Reaction engineering
Mehrsa Emami; Mahmoud Parvazinia; Hossein Abedini
Abstract
Gas phase polymerization of propylene was carried out in a semi-batch minireactor using a commercially supported Ziegler–Natta (ZN) catalyst. The influence of variables including monomer partial pressure, external electron donor, reaction temperature and time on the particle morphology and size ...
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Gas phase polymerization of propylene was carried out in a semi-batch minireactor using a commercially supported Ziegler–Natta (ZN) catalyst. The influence of variables including monomer partial pressure, external electron donor, reaction temperature and time on the particle morphology and size distribution was investigated. Generally, more uniform fragmentation and particle densities were obtained at lower reaction rates. Monomer partial pressure showed a significant role of particle size and its distribution, the higher the monomer partial pressure, the broader particle size distribution was obtained. Polymerization pressure had a significant role on the morphology of particles. Wider cracks and more porosity were resulted from the polymerizations at higher pressures. Furthermore, a broader particle size distribution was obtained from the polymerization at higher pressures. The particle size analysis revealed the monomer partial pressure as the most effective parameter on the distribution of particles. The SEM images showed that three different steps could be distinguished in the development of particle morphology within the particle, showing the initiation and development of cracks and appearance of fragments inside the particle.
Catalysis
Gregory G. Arzoumanidis
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 ...
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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.
