Catalytic Cracking

Catalytic cracking, like thermal cracking, breaks heavy fractions, principally gas oils, into lower molecular weight fractions. The use of catalyst permits operations at lower temperatures and pressures than with thermal cracking, and inhibits the formation of undesirable products. Catalytic cracking is probably the key process in the production of large volumes of high-octane gasoline stocks; furnace oils and other useful middle molecular weight distillates are also produced.

Fluidized catalytic processes, in which the finely powdered catalyst is handled as a fluid, have largely replaced the fixed-bed and moving-bed processes, which use a beaded or pelleted catalyst. A schematic flow diagram of fluid catalytic cracking (FCC) is shown in Fig. 4.

The FCC process involves at least four types of reactions: (1) thermal decomposition; (2) primary catalytic reactions at the catalyst surface; (3) secondary catalytic reactions between the primary products; and (4) removal of polymerization products from further reactions by adsorption onto the surface of the catalyst as coke. This last reaction is the key to catalytic cracking because it permits decomposition reactions to move closer to completion than is possible in simple thermal cracking.

Cracking catalysts include synthetic and natural silica-alumina, treated bentonite clay, fuller's earth, aluminum hydrosilicates, and bauxite. These catalysts are in the form of beads, pellets, and powder, and are used in a fixed, moving, or fluidized bed. The catalyst is usually heated and lifted into the reactor area by the incoming oil feed which, in turn, is immediately vaporized upon contact. Vapors from the reactors pass upward through a cyclone separator which removes most of the entrained catalyst. The vapors then enter the fractionator, where the desired products are removed and heavier fractions are recycled to the reactor.

Catalytic cracking units are one of the largest sources of sour and phenolic wastewaters in a refinery. Pollutants from catalytic cracking generally come from the steam strippers and overhead accumulators on fractionators, used to recover and separate the various hydrocarbon fractions produced in the catalytic reactors.

The major pollutants resulting from catalytic cracking operations are oil, sulfides, phenols, cyanides, and ammonia. These pollutants produce an alkaline wastewater with high BOD and COD concentrations. Sulfide and phenol concentrations in the wastewater vary with the type of crude oil being processed, but at times are significant.

Regeneration of spent catalyst in the steam stripper may produce enough carbon monoxide and fine catalyst particles to constitute an air pollution problem.

Figure 4 Catalytic cracking (fluid catalytic cracking). Heavy fraction gas oils are cracked (broken down) into lower molecular weight fractions in the presence of finely powdered catalyst, handled as a fluid. (From Ref. 5.)

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