Review on Development of Polypropylene Manufacturing Process

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1 Review on Development of Polypropylene Manufacturing Process Sumitomo Chemical Co., Ltd. Process & Production Technology Center Hideki SATO Hiroyuki OGAWA Polypropylene () is a typical commodity plastic and has been widely used in many application fields including packaging films, industrial components and miscellaneous goods, due to its excellence in properties such as stiffness, heat resistance and processability in addition to light weight material density and also a relatively low price. The continued demands from the market for higher performances have stimulated, particularly in recent time, the improvement of manufacturing processes with newly created ideas. This review describes, mainly based on the information published in literature and patents, an outline of the development history of manufacturing processes and an introduction to recent progress, including our own technologies G. Natta 1) 50 4,700 t ) α-

2 Å µm 3) AP 4) 1st Generation Solvent polymerization process 2nd Generation a) Solvent polymerization process (Non-deashing) Fig. 1 Monomer Recovery Degassing Solvent Recovery Deashing b) Bulk polymerization process (Non-solvent) Drying 3rd Generation Vaper phase polymerization process (Non-deashing, Non-AP) AP, Ash Monomer Recovery Degassing Solvent Recovery AP Monomer Recovery Extraction AP, Ash Drying Polypropylene manufacturing process APAP, AP Fig. 1 Fig. 1 Fig. 2 5) Montecatini MPa 1 AP AP AP AP

3 Solvent Propylene Water Centrifuge Solvent Recovery Reactor Degasser Deashing Tank Slurry Tank Dryer N2 Alcohol Propylene Recovery Compressor Drainage AP Heavy Solvent Recovery Fraction Fig. 2 Schematic flow diagram of Sumitomo s solvent polymerization process Fig. 3 Fig. 2 Propylene Fig. 3 AP Extraction AP Separation Recycle Monomer Compressor Heavy Fraction Monomer Purification Schematic flow diagram of Sumitomo s bulk polymerization process Powder Powder Separation 5) AP MPa

4 AP AP Fig. 4 6) 2 1 Propylene Ethylene Fig. 4 Recycle Monomer Powder Separation Schematic flow diagram of Sumitomo s vaper phase polymerization process Powder MPa 7)

5 Distribution of Composition/Molecluar Weight (a) Perfect mixing type reactor Distribution of Residence Time Model Structure of Particle (Red-color portion indicates schematically a part polymerized in the second stage.) wide wide (b) Circulation type reactor (excluding impact co-polymer manufacturing) nallow wide (c) Nallow residence time distribution type reactor (including batch type reactor) nallow nallow Fig. 5 Schematic structure of polymer particle produced by two polymerization zone type reactor Fig. 5Fig. 5 a Fig. 5 b Fig. 6 External circulation fluidized bed type reactor 1 FCC Riser Downcomer 8), 9) Riser m/s 3 10) Riser Riser Zone Fig. 6 Gas Powder Separator Zone Gas Barrier Liq. Monomer Downcomer Zone Product Discharge Gas External circulation fluidized bed type reactor (1) Downcomer Riser Downcomer RiserDowncomer 10), 11) RiserDowncomer 12)

6 Liq. Monomer Liq. or Gas Monomer Fig. 7 Gas External circulation fluidized bed type reactor (2) Fig. 7 External circulation fluidized bed type reactor 2 13) 14) Fig. 8 Internal circulation fluidized bed type reactor 15) Valve Fig. 8 Gas Barrier Gas Gas Barrier Product Discharge Product Discharge Gas Liq. Monomer Product discharge Internal circulation fluidized bed type reactor Fig. 5 c 16) 2

7 Fig. 9 a Horizontal, mechanically stirred type reactor 1 17) ) Fig. 9 b Horizontal, mechanically stirred type reactor 2 Fig. 9 a 19) 20) Liq. Monomer 21) 24) Fig. 10 Multi-stage fluidized bed type reactor 24) Supplemental Gaseous Monomer Cooling Fluid Blower Plate Coil Heat Exchanger Downcomer Cooling Fluid Outlet Cooling Jacket (a) Weir Weir Weir Horizontal Shaft Agitator Product discharge Gas Gas Distribution Plate N2 Gas Surge Vessel Liq. Monomer Liq. Monomer Fig. 10 Gas Product Discharge Multi-stage fluidized bed type reactor (b) Fig. 9 Weir Weir Weir Horizontal, mechanically stirred type reactor (1)(2) Horizontal Shaft Agitator Product discharge Gas Gas 25) 29) Fig. 11 Fluidized bed type reactor with particle segregation zone 29)

8 Gas Particle Segregation Zone Internal Product Discharge 200m 15 31), 32) 2 2 Fig. 11 Fluidized bed type reactor with particle segregation zone Fig. 12 Tubular type reactor 30) ) Gas Circulation Cyclone Separator Product Discharge Gas Gas Distributor Fresh (co) monomer (Optional) Fresh (co) monomer (Optional) Fig. 12 Tubular type reactor

1) G. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, G. Mazzaniti and G. Moraglio, J. Am. Chem. Soc., 77, 1708 (1955). 2), (2008). 3),,, 1984-@, 15 (1984). 4) 15 16, (2005).

9) Montell, European Patent 1012195-A (2000). 10) M. Covezzi and G. Mei, Chem. Eng. Sci., 56, 4059 (2001). 11) A. de Vries and N. Izzo-Iammarrone, DECHEMA Monographs, 137, 43 (2001).

9 1) G. Natta, P. Pino, P. Corradini, F. Danusso, E. Mantica, G. Mazzaniti and G. Moraglio, J. Am. Chem. Soc., 77, 1708 (1955). 2), (2008). 3),,, 15 (1984). 4) 15 16, (2005). 5),,,,, 52 (1980). 6),,,,,, 4 (1986). 7) K. B. Sinclair, Hydrocarbon Processing, July, 81 (1985). 8) Montell, International Patent WO97/04015 (1997). 9) Montell, European Patent A (2000). 10) M. Covezzi and G. Mei, Chem. Eng. Sci., 56, 4059 (2001). 11) A. de Vries and N. Izzo-Iammarrone, DECHEMA Monographs, 137, 43 (2001). 12) Spherliene and Himont, European Patent A2 (1993). 13) Basell, International Patent WO2004/ (2004). 14) G. Weickert and C. Dittrich, Chemie Ingenieur Technik, 77 (8), 977 (2005). 15) Universiteit Twente, European Patent A1 (2004). 16) J. J. Zacca, J. A. Debling and W. H. Ray, Chem. Eng. Sci., 51, 4859 (1996). 17), (1984). 18) C. J. Dittrich and S. M. P. Mutsers, Chem. Eng. Sci., 62, 5777 (2007). 19), (1996). 20),,, (1998), p ) Phillips, U.S. Patent (1960). 22) Union Carbide Chem., International Patent WO98/47611 (1998). 23), (2003). 24) Phillips, U.S. Patent (1993). 25), (1980). 26), (1995). 27), (1998). 28), (1998). 29), (2006). 30) Elenac, International Patent WO00/49055 (2000). 31), (2007). 32), (2007). 33) Hydrocarbon Processing, March, 136 (1999). PROFILE Hideki SATO Hiroyuki OGAWA

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