The Phillips process

In this process ethylene, dissolved in a liquid hydrocarbon such as cyclohexane, is polymerised by a supported metal oxide catalyst at about 130-160°C and at about 200-500 Ibf/in (1.4-3.5 MPa) pressure. The solvent serves to dissolve polymer as it is formed and as a heat transfer medium but is otherwise inert. 

The preferred catalyst is one which contains 5% of chromium oxides, mainly Cr03, on a finely divided silica-alumina catalyst (75-90% silica) which has been activated by heating to about 250°C. After reaction the mixture is passed to a gas-liquid separator where the ethylene is flashed off, catalyst is then removed from the liquid product of the separator and the polymer separated from the solvent by either flashing off the solvent or precipitating the polymer by cooling. 

Polymers ranging in melt flow index (an inverse measure of molecular weight) from less than 0.1 to greater than 600 can be obtained by this process but commercial products have a melt flow index of only 0.2-5 and have the highest density of any commercial polyethylenes ( 0.96 g/cm ). 

In a variation of the process polymerisation is carried out at about 90-100°C, which is below the crytalline melting point and at which the polymer has a low 

---

The Phillips process is a two-stage crystallisation process that uses a pulsed column in the second stage to purify the crystals (79,80). In the pulsed column, countercurrent contact of the high purity PX Hquid with cold crystals results in displacement of impurities. In the first stage, a rotary filter is used. In both stages, scraped surface chillers are used. This process was commercialized in 1957, but no plants in operation as of 1996 use this technology. 

Polymerization in Hquid monomer was pioneered by RexaH Dmg and Chemical and Phillips Petroleum (United States). In the RexaH process, Hquid propylene is polymerized in a stirred reactor to form a polymer slurry. This suspension is transferred to a cyclone to separate the polymer from gaseous monomer under atmospheric pressure. The gaseous monomer is then compressed, condensed, and recycled to the polymerizer (123). In the Phillips process, polymerization occurs in loop reactors, increasing the ratio of available heat-transfer surface to reactor volume (124). In both of these processes, high catalyst residues necessitate post-reactor treatment of the polymer. 

There are two commercial PPS processes being practiced worldwide the Phillips process and the Kureha process. Although these processes contain some common steps, there are distinguishing features, most notably in the reagents used to faciUtate the synthesis of high molecular weight linear PPS. 

The first commercial PPS process by Phillips synthesized a low molecular weight linear PPS that had modest mechanical properties. It was usehil in coatings and as a feedstock for a variety of cured injection-molding resins. The Phillips process for preparing low molecular weight linear PPS consists of a series of nucleophilic displacement reactions that have differing reactivities (26). 

The modern HF alkylation processes are also differentiated primarily by the reactor system that is used. The Phillips process employs a gravity acid circulation system and a riser reactor (19). The UOP process uses a pumped acid circulation system and an exchanger reactor (20). 

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). 

Solution Polymerization These processes may retain the polymer in solution or precipitate it. Polyethylene is made in a tubular flow reactor at supercritical conditions so the polymer stays in solution. In the Phillips process, however, after about 22 percent conversion when the desirable properties have been attained, the polymer is recovered and the monomer is flashed off and recyled (Fig. 23-23 ). In another process, a solution of ethylene in a saturated hydrocarbon is passed over a chromia-alumina catalyst, then the solvent is separated and recyled. Another example of precipitation polymerization is the copolymerization of styrene and acrylonitrile in methanol. Also, an aqueous solution of acrylonitrile makes a precipitate of polyacrylonitrile on heating to 80°C (176°F). 

In the mid-1950s a number of new thermoplastics with some very valuable properties beeame available. High-density polyethylenes produced by the Phillips process and the Ziegler process were marketed and these were shortly followed by the discovery and rapid exploitation of polypropylene. These polyolefins soon became large tonnage thermoplastics. Somewhat more specialised materials were the acetal resins, first introduced by Du Pont, and the polycarbonates, developed simultaneously but independently in the United States and Germany. Further developments in high-impact polystyrenes led to the development of ABS polymers. 

