Phillips polyethylene catalysts operation

The nature of polymerization with Standard Oil catalysts is not at present completely understood. Nor is it certain whether the Phillips and Standard Oil catalysts operate by the same or different mechanisms. However, the polyethylene obtained by the Standard Oil processes resembles that produced in the Phillips processes in that it, too, is almost completely linear. 

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). 

Phillips (1) A process for polymerizing ethylene and other linear olefins and di-olefins to make linear polymers. This is a liquid-phase process, operated in a hydrocarbon solvent at an intermediate pressure, using a heterogeneous oxide catalyst such as chromia on silica/ alumina. Developed in the 1950s by the Phillips Petroleum Company, Bartlesville, OK, and first commercialized at its plant in Pasadena, TX. In 1991, 77 reaction fines were either operating or under construction worldwide, accounting for 34 percent of worldwide capacity for linear polyethylene. 

It may be interesting that chain termination with hydrogen, which is utilised in Ziegler-Natta polymerisations, does not operate in polymerisation systems with Phillips catalysts no influence of hydrogen to control the molecular weight of polyethylene in the latter case was achieved [37],... 

The loop reactors, which are recycled tubular reactors, are used by the Phillips Petroleum Co. and Solvay et Cie. The Phillips process is characterized by the use of a light hydrocarbon diluent such as isopentane or isobutane in loop reactors which consist of four jacketed vertical pipes. Figure 1 shows the schematic flow diagram for the loop reactor polyethylene process. The use of high-activity supported chromium oxide catalyst eliminates the need to deash the product. This reactor is operated at about 35 atm and 85-110° C with an average polymer residence time of 1.5 hr. Solid concentrations in the reactor and effluent are reported as 18 and 50 wt %, respectively. The reactor diameter is 30 in. (O.D.) and the length of the reactor loop is about 450 ft. 

Two unique features of a solution polymerization process is the need to operate at relatively higher ethylene pressures in order to maintain a sufficient ethylene concentration due to the higher temperatures used, and the need to utilize an organic solvent such as cyclohexane that readily dissolves polyethylene. For the Phillips catalyst, polymerization temperature was used to control polymer molecular weight. 

At about the same time that news of the Ziegler discovery was released, the Phillips Petroleum Company in the United States atmounced that it had developed a medium-pressure, catalytic process (500 psig) to produce a high-density, crystalline polyethylene. The process was discovered when traces of ethylene in a flue gas had polymerized over conventional cracking catalysts. The Phillips catalyst contained chromic oxide supported on silica. The Standard Oil Company of Indiana (later Amoco) also introduced a medium pressure process using a catalyst comprising molybdenum oxide supported on carbon or alumina, but it did not enjoy the success of the Ziegler or Phillips processes and was only operated in three full-scale plants. ... 

The early Phillips catalysts only needed to be activated and reduced to generate active centers, but several patents since have described the use of co-catalysts to promote the production of LLDPE. For example, a typical catalyst that had been modified with titanium, activated in air and reduced in caibon monoxide was then further activated by addition of triethylboron prior to operation." This procedure led to the production of linear low density polyethylene, LLDPE, which had a density of 0.9726 g cm, directly, without the need for the addition of an a-olefin to the pure ethylene feed. Olefins were produced in situ and these were incorporated into the polyethylene. A second catdyst was made using silica with a very high pore volume, modified with titanium, activated in air, and finally reduced with caibon monoxide at 350°C. This catalyst was then treated with triethylboron before use. LLDPE polymers with densities in the range 0.890 to 0.915 were obtained from a feedstock of ethylene and hexene-1, but the addition of some hydrogen to the gas stream was required to limit the length of the polymer chain. 

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