental results ....................................................................... 97 3.2.3.1 Lignin ......................................................................................................... 97 3.2.3.2 Cellulose................................................................................................... 100 3.2.3.3 Ethylene vinyl acetate............................................................................. 101 3.2.3.4 Polystyrene.............................................................................................. 103 3.2.3.5 Polyvinyl chloride................................................................................... 105 3.2.4 Discussion and conclusions ............................................................................. 107 3.3 PART B – Kinetic study of thermal degradation of polymers – numerical resolution of kinetic equations obtained from reaction pseudo-schemes (model-fitting method) .............................................................................................. 111 3.3.1 Lignin ................................................................................................................ 111 3.3.2 EVA ................................................................................................................... 125 3.3.3 Study of the degradation kinetics of binary mixtures of polymers .............. 135 3.3.4 Simulation of kinetic models in MatLab......................................................... 156 3.3.5 FTIR analysis of released gases....................................................................... 166 3.3.6 Discussion and conclusions ............................................................................. 178 4. DISCUSSION AND CONCLUSION .................................................................................. 179 5. REFERENCES.................................................................................................................... 181 6. REFERENCES – selected papers on kinetics................................................................... 190 — 4 —
Appendices Appendix A: FTIR working protocol..................................................................................... 197 Appendix B: Experimental results, EVA kinetics................................................................. 200 Appendix C: Detailed description of the thermobalance ..................................................... 203 Appendix D: Description of the FTIR spectrometer............................................................ 206 Appendix E: Tables for Part 1............................................................................................... 208 Appendix F: Figures for Part 1.............................................................................................. 219 Appendix G: Polymer generalities ......................................................................................... 257 Appendix H: List of publications and presentations of professional activities .................. 259 Appendix I: Notation used...................................................................................................... 261 List of figures Fig. 1: Plastic materials susceptible to recycling .................................................................... 14 Fig. 2: Industrial pyrolysing unit P.I.T. – PYROFLAM® with energy valorization ........... 15 Fig. 3: Thermal conductivity of furnace atmosphere gases.................................................... 22 Fig. 4: Linear, branched, and network polymer configuration.............................................. 39 Fig. 5: Chain polymerization and step polymerization........................................................... 43 Fig. 6: Free-radical polymerization: example of styrene........................................................ 44 Fig. 7: Polystyrene prepared by free-radical polymerization................................................ 44 Fig. 8: Polymerization of terephthalic acid and ethylene glycol............................................ 45 Fig. 9: Polyethylene terephthalate ........................................................................................... 46 Fig. 10: Cut through a young black conifer............................................................................. 49 Fig. 11: Lignin monomer (coniferine and syringine) .............................................................. 50 Fig. 12: Formulae of three principal lignin alcohols .............................................................. 50 Fig. 13: Lignin polymerisation. R1, R2 = H or OCH 3 ............................................................ 51 Fig. 14: Types of bonds that occur in lignine..............................................................51 and 52 Fig. 15: Model of lignin based on coniferyne ......................................................................... 53 Fig. 16: Model of lignin based on syringine............................................................................. 54 Fig. 17: Kraft extraction process.............................................................................................. 56 Fig. 18: Sulfite extraction ......................................................................................................... 57 Fig. 19: Sulfonation of Kraft lignins ........................................................................................ 59 Fig. 20: Chemical formula of cellulose..................................................................................... 60 Fig. 21: Principal cellulose monomer ...................................................................................... 60 Fig. 22: Chemical formula of EVA ........................................................................................... 62 Fig. 23: Elementary motive of polystyrene molecule – styrene.............................................. 67 Fig. 24: Radical polymerisation of styrene into PS ................................................................ 68 Fig. 25: Reaction of synthesis of polyvinyl chloride............................................................... 70 Fig. 26: Distribution of various materials used in conditioning of drinking waters ............ 70 Fig. 27: Experimental apparatuses .......................................................................................... 73 Fig. 28: Temperature sensor location ...................................................................................... 74 Fig. 29: Cellulose depolymerisation scheme............................................................................ 83 Fig. 30: Scheme of the 1 st stage of the EVA decomposition .................................................... 87 Fig. 31: Scheme of the reactions of the second stage of the EVA decomposition – formation of transvinyls and disproportionation of free radicals........................................................... 87 Fig. 32: Formation of lacton (a), formation of ketones and acetaldehyde (b) ...................... 88 Fig. 33: Influence of temperature on PS degradation products ............................................ 90 Fig. 34: Mass loss theoretical and experimental values at 226 °C isothermal plateau ....... 119 — 5 —
Page 1 and 2: N° d’ordre : 2283 THESE présent
Page 3: — 3 —
Page 7 and 8: Appendix D Fig. D-1: Michelson inte
Page 9 and 10: Acknowledgements Firstly I must exp
Page 11 and 12: 1. Introduction Accumulation of var
Page 13 and 14: Oil is produced by condensation of
Page 15 and 16: There are 4 main techniques of recy
Page 17 and 18: 2.2 Thermal analysis A typical meth
Page 19 and 20: Tab. 1: Principal thermoanalytical
Page 21 and 22: a point of inflection at a faster h
Page 23 and 24: can react with porcelain or alumina
Page 25 and 26: The use of Arrhenius equation which
Page 27 and 28: their kinetic parameters are false.
