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The Phillips catalyst, or the Phillips supported chromium catalyst, is the
The Phillips catalyst, or the Phillips supported chromium catalyst, is the catalyst
Catalysis () is the process of increasing the rate of a chemical reaction by adding a substance known as a catalyst (). Catalysts are not consumed in the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recyc ...
used to produce approximately half of the world's polyethylene
Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including ...
. A heterogeneous catalyst
In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reactants or products. The process contrasts with homogeneous catalysis where the reactants, products and catalyst exist in the same phase. ...
, it consists of a chromium
Chromium is a chemical element with the symbol Cr and atomic number 24. It is the first element in group 6. It is a steely-grey, lustrous, hard, and brittle transition metal.
Chromium metal is valued for its high corrosion resistance and h ...
oxide supported on silica gel
Silica gel is an amorphous and porous form of silicon dioxide (silica), consisting of an irregular tridimensional framework of alternating silicon and oxygen atoms with nanometer-scale voids and pores. The voids may contain water or some other ...
. Polyethylene, the most abundant synthetic polymer, is produced industrially by the polymerization
In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many fo ...
of ethylene
Ethylene ( IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds).
Ethylene ...
:
:n C2H4 → (C2H4)n
Although exergonic (i.e., thermodynamically favorable), the reaction requires catalysts. Three main catalysts are employed commercially: the Phillips catalyst, Ziegler–Natta catalyst A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes ( alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility:
* ...
s (based on titanium trichloride
Titanium(III) chloride is the inorganic compound with the formula TiCl3. At least four distinct species have this formula; additionally hydrated derivatives are known. TiCl3 is one of the most common halides of titanium and is an important cataly ...
), and, for specialty polymers, metallocene
A metallocene is a compound typically consisting of two cyclopentadienyl anions (, abbreviated Cp) bound to a metal center (M) in the oxidation state II, with the resulting general formula Closely related to the metallocenes are the metallocene d ...
-based catalysts.
Preparation and mechanism of action
The Phillips catalyst is prepared by impregnating high surface area silica gel withchromium trioxide
Chromium trioxide (also known as chromium(VI) oxide or chromic anhydride) is an inorganic compound with the formula CrO3. It is the acidic anhydride of chromic acid, and is sometimes marketed under the same name.
This compound is a dark-purple ...
or related chromium compounds. The solid precatalyst is then calcined in air to give the active catalyst. Only a fraction of the chromium is catalytically active, a fact that interferes with elucidation of the catalytic mechanism. The active catalyst is often depicted as a chromate ester
In chemistry, an ester is a compound derived from an oxoacid (organic or inorganic) in which at least one hydroxyl group () is replaced by an alkoxy group (), as in the substitution reaction of a carboxylic acid and an alcohol. Glycerides ...
bound to the silica surface. The mechanism for the polymerization process is the subject of much research, the central question being the structure of the active species, which is assumed to be an organochromium compound Organochromium chemistry is a branch of organometallic chemistry that deals with organic compounds containing a chromium to carbon bond and their reactions. The field is of some relevance to organic synthesis. The relevant oxidation states for organ ...
. Robert L. Banks and J. Paul Hogan
John Paul Hogan (August 7, 1919 – February 19, 2012) was an American research chemist. Along with Robert Banks, he discovered methods of producing polypropylene and high-density polyethylene.
Hogan was born in Lowes, Kentucky to Charles Frankli ...
, both at Phillips Petroleum
Phillips Petroleum Company was an American oil company incorporated in 1917 that expanded into petroleum refining, marketing and transportation, natural gas gathering and the chemicals sectors. It was Phillips Petroleum that first found oil in th ...
, filed the first patents on the Phillips catalyst in 1953. Four years later, the process was commercialized.J.P. Hogan, R.L. Banks, U.S. Patent 2,825,721 to Phillips Petroleum Company, filed August, 1954 and issued March, 1958.
References