Pyrolysis of Bioplastics Based on Bovine Gelatin-Potato Flour and Whey Protein-Potato Flour Blends and Their Kinetics and Thermodynamic Analysis

Document Type : Research Paper

Authors

1. Department of Biosystems Engineering, Faculty of Agriculture; 2. Department of Chemical Engineering, Faculty of Engineering; Ferdowsi University of Mashhad, P.O. Box: 9177948978, Mashhad, Iran

Abstract

Hypothesis: The pyrolysis process of bioplastics, prepared from a mixture of two animal proteins and whole potato flour, was studied and their kinetics and thermodynamic behavior during pyrolysis was investigated. The proteins used in this study included whey protein and bovine gelatin, which were extracted from the wastes of animal breeding and processing industries.
Methods: To study kinetics of thermal decomposition, various isoconversional methods including Friedman, Flynn-Wall-Ozawa, Kissinger-Akahira-Sunose, and Starink were used and the kinetic parameters of thermal decomposition were calculated for bioplastic samples consisting of bovine gelatin-whole potato flour (BG), whey protein-whole wheat flour (Wh) and whole potato flour (P) as control.
Findings: The results showed that the variation in activation energy calculated by the Friedman method for BG, Wh and control (P) bioplastic samples was 60.15-214.65 kJ/mol, 59.16-264.07 kJ/mol and 50.38-216.68 kJ/mol, respectively. Prediction of reaction model using Criado’s method in the conversion ranges of 0.1-0.4, and 0.1-0.9, in order to cover the behavior of the bioplastics in two modes of processing and producing renewable energy, respectively, showed that in all investigated bioplastics, Valensi model (D2) in processing mode and Jander model (D3) in the second mode had the best linearity coefficient (R2) between theoretical master plots and experimental reduced rates. Thermodynamic analysis showed that the maximum enthalpy change for BG was observed in the conversion of 0.5 and was equal to ~210 kJ/mol and for the control and Wh bioplastics were observed in the conversion of 0.6 and were equal to ~259 kJ/mol and ~212 kJ/mol, respectively. The results of this study not only determined the thermal behavior of potato-based bioplastics at different temperatures and the thermal decomposition process, but also helped to generate renewable energy from bioplastic wastes.

