Phillips Petroleum

Reference Data for Hydrocarbons and Petro-Sulfur Compounds, Phillips Petroleum Company, 1962. 

The Provesteen process, developed by Phillips Petroleum Company, employs a proprietary 25,000-L continuous fermentor for producing Hansenu/a jejunii the sporulating form of C. utilis from glucose or sucrose at high cell concentrations up to 150 g/L. The fermentor is designed to provide optimum oxygen and heat transfer (69,70). 

Ryton fibers are high performance products developed by Phillips Petroleum Co. by reaction of -dichloroben2ene with sodium sulfide in the presence of a polar solvent according to the following ... 

Phillips 66 Engineering Standards, Phillips Petroleum Co., BartiesviUe, OHa., 1976. 

Older rerefining units used 2-5 kg/L of activated clay at 40—70°C and higher temperatures in place of TEE to clean the oil (80). More elaborate chemical and hydrotreating of used engine oils without a distillation step has been developed by Phillips Petroleum for processing 40,000 /yr (10 X 10 gal/yr). Establishment of a reflable feedstock supply is a critical consideration for larger rerefining plants. 

Second, in the early 1950s, Hogan and Bank at Phillips Petroleum Company, discovered (3,4) that ethylene could be catalyticaHy polymerized into a sohd plastic under more moderate conditions at a pressure of 3—4 MPa (435—580 psi) and temperature of 70—100°C, with a catalyst containing chromium oxide supported on siUca (Phillips catalysts). PE resins prepared with these catalysts are linear, highly crystalline polymers of a much higher density of 0.960—0.970 g/cnr (as opposed to 0.920—0.930 g/cnf for LDPE). These resins, or HDPE, are currentiy produced on a large scale, (see Olefin polymers, HIGH DENSITY POLYETHYLENE). 

High density polyethylene (HDPE) is defined by ASTM D1248-84 as a product of ethylene polymerisation with a density of 0.940 g/cm or higher. This range includes both homopolymers of ethylene and its copolymers with small amounts of a-olefins. The first commercial processes for HDPE manufacture were developed in the early 1950s and utilised a variety of transition-metal polymerisation catalysts based on molybdenum (1), chromium (2,3), and titanium (4). Commercial production of HDPE was started in 1956 in the United States by Phillips Petroleum Company and in Europe by Hoechst (5). HDPE is one of the largest volume commodity plastics produced in the world, with a worldwide capacity in 1994 of over 14 x 10 t/yr and a 32% share of the total polyethylene production. 

One of the most efficient implementations of the slurry process was developed by Phillips Petroleum Company in 1961 (Eig. 5). Nearly one-third of all HDPE produced in the 1990s is by this process. The reactor consists of a folded loop with four long (- 50 m) vertical mns of a pipe (0.5—1.0 m dia) coimected by short horizontal lengths (around 5 m) (58—60). The entire length of the loop is jacketed for cooling. A slurry of HDPE and catalyst particles in a light solvent (isobutane or isopentane) circulates by a pump at a velocity of 5—12 m/s. This rapid circulation ensures a turbulent flow, removes the heat of polymeriza tion, and prevents polymer deposition on the reactor walls. 

Commercial production of PE resias with densities of 0.925 and 0.935 g/cm was started ia 1968 ia the United States by Phillips Petroleum Co. Over time, these resias, particularly LLDPE, became large volume commodity products. Their combiaed worldwide productioa ia 1994 reached 13 X 10 metric t/yr, accouatiag for some 30% market share of all PE resias ia the year 2000, LLDPE productioa is expected to iacrease by 50%. A aew type of LLDPE, compositioaaHy uniform ethylene—a-olefin copolymers produced with metallocene catalysts, was first introduced by Exxon Chemical Company in 1990. The initial production volume was 13,500 t/yr but its growth has been rapid indeed, in 1995 its combiaed production by several companies exceeded 800,000 tons. 

Chromium Oxide-Based Catalysts. Chromium oxide-based catalysts were originally developed by Phillips Petroleum Company for the manufacture of HDPE resins subsequendy, they have been modified for ethylene—a-olefin copolymerisation reactions (10). These catalysts use a mixed sihca—titania support containing from 2 to 20 wt % of Ti. After the deposition of chromium species onto the support, the catalyst is first oxidised by an oxygen—air mixture and then reduced at increased temperatures with carbon monoxide. The catalyst systems used for ethylene copolymerisation consist of sohd catalysts and co-catalysts, ie, triaLkylboron or trialkyl aluminum compounds. Ethylene—a-olefin copolymers produced with these catalysts have very broad molecular weight distributions, characterised by M.Jin the 12—35 and MER in the 80—200 range. 

Phillips Petroleum Company developed an efficient slurry process used for the production of both HDPE and LLDPE (Eig. 6). The reactor is built as a large folder loop containing long mns of pipe from 0.5 to 1 m ia diameter coimected by short horizontal stretches of pipe. The reactor is filled with a light solvent (usually isobutane) which circulates through the loop at high speed. A mixed stream containing ethylene and comonomers (1-butene,... 

Countries produciug commodity LLDPE and their capacities, as well as production volumes of some U.S. companies, are Hsted iu Table 5. Iu most cases, an accurate estimate of the total LLDPE production capacity is compHcated by the fact that a large number of plants are used, iu turn, for the manufacture of either HDPE or LLDPE iu the same reactors. VLDPE and LLDPE resius with a uniform branching distribution were initially produced in the United States by Exxon Chemical Company and Dow Chemical Company. However, since several other companies around the world have also aimounced their entry into this market, the worldwide capacity of uniformly branched LLDPE resins in 1995 is expected to reach a million tons. Special grades of LLDPE resins with broad MWD are produced by Phillips Petroleum Co. under the trade name Low Density Linear Polyethylenes or LDLPE. 

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