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Chemistry Of Petrochemical Processes 3

Chemistry Of Petrochemical Processes 3

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Crude Oil Processing andProduction of HydrocarbonIntermediates
The hydrocarbon intermediates referred to in the previous chapter areproduced by subjecting crude oils to various processing schemes. Theseinclude a primary distillation step to separate the crude oil complex mix-ture into simpler fractions. These fractions are primarily used as fuels.However, a small percentage of these streams are used as secondary rawmaterials or intermediates for obtaining olefins, diolefins, and aromaticsfor petrochemicals production. Further processing of these fractions maybe required to change their chemical composition to the required prod-ucts. These new products may also be used as fuels of improved qualitiesor as chemical feedstocks. For example, reforming a naphtha fractioncatalytically produces a reformate rich in aromatics. The major use of the reformate is to supplement the gasoline pool due to its high octanerating. However, the reformate is also used to extract the aromatics forpetrochemicals use. At this point, the production of intermediates forpetrochemicals is not separable from the production of fuels. In thischapter, the production of hydrocarbon intermediates is discussed in con- junction with different crude oil processing schemes. These includephysical separation techniques and chemical conversion processes. Theproduction of olefins is also discussed in the last section.
Physical separation techniques separate a mixture such as a crude oilwithout changing the chemical characteristics of the components. The
separation is based on differences of certain physical properties of theconstituents such as the boiling and melting points, adsorption affinitieson a certain solid, and diffusion through certain membranes.The important physical separation processes, discussed here, are dis-tillation, absorption, adsorption, and solvent extraction.
Atmospheric distillation separates the crude oil complex mixture intodifferent fractions with relatively narrow boiling ranges. In general, sep-aration of a mixture into fractions is based primarily on the difference inthe boiling points of the components. In atmospheric distillation units,one or more fractionating columns are used.Distilling a crude oil starts by preheating the feed by exchange withthe hot product streams. The feed is further heated to about 320°C as itpasses through the heater pipe (pipe still heater).The hot feed enters the fractionator, which normally contains 30–50fractionation trays. Steam is introduced at the bottom of the fractionatorto strip off light components. The efficiency of separation is a function of the number of theoretical plates of the fractionating tower and the refluxratio. Reflux is provided by condensing part of the tower overheadvapors. Reflux ratio is the ratio of vapors condensing back to the still tovapors condensing out of the still (distillate). The higher the reflux ratio,the better the separation of the mixture.Products are withdrawn from the distillation tower as side streams,while the reflux is provided by returning a portion of the cooled vaporsfrom the tower overhead condenser. Additional reflux could be obtainedby returning part of the cold side stream products to the tower. In prac-tice, the reflux ratio varies over a wide range according to the specificseparations desired. From the overhead condenser, the uncondensedgases are separated, and the condensed light naphtha liquid is withdrawnto storage. Heavy naphtha, kerosine, and gas oil are withdrawn as sidestream products. Table 3-1 shows the approximate boiling ranges forcrude oil fractions. The residue (topped crude) is removed from the bot-tom of the distillation tower and may be used as a fuel oil. It may also becharged to a vacuum distillation unit, a catalytic cracking or steam crack-ing process. Figure 3-1 is a flow diagram for atmospheric and vacuumdistillation units.
Chemistry of Petrochemical Processes
Vacuum distillation increases the amount of the middle distillates andproduces lubricating oil base stocks and asphalt. The feed to the unit isthe residue from atmospheric distillation. In vacuum distillation, reducedpressures are applied to avoid cracking long-chain hydrocarbons presentin the feed.The feed is first preheated by exchange with the products, charged tothe vacuum unit heater, and then passed to the vacuum tower in an atmos-phere of superheated steam. Using superheated steam is important: it
Crude Oil Processing and Production of Hydrocarbon Intermediates
Table 3-1Approximate ASTM boiling point ranges for crude oil fractionsBoiling rangeFractions°F°C
Light naphtha852103099Heavy naphtha19040088204Kerosine340520171271Atmospheric gas oil540820288438Vacuum gas oil7501,050399566Vacuum residue1,000+538+
Figure 3-1.
Flow diagram of atmospheric and vacuum distillation units:
(1,3)heat exchangers; (2) desalter, (3,4) heater; (5) distillation column, (6) overheadcondenser, (7–10) pump around streams, (11) vacuum distillation heater; (12)vacuum tower.

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