Keywords


  1. Chuaynukul, K., Prodpran, T., and Benjakul, S., Preparation, Thermal Properties and Characteristics of Gelatin Molding Compound Resin, Res. J. Chem. Env. Sci., 2, 1-9, 2014.
  2. Nur Hanani Z.A., Beatty E., Roos Y.H., Morris M.A., and Kerry J.P., Manufacture and Characterization of Gelatin Films Derived from Beef, Pork and Fish Sources Using Twin Screw Extrusion, Food Eng., 113, 606-614, 2012.
  3. Azevedo V.M., Borges S.V., Marconcini J.M., Yoshida M.I., Neto, A.R.S., Pereira T.C., and Pereira C.F.G., Effect of Replacement of Corn Starch by Whey Protein Isolate in Biodegradable Film Blends Obtained by Extrusion, Carbohy. Polym., 157, 971-980, 2017.
  4. Cao H., Xin Y., Wang D., and Yuan Q., Pyrolysis Characteristics of Cattle Manures Using a Discrete Distributed Activation Energy Model, Biores. Technol., 172, 219-225, 2014.
  5. Mezzullo W.G., Mcmanus M.C., and Hammond G.P., Life Cycle Assessment of a Small-Scale Anaerobic Digestion Plant from Cattle Waste, Appl. Ener., 102, 657-664, 2013.
  6. Yuan X., He T., Cao H., and Yuan Q., Cattle Manure Pyrolysis: Kinetic and Thermodynamic Analysis with Isoconversional Methods, Rene.Ener.,107, 489-496, 2017.
  7. Baniasadi M., Tugnoli A., Conti R., Torri C., Fabbri D., and Cozzani V., Waste to Energy Valorization of Poultry Litter by Slow Pyrolysis, Rene.Ener., 90, 458-468, 2016.
  8. Thanapal S.S., Annamalai K., Sweeten J.M., and Gordillo G., Fixed Bed Gasification of Dairy Biomass with Enriched Air Mixture, Appl. Ener., 97, 525-531, 2012.
  9. Qian, Q., Machida, M., and Tatsumoto, H., Preparation of Activated Carbons from Cattle Manure Compost by Zinc Chloride Activation, Biores. Technol., 98, 353-360, 2007.
  10. Ro K.S., Hunt, P.G., Jackson, M.A., Compton D.L., Yates S.R., Cantrell, K., and Chang, S., Co-pyrolysis of Swine Manure with Agricultural Plastic Waste: Laboratory-Scale Study, Was. Mana., 34, 1520-1528, 2014.
  11. Vyazovkin S., Modification of the Integral Isoconversional Method to Account for Variation in the Activation Energy, Compu. Chem., 22, 178-183, 2001.
  12. Swain S., Rao K., and Nayak P., Biodegragable Polymers. Part II. Thermal Degradation of Biodegradable Plastics Cross-Linked from Formaldehyde-Soy Protein Concentrate, Ther. Analy. Calo.,79, 33-38, 2005.
  13. Das P. and Tiwari P., Thermal Degradation Kinetics of Plastics and Model Selection, Thermo. Act., 654, 191-202, 2017.
  14. Sun S., Song Y., and Zheng Q., Morphologies and Properties of Thermo-Molded Biodegradable Plastics Based on Glycerol-Plasticized Wheat Gluten, Food Hydro., 21, 1005-10013, 2007.
  15. Ramos O.L., Reinas I., Silva S.I., Fernandes J.C., Cerqueira M.A., Pereira R.N., Vicente A.A., Poças M.F., Pintado M.E., and Malcata F.X., Effect of Whey Protein Purity and Glycerol Content upon Physical Properties of Edible Films Manufactured Therefrom, Food Hydro., 30, 110-122, 2013.
  16. Mariani P.D.S.C, Allganer K., Oliveira F.B, Cardoso E.J.B.N., and Innocentini-Mei L.H., Effect of Soy Protein Isolate on the Thermal, Mechanical and Morphological Properties of Poly(ε-Caprolactone) and Corn Starch Blends, Polym. Tes., 28, 824-829, 2009.
  17. Mendes J., Paschoalin R., Carmona V., Neto A. R.S., Marques A., Marconcini J., Mattoso L.H.C., Medeiros E.S., and Oliveira J.E., Biodegradable Polymer Blends Based on Corn Starch and Thermoplastic Chitosan Processed by Extrusion, Carboh. Polym., 137, 452-458, 2016.
  18. Vyazovkin S., Chrissafis K., Di Lorenzo M.L., Koga N., Pijolat M., Roduit B., Sbirrazzuoli N., and Suñol J.J., ICTAC Kinetics Committee Recommendations for Collecting Experimental Thermal Analysis Data for Kinetic Computations, Thermo. Act., 590, 1-23, 2014.
  19. Yao F., Wu Q., Lei Y., Guo W., and Xu Y., Thermal Decomposition Kinetics of Natural Fibers: Activation Energy with Dynamic Thermogravimetric Analysis, Polym. Deg. Stab., 93, 90-98, 2008.
  20. Uttaravalli A.N. and Dinda, S., Kinetics of Thermal Decomposition of Ketonic Resins, Mat. Tod.Commu., 12, 88-94, 2017.
