Phillips polyethylene catalysts catalyst activation

ESR Studies of Surface Species. ESR has been applied widely in heterogeneous catalysis as a technique for examining the nature and concentration of possible catalytic sites when a material is activated either chemically or thermally (64, 65, 66). ESR studies on the Phillips polyethylene catalyst, Cr03/Si02, are a classical example of this application (67). The interpretation of such ESR studies is questionable since the chemical changes during activation are not well understood, and the nature of the surface species may have to be assumed. 

Ziegler Catalysts. For his work in the discovery of a new class of highly active catalysts for polymerization of ethylene, propylene, and dienes, Karl Ziegler shared the 1963 Nobel Prize in Chemistry with Guilio Natta whose contributions were predominantly related to polypropylene. Today, these catalysts together with the Phillips catalyst are responsible for the majority of the world s polyethylene production. Loosely defined, Ziegler catalysts are polyethylene catalysts derived from transition-metal halides and main group metal alkyls (46,50-53). In modem... 

The ethylene polymerization of this catalyst was carried out in an autoclave reactor at 221°F in isopentane as the slurry solvent in the presence of triisobutylaluminum as cocatalyst and 50 psig of hydrogen and sufficient ethylene to achieve a total reactor pressure of 550 psig. The catalyst activity was 10,540 g of PE/g of catalyst/ hr, which corresponded to an activity of 146,000 g PE/g Ti/hr. The granular polyethylene product obtained was considered suitable for a particle-form slurry process such as the Phillips slurry process. The polyethylene sample displayed a Melt Index (I value of 0.70 and a High Load Melt Index ) value (HLMI) of 3 1 with a HLMI/MI ratio of 45, which indicates tfiat the polyethylene molecular weight distribution was of an intermediate value. 

Figure 3.12 Relative Melt Index potential (RMIP) vs secondary catalyst activation temperature. RMIP is the melt index of the polyethylene sample normalized by the Melt Index of the standard Phillips catalyst containing 1 wt% Cr and activated with one thermal treatment in air at 870°C. Melt Index is inversely proportional to polymer MW. Reprinted from [12] with permission from Elsevier Publishing.

Examination of Table 3.4 shows that the deposition of Bis(triphenylsilyl) chromate into porous silica/alumina support increased catalyst activity by at least a factor of 500. The FI/MI ratio of 86-137 indicates that the molecular weight distribution of polyethylene prepared with this catalyst is relatively very broad compared to the Phillips catalyst, which may provide significant product advantages in certain applications over a similar grade of polyethylene prepared with the Phillips catalyst. 

For example, prior to the discovery of this new single-site catalyst type, commercial grades of polyethylene were primarily manufactured over the compositional range of 0-4 mol% of comonomer (1-butene, 1-hexene or 1 -octene) that provided ethylene copolymers over the density range of 0.915-0.970 g/cc. Commercial catalysts were primarily the Cr-based Phillips-type of catalyst or a Ti-based Ziegler catalyst with the xmderstand-ing that both types of catalyst consisted of many different types of active sites. Each type of active site produced a different composition of polyethylene (different molecular weight and branching content) which resulted in a final polyethylene material with a complex molecular structure. These multi-site catalysts limited the composition of the polyethylene that was commercially available due to both process and product constraints imposed by such catalysts. 

As discussed above with Chevron-Phillips metallocene-based catalyst which is activated with solid acid catalyst supports, the introduction of low levels of long-chain branching is an important structural feature of polyethylene manufactured for commercial applications with single-site catalysts. Dow s CGC system is able to incorporate low levels of long-chain branching into the polyethylene due to the high level of vinyl-terminated polymer molecules, the relatively high polymerization temperature that is... 

Aubriet F, Muller JF, Poleunis C, et al Activation processes and polyethylene formation on a Phillips model catalyst studied by laser ablation, laser desorption, and static secondary ion mass spectrometry, J Am Soc Mass Spectrom 17(3) 406-414, 2006. 

Polyethylene. Low pressure polymerization of ethylene produced in the Phillips process utilizes a catalyst comprised of 0.5—1.0 wt % chromium (VI) on siUca or siUca-alumina with pore diameter in the range 5—20 nanometers. In a typical catalyst preparation, the support in powder form is impregnated with an aqueous solution of a chromium salt and dried, after which it is heated at 500—600°C in fluid-bed-type operation driven with dry air. The activated catalyst is moisture sensitive and usually is stored under dry nitrogen (85). 

