Distillation curve

FIGURE 4.9 Typical distillation curves for samples retrieved from a coalesced LNAPL pool from beneath a refinery site. 

UNIT Buiane Gasoline Naniha Kerosene Lighi Gas Heavy Gas Residue 

FIGURE 4.10 Typical distillation curve for (a) predominantly gasoline with trace heavy residual fuel oil and (b) predominantly gasoline with a middle distillate of diesel fuel. 

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One distinguishes preparatory distillations that are designed to separate the fractions for subsequent analysis from non-preparatory analytical distillations that are performed to characterize the feed itself. For example, the distillation curve that gives the recovered volume or weight as a function of the distillation temperature characterizes the volatility of the sample. 

Commercial equipment is available which automatically switches from atmospheric distillation to vacuum distillation and calculates the distillation curve as temperatures under atmospheric pressure conditions as a function of weight or volume per cent recovery. 

The results are presented as a distillation curve showing the boiling temperature (corrected to atmospheric pressure) as a function of the distilled volume. 

To extend the applicability of the characterization factor to the complex mixtures of hydrocarbons found in petroleum fractions, it was necessary to introduce the concept of a mean average boiling point temperature to a petroleum cut. This is calculated from the distillation curves, either ASTM or TBP. The volume average boiling point (VABP) is derived from the cut point temperatures for 10, 20, 50, 80 or 90% for the sample in question. In the above formula, VABP replaces the boiling point for the pure component. 

In this manner, the KuQp of a petroieum cut can be calcuiated quickly from readily avkilable data, i. e., the specific gravity and the distillation curve. The A //np value is between 10 and 13 and defines the chemical nature of the cut as it will for the pure components. The characterization factor is extremely Va luable and widely used in refining although the discriminatory character of the Kuqp is less than that obtained by more modern physical methods described in 3.2 and 3.3. 

It is common that a mixture of hydrocarbons whose boiling points are far enough apart petroleum cut) is characterized by a distillation curve and an average standard specific gravity. It is then necessary to calculate the standard specific gravity of each fraction composing the cut by using the relation below [4.8] ... 

The result is a distillation curve showing the temperature as a function of the per cent volume distilled (initial point, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 95% distilled volume, and final boiling point). 

The normalized distillation curves, TBP, ASTM D 86, and ASTM D 1160, provide a way to judge the quality of a fractionation performed on petroleum cuts. 

For the units for which a calculation is made to simulate operations, or for which a calculation is made for sizing purposes, the compositions are known it is necessary then to calculate the distillation curves starting from the characteristics of the components. 

The density and the volatility, expressed by the distillation curve and the vapor pressure, constitute the most important physical characteristics of motor fuels for obtaining satisfactory operation of a vehicle in all circumstances. 

The volatility of the fuel is expressed then by the temperature levels for which the V/L ratio is equal to certain particular values for example V/L = 12, V/L = 20, V/L = 36. There are correlations between the temperatures corresponding to these vaporization ratios and the conventional volatility parameters such as the RVP and the distillation curve. 

The density, distillation curve, viscosity, and behavior at low temperature make up the essential characteristics of diesei fuel necessary for satisfactory operation of the engine. 

Specifications for density, distillation curve and viscosity shown above are for products distributed in temperate climates. Other limits are required for arctic regions, particularly the Scandinavian countries. See Tables 5.13 and 5.14. 

For optimum combustion, the fuel should vaporize rapidly and mix intimately with the air. Even though the design of the injection system and combustion chamber play a very important role, properties such as volatility, surface tension, and fuel viscosity also affect the quality of atomization and penetration of the fuel. These considerations justify setting specifications for the density (between 0.775 and 0.840 kg/1), the distillation curve (greater than 10% distilled at 204°C, end point less than 288°C) and the kinematic viscosity (less than 8 mm /s at -20°C). 

Dearomatized or not, lamp oils correspond to petroleum cuts between Cio and C14. Their distillation curves (less than 90% at 210°C, 65% or more at 250°C, 80% or more at 285°C) give them relatively heavy solvent properties. They are used particularly for lighting or for emergency signal lamps. These materials are similar to kerosene solvents , whose distillation curves are between 160 and 300°C and which include solvents for printing inks. 

Volatility is generally characterized by a distillation curve (the quantity distilled as a function of temperature). Often, only the initial and final boiling points are taken into account along with, possibly, a few intermediary points. 

Composition is normally expressed by a distillation curve, and can be supplemented by compositional analyses such as those for aromatics content. Some physical properties such as density or vapor pressure are often added. The degree of purity is indicated by color or other appropriate test (copper strip corrosion, for example). 

The most important curve is the TBP distillation, properly defined as T = f (% volume or weight). Figure 8.4 shows the distillation curves for an Arabian Light crude. The chart is used to obtain yields for the different cuts as a function of the selected distillation range. 

The products could be classified as a function of various criteria physical properties (in particular, volatility), the way they are created (primary distillation or conversion). Nevertheless, the classification most relevant to this discussion is linked to the end product use LPG, premium gasoline, kerosene and diesel oil, medium and heavy fuels, specialty products like solvents, lubricants, and asphalts. Indeed, the product specifications are generally related to the end use. Traditionally, they have to do with specific properties octane number for premium gasoline, cetane number for diesel oil as well as overall physical properties such as density, distillation curves and viscosity. 

A crude-oil assay always includes a whole crude API gravity and a TBP curve. As discussed by Nelson (op. cit., pp. 89-90) and as shown in Fig. 13-85, a reasonably consistent correlation (based on more than 350 distillation curves) exists between whole crude API gravity and the TBP distillation curve at 101.3 kPa (760 torr). Exceptions not correlated by Fig. 13-85 are highly paraffinic or naphthenic crude oils. 

Because of the time and expense involved in conducting laboratoiy distillation tests of all three basic types, it has become increasingly common to use empirical correlations to estimate the other two distillation curves when either the ASTM, TBP, or EFN- curve is available. Preferred correlations given in the API Technical Data Book—Petroleum Refining (op. dt.) are based on the work of Edmister and Pollock [Chem. Eng. Prog., 44, 905 (1948)], Edmister and Okamoto [Pet. Refiner, 38(8), 117 (1959) 38(9), 271 (1959)], Maxwell Data Book on... 

FIG. 13-85 Average tnie-boiling-point distillation curves of crude oils. (Prom VP E. Edmister, Applied Hydrocarbon Thermodynamics, vol. I, 1st ed, 1961 Gulf Publishing Companif, Houston, Texas, Used with peirrussion All nghts leseived.)... 

FIG. 13-86 Relationship between ASTM and TBP distillation curves. (From VF C. Edmistet Applied Hydrocarbon Thermodynamics, -ool. 1, 1st ed., 1961 Gulf Publishing Company, Houston, Texas. Used with permission. All tights reserved.)... 

Regardless of the procedure used, certain initial steps must be taken for the determination or specification of certain product properties and yields based on the TBP distillation curve of the column feed, method of providing column reflux, column-operating pressure, type of condenser, and type of side-cut strippers ana stripping requirements. These steps are developed and ilhistrated with several detailed examples by Watkins (op. cit.). Only one example, modified from one given by Watkins, is considered briefly here to indicate the approach taken during the initial steps. 

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