Kinetic study on liquid propylene polymerization using a modified heat flow reaction calorimeter

Document Type : Original research

Authors

Department of Process and Modeling, Iran Polymer and Petrochemical Institute, P.O. Box 14185/458, Tehran, Iran

Abstract

Bulk phase polymerization of propylene with a 4th generation of Ziegler-Natta catalyst was kinetically investigated by means of heat flow calorimetry. The assumptions and modifications on isothermal calorimetric method were demonstrated. Our calibration method showed that heat exchange with the reactor cover plate is not constant over time. Therefore, the dynamic of cover plate temperature was considered in the calorimetric method. The polymerization rate profiles depending on hydrogen and external electron donor concentration have been investigated. Normalized polymerization profiles (Rp /Rpmax) are plotted and expressed as an exponential function of time. Effects of hydrogen and external electron donor (ED) concentration on Rpmax and polymerization rate were investigated as well. The results showed that by increasing hydrogen concentration, initial polymerization rate (Rpmax) increased. Hydrogen increased productivity by increasing the initial polymerization rate, while it had no negative effect on the rates of decay or its effect was small. The ED concentration was optimized so that the catalyst deactivation rate was at its lowest level. Also, changes in the ratio of activation to inactivation with ED concentration were examined, and a proportional change was observed.

Keywords

Main Subjects


  1. Levenspiel O (1999) Chemical reaction engi­neering. Industrial & engineering chemistry re­search. Ind Eng Chem Res 38: 4140-4043
  2. Choi KY, Ray WH (1985) Polymerization of ole­fins through heterogeneous catalysis. II. Kinet­ics of gas phase propylene polymerization with Ziegler–Natta catalysts. J Appl Polym Sci 30: 1065-1081
  3. Soares JB, Hamielec AE (1996) Kinetics of propylene polymerization with a non-supported heterogeneous Ziegler-Natta catalyst-effect of hydrogen on rate of polymerization, stereoregu­larity, and molecular weight distribution. Poly­mer 37: 4607-4614
  4. Lavoisier AL, De Laplace PS (1892) Abhand­lungen über die Wärme 1780 and 1784. In: Ost­wald's Klassiker der Exakten Wissenschafen 40: 28, ed. Rosenthal J Wilhelm Engelmann, Leipzig
  5. Tisse VF, Sheibat-Othman N, McKenna TF (2010) A lab-scale reaction calorimeter for olefin polymerization. Canadian J Chem Eng 88: 783- 792
  6. Samson JJ, van Middelkoop B, Weickert G, Westerterp KR (1999) Gas-phase polymerization of propylene with a highly active Ziegler-Natta catalyst. AIChE J 45: 1548-1558
  7. Karlsen LG, Villadsen J (1987) Isothermal reac­tion calorimeters-I. A literature review. Chem Eng Sci 42:1153-1164
  8. Hansen LD, Hart RM (2004) The art of calorim­etry. Thermochimica acta 17: 257-273
  9. Samson JJ, Weickert G, Heerze AE, Westerterp KR (1998) Liquid-phase polymerization of pro­pylene with a highly active catalyst. AIChE J 44:1424-1437
  10. Meier GB, Weickert G, Van Swaaij WP (2001) Gas-phase polymerization of propylene: Reac­tion kinetics and molecular weight distribution. J Polym Sci Pol Chem 15: 500-513
  11. Kettner J, Valaei S, Bartke M (2020) Reaction calorimetry for studying kinetics in bulk phase polymerization of propene. Macromol React Eng 26: 2000031
  12. Ali MA, Betlem B, Roffel B, Weickert G (2007) Estimation of the polymerization rate of liquid propylene using adiabatic reaction calorimetry and reaction dilatometry. Macromol React Eng 8: 353-363
  13. Samson JJ, Bosman PJ, Weickert G, Westerterp KR (1999) Liquid-phase polymerization of pro­pylene with a highly active Ziegler–Natta cata­lyst. Influence of hydrogen, cocatalyst, and elec­tron donor on the reaction kinetics. J Polym Sci Pol Chem 15: 219-232
  14. Shimizu F, Pater JT, Weickert G (2001) Three-site mechanism and molecular weight: Time dependency in liquid propylene batch polymer­ization using a MgCl2-supported Ziegler-Natta catalyst. J Appl Polym Sci 81:1035-1047
  15. Pater JT, Weickert G, Van Swaaij WP (2002) Po­lymerization of liquid propylene with a 4th gen­eration Ziegler-Natta catalyst-influence of tem­perature, hydrogen and monomer concentration and prepolymerization method on polymeriza­tion kinetics. Chem Eng Sci 57: 3461-3477
  16. Mckenna TF, Févotte G, Graillat C, Guillot J (1996) Joint use of calorimetry, densimetry and mathematical-modeling for multiple component polymerization. Chem Eng Res des 74: 340-348
  17. Korber F, Hauschild K, Winter M, Fink G. (2001) Reaction calorimetric investigation of the pro­pylene slurry phase polymerization with a silica-supported metallocene/MAO catalyst. Macromol Chem Phys 202: 3323-3328
  18. Rouquerol J, Zielenkiewicz W (1986) Suggested practice for classification of calorimeters. Ther­mochimica Acta. 109: 121-37
  19. Zogg A, Stoessel F, Fischer U, Hungerbühler K (2004) Isothermal reaction calorimetry as a tool for kinetic analysis. Thermochimica acta 419: 1-7
  20. McKenna TF, Othman S, Fevotte G, Santos AM, Hammouri H (2000) An integrated approach to polymer reaction engineering: A review of calo­rimetry and state estimation. Polym React Eng 8: 1-38
  21.  Guastalla G, Giannini U (1983) The influence of hydrogen on the polymerization of propylene and ethylene with an MgCl2 supported catalyst. Makromol Chem Rapid Commun 4: 519-527
  22. Rishina LA, Vizen EI, Sosnovskaja LN, Dy­achkovsky FS (1994) Study of the effect of hy­drogen in propylene polymerization with the MgCl2-supported Ziegler-Natta catalyst-part 1. Kinetics of polymerization. Eur Polym J 30: 1309-1313