Conversion processes, such as cracking, combining and rearranging, change the size and structure of hydrocarbon molecules in order to convert fractions into more desirable products. (See table 3.)
Table 3. Overview of petroleum refining processes
A number of hydrocarbon molecules not normally found in crude oil but important to the refining process are created as a result of conversion. Olefins (alkenes, di-olefins and alkynes) are unsaturated chain- or ring-type hydrocarbon molecules with at least one double bond. They are usually formed by thermal and catalytic cracking and rarely occur naturally in unprocessed crude oil.
Alkenes are straight-chain molecules with the formula CnHn containing at least one double bond (unsaturated) linkage in the chain. The simplest alkene molecule is the mono-olefin ethylene, with two carbon atoms, joined by a double bond, and four hydrogen atoms. Di-olefins (containing two double bonds), such as 1,2-butadiene and 1,3-butadiene, and alkynes (containing a triple bond), such as acetylene, occur in C5 and lighter fractions from cracking. Olefins are more reactive than paraffins or naphthenes, and readily combine with other elements such as hydrogen, chlorine and bromine.
Following distillation, subsequent refinery processes are used to alter the molecular structures of the fractions to create more desirable products. One of these processes, cracking, breaks (or cracks) heavier, higher-boiling-point petroleum fractions into more valuable products such as gaseous hydrocarbons, gasoline blending stocks, gas oil and fuel oil. During the process, some of the molecules combine (polymerize) to form larger molecules. The basic types of cracking are thermal cracking, catalytic cracking and hydro-cracking.
Thermal cracking processes
Thermal cracking processes, developed in 1913, heat distillate fuels and heavy oils under pressure in large drums until they crack (divide) into smaller molecules with better anti-knock characteristics. This early method, which produced large amounts of solid, unwanted coke, has evolved into modern thermal cracking processes including visbreaking, steam cracking and coking.
Visbreaking is a mild form of thermal cracking which reduces the pour point of waxy residues and significantly lowers the viscosity of feedstock without affecting its boiling-point range. Residual from the atmospheric distillation tower is mildly cracked in a heater at atmospheric pressure. It is then quenched with cool gas oil to control overcracking, and flashed in a distillation tower. The thermally cracked residue tar, which accumulates in the bottom of the fractionation tower, is vacuum flashed in a stripper and the distillate is recycled.
Steam cracking produces olefins by thermally cracking large hydrocarbon molecule feedstocks at pressures slightly above atmospheric and at very high temperatures. Residual from steam cracking is blended into heavy fuels. Naphtha produced from steam cracking usually contains benzene, which is extracted prior to hydrotreating.
Coking is a severe form of thermal cracking used to obtain straight-run gasoline (coker naphtha) and various middle distillate fractions used as catalytic cracking feedstocks. This process so completely reduces hydrogen from the hydrocarbon molecule, that the residue is a form of almost pure carbon called coke. The two most common coking processes are delayed coking and continuous (contact or fluid) coking, which, depending upon the reaction mechanism, time, temperature and the crude feedstock, produce three types of coke—sponge, honeycomb and needle coke.
- Delayed coking.In delayed coking, the feedstock is first charged to a fractionator to separate lighter hydrocarbons, and then combined with heavy recycle oil. The heavy feedstock is fed to the coker furnace and heated to high temperatures at low pressures to prevent premature coking in the heater tubes, producing partial vaporization and mild cracking. The liquid/vapour mixture is pumped from the heater to one or more coker drums, where the hot material is held approximately 24 hours (delayed) at low pressures until it cracks into lighter products. After the coke reaches a predetermined level in one drum, the flow is diverted to another drum to maintain continuous operation. Vapour from the drums is returned to the fractionator to separate out gas, naphtha and gas oils, and to recycle heavier hydrocarbons through the furnace. The full drum is steamed to strip out uncracked hydrocarbons, cooled by water injection and decoked mechanically by an auger rising from the bottom of the drum, or hydraulically by fracturing the coke bed with high-pressure water ejected from a rotating cutter.
- Continuous coking.Continuous (contact or fluid) coking is a moving bed process which operates at lower pressures and higher temperatures than delayed coking. In continuous coking, thermal cracking occurs by using heat transferred from hot recycled coke particles to feedstock in a radial mixer, called a reactor. Gases and vapours are taken from the reactor, quenched to stop further reaction and fractionated. The reacted coke enters a surge drum and is lifted to a feeder and classifier where the larger coke particles are removed. The remaining coke is dropped into the reactor preheater for recycling with feedstock. The process is automatic in that there is a continuous flow of coke and feedstock, and coking occurs both in the reactor and in the surge drum.