  21. Dhyani V., Kumar J., and Bhaskar T., Thermal Decomposition Kinetics of Sorghum Straw via Thermogravimetric Analysis, Biores. Technol., 245, 1122-1129, 2017.
  22. Oleyaei A., Moayedi A.A., and Ghanbarzadeh B., The Effect of Montmorillonite (MMT) on Structural, Thermal and Optical Properties of Iranian Potato Starch Based Nanobiocomposite Films, Innov. Food Technol. (Persian), 4: 89-105, 2017.
  23. Nicolas-Somonnot M.O., Treguer V., Leclerc J.P., Sardin M., Brajoux J.P., Moy J., and Takerkart G., Experimental Study and Modeling of Gelatin Production from Bone Powder: Elaboration of an Overall Kinetic Scheme for the Acid Process, Chem. Eng. Jour., 67, 55-64, 1997.
  24. Hosseiniparvar S.H., Keramat J., Kadivar M., Khanipour E., and Milani E., Optimization of Enzymic Extraction of Edible Gelatin from Cattle Bones Using Response Surface Methodology (RSM), Iran. Food Sci. Technol. Res. J. (Persian), 2, 1-14, 2006.
  25. Jerez A., Partal P., Martinez I., Gallegos C., and Guerrero A., Protein-Based Bioplastics: Effect of Thermo-Mechanical Processing, Rheol. Act., 46, 711-720, 2007.
  26. Vyazovkin S., Burnham A.K., Criado J.M., Pérez-Maqueda L.A., Popescu C., and Sbirrazzuoli N., ICTAC Kinetics Committee Recommendations for Performing Kinetic Computations on Thermal Analysis Data, Thermo Chim. Act, 520, 1-19, 2011.
  27. Friedman H.L., Kinetics of Thermal Degradation of Char-Forming Plastics from Thermogravimetry. Application to a Phenolic Plastic, Polym. Sci., 6, 183-185, 1964.
  28. Flynn J.H., The Temperature Integral-Its Use and Abuse, Thermo. Chim. Act, 300, 83-92, 1997.
  29. Ozawa T., A New Method of Analyzing Thermogravimetric Data, Bull. Chem. Soc. Japan. 38, 1881-1886, 1965.
  30. Doyle C.D., Estimating Isothermal Life from Thermogravimetric Data, Appl. Polym. Sci., 6, 639-642, 1962.
  31. Akahira T. and Sunose T., Method of Determining Activation Deterioration Constant of Electrical Insulating Materials, Res. Rep., Chiba. Inst. Technol., 16, 22-31, 1971.
  32. Murray P. and White J., Kinetics of the Thermal Dehydration of Clays. Part IV. Interpretation of the Differential Thermal Analysis of The Clay Minerals, Trans. Brit. Cer. Soc., 54, 204-238, 1955.
  33. Starink M.J., TheDetermination of Activation Energy from Linear Heating Rate Experiments: AComparison of the Accuracy of Isoconversion Methods, Thermo. China. Act. 404, 163-176, 2003.
  34. Kim Y.S., Kim Y.S., and Kim S.H., Investigation of Thermodynamic Parameters in the Thermal Decomposition of Plastic Waste-Waste Lube Oil Compounds, Environ. Sci. Technol., 44, 5313-5317, 2010.
  35. Criado J.M., Kinetic Analysis of DTG Data from Master Curve, Thermo. Chim. Act., 24, 186-189, 1978.
  36. Xu Y. and Chen B., Investigation of Thermodynamic Parameters in the Pyrolysis Conversion of Biomass and Manure to Biochars Using Thermogravimetric Analysis, Bioresource Technol., 146, 485-493,  2013.
  37. Liang Y., Cheng B., Si, Y., Cao D., Jiang H., Han G., and Liu X., Thermal Decomposition Kinetics and Characteristics of Spartina Alterniflora via Thermogravimetric Analysis, Renew. Energ., 68, 111-117, 2014.
  38. Omrani Fard, H.,Ghazanfari Moghaddam A., Shamsi M., and Ataei S.A., Mechanical Properties and Kinetics of Thermal Degradation of Bioplastics Based on Straw Cellulose and Whole Wheat Flour, Iran. J.  Polym. Sci. Technol. (Persian), 25, 74-65, 2012.
  39. Shlensky O.F., Vaynsteyn E.F., and Matyukhin A.A., Dynamic Thermal Decomposition of Linear Polymers and Its Study by Thermoanalytical Methods, J. Therm. Anal.., 34, 645-655, 1988.
  40. Ounas A., Aboulkas A., El Harfi K., Bacaoui A., and Yaacoubi A., Pyrolysis of Olive Residue and Sugar Cane Bagasse: Non-Isothermal Thermogravimetric Kinetic Analysis, Biores. Technol., 102, 11234-11238, 2011.
  1. Ruvolo-Filho A. and Curti P.S., Chemical Kinetic Model and Thermodynamic Compensation Effect of Alkaline Hydrolysis of Waste Poly(Ethylene Terephthalate) in Nonaqueous Ethylene Glycol Solution, Indus. Eng. Chem. Res., 45, 7985-7996, 2006.