Amoco CD commercial polypropylene catalyst tailor-made for the Amoco-Chisso gas phase process

Document Type: Review

Author

Oakwood Consulting, Inc., Wheaton, Illinois, 60187, USA

Abstract

The commercial profile of the Amoco CD MgCl2 supported polypropylene catalyst is presented. The development, the unique method of preparation/production, with emphasis on particle morphology, and the parameters affecting particle size (PS), particle size distribution (PSD), and particle shape are discussed in detail. The outstanding performance of the catalyst, tailoredmade for the Amoco-Chisso gas phase process, is attributable to synergistic effects, originating from catalyst and process design factors. Catalyst median particle size (d50) may be controlled in the 7-100 microns range. Parameters affecting PS and PSD during catalyst support preparation include: agitation speed, temperature, organic reagent to Mg ratios, morphology controlling agents, and deliberate spiking of the aromatic solvent used with appropriate contaminants. Particle shape variation between the cubic and spheroidal is affected by the types of reagents used, the ratios of these reagents to Mg, the time/temperature profile of the procedure, and the sequence of reagent addition during catalyst support preparation. Catalyst activation takes place in several steps by thermal treatment of the support with TiCl4/toluene solutions. Cost-effective TiCl4/toluene reuse system from the
activation streams has been put in place to reduce waste material considerably. There is an optimum temperature of activation close to 120˚C. The progress of activation as well as catalyst quality may be monitored by IR spectroscopy, expressed in easily identifiable IR fingerprint patterns, which correlate well with the catalyst performance. More recently a new concept of supported catalysts based on the CD technology has been developed. It features organometallic complexes instead of just TiCl4 as the polymerization active centers. The new catalysts show improved performance and advantageous polymer product properties. We suggest that the newly invented organometallic complexes may open a new era in polyolefin catalysis, including polyethylene copolymers. The success of the CD and Amoco-Chisso process is illustrated by the two dozen commercial plants worldwide that use the technology, and the recent licensing advances by Ineos, the successor of Amoco, for this polypropylene technology.

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Main Subjects


  1. Arzoumanidis G, Karayannis N, Khelghatian M, Lee S (1992) Commercial polypropylene catalysts. Catal. Today 13:59-71
  2. Arzoumanidis G, Karayannis N (1993) Fine-tuning polypropylene. Chem Tech 23:43-48
  3. Arzoumanidis G (2014) Novel Ti-Aryl complexes as internal or external modifiers, improving performance of MgCl2 supported polypropylene catalysts. In: SPE polyolefins conference, Houston, TX
  4. Hadian N, Hakim S, Nokoomanesh-Haghighi M, Bahri-Laleh N (2014) Storage time effect on dynamic structure of MgCl2.nEtOH adducts in heterogeneous Ziegler-Natta catalysts. Polyolefins J. 1:33-41
  5. Arzoumanidis G, Karayannis N, Khelghatian H, Lee S (1989 Dec 9) Olefin polymerization catalyst, US Patent 4,866,022; (1991 Jan 29) US Patent 4,988,656; (1991 May 7) US Patent 5,013,702
  6. Corbin G, Lee K (1993) Paper O-Amoco impact copolymer. In: DeWitt petrochemical review. Houston, TX
  7. Ineos Technologies (2014) Website
  8. Cohen S, Arzoumanidis G, Karayannis M, Khelghatian H, Lee S (1990 Aug 7) Morphology-controlled olefin polymerization catalyst, US Patent 4,946,816
  9. Arzoumanidis G, Drezdzon M, Lee S (1992 Jun 23) Olefin polymerization and copolymerization catalyst, US Patent 5,124,297
  10.  Lee S, Karayannis M (1993 Jun 29) Olefin polymerization and copolymerization catalyst, US Patent 5,223,466
  11.  Arzoumanidis G, Peaches C (1993 Jan 26) Olefin polymerization and copolymerization catalyst, US patent 5,182,245
  12.  Tachibana M, Uwai T, Matsukawa T, Hayashida T (1992 Jan 28) Catalysts for Polymerization of Olefins, US Patent 5,084,429
  13. Gnomakumar S (2013) Synthesis and molecular properties of new MgCl2-based molecular adducts towards catalytic polyolefin production. PhD Thesis, CSIR-National Chemical Laboratory, Pune, India
  14. Arzoumanidis G, Karayannis N (1989) Infrared characterization of supported polypropylene polymerization catalysts-a link to catalyst performance. In: International symposium on recent developments in olefin polymerization catalysts. Tokyo, Japan
  15. Caracotsios M (1992) Theoretical modeling of Amoco's gas phase horizontal stirred bed reactor for the manufacturing of polypropylene resins. Chem Eng Sci 47: 2591-2596
  16. Novac M (1992) New polypropylene products. In: Polypropylene world congress. Zurich, Switzerland
  17.  Haruyuki M, Hirashi T, Akihiko I, Terumori F (2011) FI catalysts for olefin polymerization-A comprehensive treatment. Chem Rev 111: 2363- 2449
  18. Kashiwa N (2003) The discovery and progress of MgCl2-supported TiCl4 Catal. J Poly Sci, Part A: Polym Chem 42: 1-8

Volume 1, Issue 2
Summer and Autumn 2014
Pages 131-137
  • Receive Date: 04 October 2014
  • Revise Date: 01 November 2014
  • Accept Date: 27 October 2014