This process has many similarities to the Phillips process and is based on the use of a supported transition metal oxide in combination with a promoter. Reaction temperatures are of the order of 230-270°C and pressures are 40-80 atm. Molybdenum oxide is a catalyst that figures in the literature and promoters include sodium and calcium as either metals or as hydrides. The reaction is carried out in a hydrocarbon solvent. 

The Phillips process for the manufacture of high-density polyethylene may be adapted to produce copolymers of ethylene with small amounts of propylene or but-l-ene and copolymers of this type have been available since 1958. These soon found application in blown containers and for injection moulding. Properties of two grades of such copolymers are compared with two grades of Phillips-type homopolymer in Table 11.11. 

Figure 27 Propagation, termination and transfer reactions in ethylene polymerisation by the Phillips process.

A major characteristic of the Phillips process chain polymerisation of ethylene is that it leads to very limited branching. The resulting polymer is thus highly linear and can reach high levels of crystallinity, hence high densities approaching 0.96-0.97. Such a polyethylene is known as HDPE for "High-density polyethylene". 

High-density polyethylene (HDPE) is a commodity chemical that is produced on a very large scale in one of two catalytic processes the Ziegler-Natta and the Phillips process. The latter accounts for about one third of all polyethylene. It uses a catalyst consisting of small amounts of chromium (0.2-1.0 wt% Cr) on a silica support, developed by Hogan and Banks at the Phillips Petroleum Company in the early 1950s [84,85]. 

The Phillips process uses a threefold excess of 2,5-dimethylpyrrole, a chromium salt, and an excess of an alkyl aluminium compound [6], In Figure 9.9 we have drawn only one ligand per chromium, but we do not know the... 

Recycled HDPE items (blow-moulding grade) produced from HDPE made by the Phillips process were analysed by IR spectroscopy. The absorption bands at 888 and 965 cm-1, corresponding to unsaturations of vinylidene and vinylene type, respectively, are common in PE produced by either the Ziegler process or metallocenes [104]. The absence of these bands in the IR spectrum of the different samples confirmed that the resins had been produced using a Cr-type catalyst [118]. 

Modifications have recently been proposed for the Dimersol and the Phillips processes by Institut Frangais du Petrol and Sasol Technologies, respectively, based on the use of an ionic liquid such as imidazolium tetra-chloroaluminate (Figure 17), which is liquid at room temperature and an excellent solvent for the organometallic catalyst. 

The Phillips process is also based on the principle of the operation of two reactors in parallel, one in the reaction phase, and the second in the regeneration phase. It operates... 

Polymerizations that use supported chromium (Phillips) catalysts are conducted predominantly in slurry processes (though a small portion employs the gas phase process, see below). The historical development of the Phillips process has been expertly reviewed by Hogan (5, 6) and McDaniel (7-9). The slurry process originally developed by Phillips Petroleum (now Chevron Phillips) has been called the "particle form loop slurry process" and the "slurry loop reactor process" for production of HDPE and LLDPE (10). Hexene-1 is most often used as comonomer for LLDPE in the Phillips process. A simplified process flow diagram for the Phillips loop-slurry reactor process is shown in Figure 7.3 and key operating features are summarized in Table 7.4. 

Ethylene dimerization and oligomerization (Dimersol and Phillips process) is much less developed, because of the economic situation. Even in the most favorable conditions, nickel catalysts unavoidably produce a mixture of 1- and 2-butenes and ethylene is generally more expensive than 2-butene and 1-bu-tene/2-butene mixtures. Feedstocks are either polymerization-grade ethylene or a 50 50 mixture with ethane. In this latter case a gas phase is inevitably present in the reactor. The product composition is strongly dependent on ethylene conversion. The Phillips process probably uses NiCl2 2 PBus as catalyst. Due to the very high reactivity of ethylene, catalyst consumption is remarkably low. 

---