Page 29 and 30: statistical analysis allows one to
Page 31 and 32: The ability to handle multi-step re
Page 33 and 34: The solution for avoiding these pro
Page 35 and 36: quantifying the experimental result
Page 37 and 38: 2.4 Polymers The word polymer has i
Page 39 and 40: - linear - branched - network Fig.
Page 41 and 42: * Hydrogen bonds (hydrogen bonding
Page 43 and 44: • Non-recyclable via standard tec
Page 45 and 46: Polymers formed via this process in
Page 47 and 48: [Mathias]: proteins, polypeptides,
Page 49 and 50: Fig. 10: Cut through a young black
Page 51 and 52: The first stage of lignin polymeris
Page 53 and 54: H 2 COH HC O HCOH OMe OMe HC CH CH
Page 55 and 56:
Notwithstanding, lignins can be mad
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monomer CH 2 OH HC O HO CH second m
Page 59 and 60:
Lignin Lignin CH 2 O, Na 2 SO 3 CH
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Cellulose is a component part ensur
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1) Extrusion of films: food packagi
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HIPS or Impact polystyrene Commerci
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H * C C H n* 2 Fig. 23: Elementary
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2.4.5 PVC PVC is the second most ut
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As a matter of fact, PVC is more an
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In all experiments, samples of EVA
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3.2 Part A Kinetic study of the the
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Now, several experiments using vari
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Otherwise, its value would have to
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3.2.2 Kinetic model in literature 3
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3.2.2.2 Cellulose From the point of
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3.2.2.3 Ethylene vinyl acetate At p
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HC H O H 2 H H 2 2 H 2 C C C C C C
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3.2.2.4 Polystyrene The PS degradat
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formation of gases that add to thos
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naphtalene and anthracene) is forme
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them to find the third stage that w
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3.2.3 Analysis of experimental resu
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degradation. Thus, the evaluation o
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3.2.3.3 Ethylene vinyl acetate The
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3.2.3.4 Polystyrene The pyrolysis b
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3.2.3.5 Polyvinyl chloride The pyro
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3.2.4 Discussion and conclusions In
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The thermal degradation consists of
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3.3 Part B Kinetic study of thermal
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Operating methods The type of ligni
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Tab. 16: Comparison of literature a
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Ad 1) Initialisation of parameters:
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77 Theoretical and experimental evo
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Reaction order as a function of tem
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Globally, results connected to acti
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3.3.2 Ethylene vinyl acetate Let us
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graph of mass loss rates of the sum
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parameters are the ones from the pa
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This equation and its coefficients
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Tab. 22: Calculation of VA percenta
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3.3.3 Study of the degradation kine
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Study of the mixture EVA/PS This ch
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EVA/PS mixture Here, three stages o
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Generally speaking, DTG value incre
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Let us remind the initial hypothesi
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The values of relative errors of fr
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The results concerning the order of
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Study of the mixture EVA/PVC and EV
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Tab. 33: Mass loss, DTG, and DTG pe
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dm1 : 30 % at 300°C dm2 : 20 % at
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Xa(T,i)*DTGa(i), (36) where Xa(T,i)
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Chart of PVC modelling: Fig. 50: Co
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dCellulose = k 0 .exp(-E a /RT) (1
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The problem of incoherence between
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Fig. 56: Comparison of experimental
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Conclusion on MatLab simulation res
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Principle of infra-red spectrometry
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Analysis of results of FTIR for pur
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5. time = 1,419.01 s, T = 510°C. T
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2. time = 922.60 s, T = 344°C. The
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Weak peaks of acetic acid can be ob
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• In the pyrolysis of mixtures, n
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4. Discussion and conclusion In the
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5. References ACS, American Chemica
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Day, M., Cooney, J. D., Touchette-B
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Lecomte, D., Bodoira, N., Mise au p
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Oliveira, A. A. M., Kaviany, M., Hr
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Turi, E. A., editor, Thermal charac
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Cao, J., Mathematical studies of mo
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Kissinger, H.E., Variation of peak
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Poutsma, M. L., Fundamental reactio
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Appendices Appendix A Working proto
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are visualized. This tool is very p
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for EVA + EVA* stage 1, T d,max1 [
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Appendix C Detailed description of
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Furnace The furnace used within the
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The above mentioned data were obtai
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Tab. E-3: Cellulose pyrolysis frequ
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Tab. E-7: EVA 25 frequency factors,
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Tab. E-11: Temperatures at various
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Tab. E-15: Activation energies of t
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Tab. E-19: PVC pyrolysis frequency
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Appendix F - Figures for PART A -
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Appendix G - Polymer generalities -
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Appendix H List of publications and
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Appendix I - Notation used A Freque
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