Petrochemicals

Olefins

The thermal cracking processes developed for refinery processing in the 1920s were focused primarily on increasing the quantity and quality of gasoline components. As a by-product of this process, gases were produced that included a significant proportion of lower-molecular-weight olefins, particularly ethylene, propylene, and butylene. Catalytic cracking is also a valuable source of propylene and butylene, but it does not account for a very significant yield of ethylene, the most important of the petrochemical building blocks. Ethylene is polymerized to produce polyethylene or, in combination with propylene, to produce copolymers that are used extensively in food-packaging wraps, plastic household goods, or building materials.

Ethylene manufacture via the steam cracking process is in widespread practice throughout the world. The operating facilities are similar to gas oil cracking units, operating at temperatures of 840 °C (1,550 °F) and at low pressures of 165 kilopascals (24 pounds per square inch). Steam is added to the vaporized feed to achieve a 50-50 mixture, and furnace residence times are only 0.2 to 0.5 second. In the United States and the Middle East, ethane extracted from natural gas is the predominant feedstock for ethylene cracking units. Propylene and butylene are largely derived from catalytic cracking units in the United States. In Europe and Japan, catalytic cracking is less common, and natural gas supplies are not as plentiful. As a result, both the Europeans and Japanese generally crack a naphtha or light gas oil fraction to produce a full range of olefin products.

Aromatics

The aromatic compounds, produced in the catalytic reforming of naphtha, are major sources of petrochemical products. In the traditional chemical industry, aromatics such as benzene, toluene, and the xylenes were made from coal during the course of carbonization in the production of coke and town gas. Today a much larger volume of these chemicals are made as refinery by-products. A further source of supply is the aromatic-rich liquid fraction produced in the cracking of naphtha or light gas oils during the manufacture of ethylene and other olefins.

Polymers

A highly significant proportion of these basic petrochemicals is converted into plastics, synthetic rubbers, and synthetic fibres. Together these materials are known as polymers, because their molecules are high-molecular-weight compounds made up of repeated structural units that have combined chemically. The major products are polyethylene, polyvinyl chloride, and polystyrene, all derived from ethylene, and polypropylene, derived from monomer propylene. Major raw materials for synthetic rubbers include butadiene, ethylene, benzene, and propylene. Among synthetic fibres the polyesters, which are a combination of ethylene glycol and terephthalic acid (made from xylenes), are the most widely used. They account for about one-half of all synthetic fibres. The second major synthetic fibre is nylon, its most important raw material being benzene. Acrylic fibres, in which the major raw material is the propylene derivative acrylonitrile, make up most of the remainder of the synthetic fibres.

Inorganic chemicals

Two prominent inorganic chemicals, ammonia and sulfur, are also derived in large part from petroleum. Ammonia production requires hydrogen from a hydrocarbon source. Traditionally, the hydrogen was produced from a coke and steam reaction, but today most ammonia is synthesized from liquid petroleum fractions, natural gas, or refinery gases. The sulfur removed from oil products in purification processes is ultimately recoverable as elemental sulfur or sulfuric acid. It has become an important source of sulfur for the manufacture of fertilizer.