The light gaseous hydrocarbons produced by catalytic cracking are highly unsaturated and are usually converted into high-octane gasoline components in polymerization or alkylation processes. In polymerization, the light olefins propylene and butylene are induced to combine, or polymerize, into molecules of two or three times their original molecular weight. The catalysts employed consist of phosphoric acid on pellets of kieselguhr, a porous sedimentary rock. High pressures, on the order of 30 to 75 bars (3 to 7.5 MPa), or 400 to 1,100 psi, are required at temperatures ranging from 175 to 230 °C (350 to 450 °F). Polymer gasolines derived from propylene and butylene have octane numbers above 90.

The alkylation reaction also achieves a longer chain molecule by the combination of two smaller molecules, one being an olefin and the other an isoparaffin (usually isobutane). During World War II, alkylation became the main process for the manufacture of isooctane, a primary component in the blending of aviation gasoline.

Two alkylation processes employed in the industry are based upon different acid systems as catalysts. In sulfuric acid alkylation, concentrated sulfuric acid of 98 percent purity serves as the catalyst for a reaction that is carried out at 2 to 7 °C (35 to 45 °F). Refrigeration is necessary because of the heat generated by the reaction. The octane numbers of the alkylates produced range from 85 to 95.

Hydrofluoric acid is also used as a catalyst for many alkylation units. The chemical reactions are similar to those in the sulfuric acid process, but it is possible to use higher temperatures (between 24 and 46 °C, or 75 to 115 °F), thus avoiding the need for refrigeration. Recovery of hydrofluoric acid is accomplished by distillation. Stringent safety precautions must be exercised when using this highly corrosive and toxic substance.

Hydrocracking

One of the most far-reaching developments of the refining industry in the 1950s was the use of hydrogen, made possible in part by the availability of hydrogen as a by-product of catalytic reforming. Since the 1980s hydrogen processing has become so prominent that many refineries now incorporate hydrogen-manufacturing plants in their processing schemes.

Though hydrocracking processes a similar feedstock to the catalytic cracking unit, it offers even greater flexibility in product yields. The process can be used for producing gasoline or jet fuels from heavy gas oils, for producing high-quality lubricating oils, or for converting distillation residues into lighter oils. The jet fuel and distillate oil products are of high quality and low sulfur content and may be blended into final products without further processing. Hydrocracked naphtha, on the other hand, is often low in octane and must be catalytically reformed to produce high-quality gasoline.

Hydrocracking is accomplished at lower temperatures than catalytic cracking—e.g., 260 to 425 °C (500 to 800 °F)—but at much higher pressures—55 to 170 bars (5.5 to 17 MPa), or 800 to 2,500 psi. The design and manufacture of large, thick-walled vessels for operation under these conditions has been a major engineering achievement.

Hydrocracking catalysts vary widely. The cracking reactions are induced by materials of the silica-alumina type. In units that process residual feedstocks, hydrogenation catalysts such as nickel, tungsten, platinum, or palladium are employed. The activity of the catalyst system can be maintained for long periods of time, so that continuous regeneration is not necessary as in catalytic cracking.

Isomerization

The demand for aviation gasoline became so great during World War II and afterward that the quantities of isobutane available for alkylation feedstock were insufficient. This deficiency was remedied by isomerization of the more abundant normal butane into isobutane. The isomerization catalyst is aluminum chloride supported on alumina and promoted by hydrogen chloride gas.

Commercial processes have also been developed for the isomerization of low-octane normal pentane and normal hexane to the higher-octane isoparaffin form. Here the catalyst is usually promoted with platinum. As in catalytic reforming, the reactions are carried out in the presence of hydrogen. Hydrogen is neither produced nor consumed in the process but is employed to inhibit undesirable side reactions. The reactor step is usually followed by molecular sieve extraction and distillation. Though this process is an attractive way to exclude low-octane components from the gasoline blending pool, it does not produce a final product of sufficiently high octane to contribute much to the manufacture of unleaded gasoline.