Phillips process

Phillips PPS process Phillips process Phillips slurry process... 

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. 

Fluorocarbons are made commercially also by the electrolysis of hydrocarbons in anhydrous hydrogen fluoride (Simons process) (14). Nickel anodes and nickel or steel cathodes are used. Special porous anodes improve the yields. This method is limited to starting materials that are appreciably soluble in hydrogen fluoride, and is most useflil for manufacturing perfluoroalkyl carboxyflc and sulfonic acids, and tertiary amines. For volatile materials with tittle solubility in hydrofluoric acid, a complementary method that uses porous carbon anodes and HF 2KF electrolyte (Phillips process) is useflil (14). 

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. 

Researchers at Phillips Petroleum Company developed a commercially viable process for the synthesis of PPS involving the polymerization of /)-dich1orohenzene and a sodium sulfide source in a polar organic compound at elevated temperature and pressure. This Phillips process was patented in 1967 (18). Between 1967 and 1973, Phillips built and operated a pilot plant, estabhshed market demand, and constmcted a hiU-scale commercial plant. In 1973, the world s first PPS plant came on-stream in Phillips faciUty in Borger, Texas. 

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). 

The first reactor in series in the Arco, lEP, and Phillips processes is adiabatic (vessel filled with catalyst). The exothermic heat of reaction is removed in a pump-around loop where a portion of the reactor contents are taken from the reactor, pumped through an external exchanger, cooled, and returned to the reactor. 

These siUca-supported catalysts demonstrate the close connections between catalysis in solutions and catalysis on surfaces, but they are not industrial catalysts. However, siUca is used as a support for chromium complexes, formed either from chromocene or chromium salts, that are industrial catalysts for polymerization of a-olefins (64,65). Supported chromium complex catalysts are used on an enormous scale in the manufacture of linear polyethylene in the Unipol and Phillips processes (see Olefin polymers). The exact stmctures of the surface species are still not known, but it is evident that there is a close analogy linking soluble and supported metal complex catalysts for olefin polymerization. 

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... 

The so-called Phillips Process was, as its name implies, devised in the laboratories of the Phillips Petroleum Company during the 1970s [53]. 

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