Supported CrC>3 catalysts, referred to as Phillips catalysts, are important industrial catalysts and are employed in high-density polyethylene production. Phillips catalysts polymerise ethylene with an induction period, which has been ascribed to the slow reduction of Cr(VI) by the monomer and to the displacement of oxidation products (mainly formaldehyde) from the catalytic species [226]. The prereduction of the catalyst with the use of H2 or CO enables the induction period to be eliminated. Active sites thus formed involve surface low-valence Cr(II) and Cr(III) centres, which can appear as mononuclear (formed from chromate species) and binuclear (formed from dichromate species) [227-232],... 

The selection and treatment of the support is fundamental to the process, and a plant may use catalysts made from a variety of supports to produce a whole range of products. Catalyst productivities are of the order of 5 kg of polyethylene per gram of catalyst or higher, with a corresponding chromium content of 2 ppm or less. The percentage of Cr atoms that form active polymerisation centres has been estimated as 12% [43]. Typically, commercial Phillips catalysts contain ca 1 % total Cr and have particle sizes of 30-150 pm [224]. 

Figure 5.2 Surface chromate structures resulting from treatment of silica with CrO. Calcination at high temperatures in air (or Op insures that Cr remains primarily in the +6 oxidation state and results in Phillips catalyst for polyethylene. Final activation occurs in reactor through reactions with ethylene (see text for details).

Second generation Phillips catalysts involve use of titanium compounds that modify the surface chemistry of the support and enables production of polyethylene with higher MI (lower MW) (12). Titanium tetraisopropoxide, also known as tetraisopropyl titanate (TIPT), is the most commonly used modifier for these catalysts. Hexavalent chromium titanate species are probably formed on the surface as shown in Figure 5.3 (13). Catalyst surfaces contain a diversity of active sites and molecular weight distribution of the polymer is broader than that from generation catalysts. 

Figure 5.4 Structures proposed for 4" generation Phillips catalyst. Because of diversity of active centers, catalyst produces polyethylene with broadest MWD (M /M > 50) relative to any other single catalyst in commercial use (7).

This paper examines some factors which affect not only the overall activity, but also the rate of termination of polyethylene chains growing on the Phillips Cr/silica polymerization catalyst. Although the theme of this symposium is not the termination but the initiation of polymer chains, the two aims are not inconsistent because on the Phillips catalyst the initiation and termination reactions probably occur together. They are both part of a continuous mechanism of polymerization. One possibility, proposed by Hogan, is shown below. The shift of a beta hydride simultaneously terminates one live chain while initiating another ... 

Commercial linear polyethylene, the most commonly used type of plastic, was bom more than half a century ago with the accidental discovery at Phillips Petroleum Company that chromium oxide supported on silica can polymerize a-olefins.1 The same catalyst system, modified and evolved, is used even today by dozens of companies throughout the world, and it accounts for a large share of the world s high-density polyethylene (HDPE) supply, as well as some low-density polymers. The catalyst is now more active and has been tailored in numerous ways for many specialized modem applications. This chapter provides a review of our understanding of the complex chemistry associated with this catalyst system, and it also provides examples of how the chemistry has been exploited commercially. It is written from an industrial perspective, drawing especially on the commercial experience and the research of numerous scientists working at Phillips Petroleum... 

Most commercial manufacture of polyethylene with the Phillips catalyst is carried out with Cr(VI)/silica as the catalyst. Cr(VI) is reduced by ethylene in the reactor to form the active precursor, probably Cr(II). However, in some cases, it is desirable to reduce the Cr(VI) to Cr(II) before the catalyst goes into the reactor. Treatment in CO at about 350 °C reduces the hexavalent chromium almost quantitatively to a divalent species. In practice, one must be careful to fully flush out the CO with an inert gas like N2 before the catalyst is allowed to cool. Otherwise, CO is chemisorbed and poisons the catalyst. Actually, CO begins to react with Cr(VI) / silica even at room temperature, although that reaction is slow. Over a period of hours, the Cr(VI) can become highly reduced at 25 °C. However, purging with N2 at higher temperatures is still needed to remove the adsorbed CO. Otherwise, the catalyst will be inactive. 

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