Determination of Enthalpy of Pyrolysis from DSC and Industrial Reactor Data: Case of Tires
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Jean-Remi Lanteigne
Abstract
This study was motivated by the fact that differential scanning calorimetry (DSC)/differential thermal analysis (DTA) results in literature showed significant exothermic peaks while in overall, pyrolysis is an endothermic phenomenon. The specific heat of the decomposing tires has been determined with a new methodology: instead of assuming constant char properties throughout pyrolysis, the specific heat of evolving solids (char) was evaluated with increasing temperature and conversion. Measured specific heat values were observed to increase until pyrolysis was triggered at 250°C. Then, the specific heat of the solids decreased continuously until 400°C at which point they started to increase. This unexpected trend pointed out that the exothermic peak observed with DSC is an artefact generated by the control system of the apparatus. To overcome this limitation, the energy balance was performed over industrial data and the newly found heat capacity values. The enthalpy of pyrolysis was found to have a term dependent on the weight loss derivative, with a constant value of 410 kJ/kg tires. Two other terms for the enthalpy of pyrolysis have been identified, which were independent of weight loss. The first one is believed to correspond to the sulphur cross-link breakage at low temperature (65 kJ/kg), while the second one, at the final stage of pyrolysis, should correspond to charring reactions approaching the thermodynamic equilibrium (75 kJ/kg). Ultimately, this work proposes a new methodology to determine the enthalpy of pyrolysis with larger scale experimental data.
References
1. BoxGEP, DraperNR. Empirical model building and response surfaces. New York: John Wiley & Sons, 1987.Search in Google Scholar
2. YangJ, TanguyPA, RoyC. Heat transfer, mass transfer and kinetics study of the vacuum pyrolysis of a large used tire particle. Chem Eng Sci1995;50:1909–22.10.1016/0009-2509(95)00062-ASearch in Google Scholar
3. YangJ, RoyC. A new method for DTA measurement of enthalpy change during the pyrolysis of rubbers. Thermochim Acta1996;288:155–68.10.1016/S0040-6031(96)03017-1Search in Google Scholar
4. CheungK-Y, LeeK-L, LamK-L, LeeC-W, HuiC-W. Integrated kinetics and heat flow modelling to optimise waste tyre pyrolysis at different heating rates. Fuel Process Technol2011;92:856–63.10.1016/j.fuproc.2010.11.028Search in Google Scholar
5. CheungK-Y, LeeK-L, LamK-L, ChanT-Y, LeeC-W, HuiC-W. Operation strategy for multi-stage pyrolysis. J Anal Appl Pyrol2011;91:165–82.10.1016/j.jaap.2011.02.004Search in Google Scholar
6. KoufopanosCA, PapayannakosN, MaschioG, LucchesiA. Modelling of the pyrolysis of biomass particles. Studies on kinetics, thermal and heat transfer effects. Can J Chem Eng1991;69:907–15.10.1002/cjce.5450690413Search in Google Scholar
7. KlasonP. Versuch einer theorie der trockendestillation von hols. J Prakt Chem1914;90:413.10.1002/prac.19140900127Search in Google Scholar
8. ThomasPH, BowesPC. Some aspects of self-heating and ignition of solid cellulosic materials. Br J Appl Phys1961;12:222.10.1088/0508-3443/12/5/305Search in Google Scholar
9. RobertsAF, CloughG. Thermal decomposition of wood in an inert atmosphere. In: Ninth symposium (international) combustion, New York, 1963;158.10.1016/B978-1-4832-2759-7.50024-8Search in Google Scholar
10. BeallFC. Differential calorimetric analysis of wood and wood components. Wood Sci Technol1971;5:159–75.10.1007/BF00353679Search in Google Scholar
11. YangJ, KaliaguineS, RoyC. Improved quantitative determination of elastomers in tire rubber by kinetic simulation of DTG curves. Rubber Chem Technol1993;66:213.10.5254/1.3538307Search in Google Scholar
12. SircarAK, LamondTG. Carbon black transfer in blends of cis-poly(butadiene) with other elastomers. J Appl Polym Sci1973;17:2569.Search in Google Scholar
13. BrazierDW, SchwartzNV. Effect of heating rate on the thermal degradation of polybutadiene. J Appl Polym Sci1978;22:113.10.1002/app.1978.070220109Search in Google Scholar
14. LahB, KlinarD, LikozarB. Pyrolysis of natural, butadiene, styrene-butadiene rubber and tyre components: modelling kinetics and transport phenomena at different heating rates and formulation. Chem Eng Sci2013;87:1–13.10.1016/j.ces.2012.10.003Search in Google Scholar
15. LanteigneJ-R, LavioletteJ-P, TremblayG, ChaoukiJ. Predictive kinetics model for an industrial waste tire pyrolysis process. Energy Fuels2013;27:1040–9.10.1021/ef301887fSearch in Google Scholar
16. DanleyRL. New heat flux DSC measurement technique. Thermochim Acta2003;395:201–8.10.1016/S0040-6031(02)00212-5Search in Google Scholar
17. MartinezJD, MurilloR, GarciaT, VesesA. Demonstration of the waste tyre pyrolysis process on pilot scale in a continuous auger reactor. J Hazard Mater2013;261:637–45.10.1016/j.jhazmat.2013.07.077Search in Google Scholar
18. DiezC, MartinezO, CalvoLF, CaraJ, MoranA. Pyrolysis of tyres. Influence of the final temperature of the process on emissions and the calorific value of the products recovered. Waste Manage2004;24:463–9.10.1016/j.wasman.2003.11.006Search in Google Scholar
19. WilliamsPT, BeslerS, TaylorDT. Pyrolysis of scrap automotive tyres. The influence of temperature and heating rate on product composition. Fuel1990;69:1474–82.10.1016/0016-2361(90)90193-TSearch in Google Scholar
20. LaresgoitiMF, CaballeroBM, De MarcoI, TorresA, CabreroMA, ChomonMJ. Characterization of the liquid products obtained in tyre pyrolysis. J Anal Appl Pyrol2004;71:245–53.10.1016/j.jaap.2003.12.003Search in Google Scholar
21. BerruecoC, EsperanzaE, MastralFJ, CeamanosJ, Garcia-BacaicoaP. Pyrolysis of waste tyres in an atmospheric static-bed batch reactor: analysis of the gases obtained. J Anal Appl Pyrol2005;74:257–69.10.1016/j.jaap.2004.10.007Search in Google Scholar
22. LopezFA, CentenoTA, AlguacilFA, LobatoB, TheUA. GRAUTHERMIC-tyres process for the recycling of granulated scrap tyres. J Anal Appl Pyrol2013;103:207–15.10.1016/j.jaap.2012.12.007Search in Google Scholar
©2015 by De Gruyter
Articles in the same Issue
- Frontmatter
- Research Articles
- Transesterification of Castor Oil with Methanol – Kinetic Modelling
- Hybrid Particle Swarm Optimization and Ant Colony Optimization Technique for the Optimal Design of Shell and Tube Heat Exchangers
- Determination of Enthalpy of Pyrolysis from DSC and Industrial Reactor Data: Case of Tires
- Modeling of a UASB Reactor by NARX Networks for Biogas Production
- Optimization of Biodiesel Ultrasound-Assisted Synthesis from Castor Oil Using Response Surface Methodology (RSM)
- Review
- Diglycolamide-Based Solvent Systems in Room Temperature Ionic Liquids for Actinide Ion Extraction: A Review
Articles in the same Issue
- Frontmatter
- Research Articles
- Transesterification of Castor Oil with Methanol – Kinetic Modelling
- Hybrid Particle Swarm Optimization and Ant Colony Optimization Technique for the Optimal Design of Shell and Tube Heat Exchangers
- Determination of Enthalpy of Pyrolysis from DSC and Industrial Reactor Data: Case of Tires
- Modeling of a UASB Reactor by NARX Networks for Biogas Production
- Optimization of Biodiesel Ultrasound-Assisted Synthesis from Castor Oil Using Response Surface Methodology (RSM)
- Review
- Diglycolamide-Based Solvent Systems in Room Temperature Ionic Liquids for Actinide Ion Extraction: A Review
