Characterization Of Petroleum And Petroleum Fractions

Although much progress has been made in identifying the chemical species present in petroleum, it is generally sufficient for purposes of design and analysis of plant operation of distillation to characterize petroleum and petroleum fractions by gravity, laboratory-distillation curves, component analysis of light ends, and hydrocarbon-type analysis of middle and heavy ends. From such data, as discussed in the Technical Data Book—Petroleum Refining [American Petroleum Institute (API), Washington], five different average boiling points and an index of paraffinicity can be determined; these are then used to predict the physical properties of complex mixtures by a number of well-accepted correlations, whose use will be explained in detail and illustrated with examples. Many other characterizing properties or attributes such as sulfur content, pour point, water and sediment content, salt content, metals content, Reid vapor pressure, Saybolt Universal viscosity, aniline point, octane number, freezing point, cloud point, smoke point, diesel index, refractive index, cetane index, neutralization number, wax content, carbon content, and penetration are generally measured for a crude oil or certain of its fractions according to well-specified ASTM tests. But these attributes are of much less interest here even though feedstocks and products may be required to meet certain specified values of the attributes.

Gravity of a crude-oil or petroleum fraction is generally measured by the ASTM D 287 test or the equivalent ASTM D 1298 test and may be reported as specific gravity (SG) 60/60°F [measured at 60°F (15.6°C) and referred to water at 60°F (15.6°C)] or, more commonly, as API gravity, which is defined as

Water, thus, has an API gravity of 10.0, and most crude oils and petroleum fractions have values of API gravity in the range of 10 to 80. Light hydrocarbons (n-pentane and lighter) have values of API gravity ranging upward from 92.8.

The volatility of crude-oil and petroleum fractions is characterized in terms of one or more laboratory distillation tests that are summarized in Table 13-25. The ASTM D 86 and D 1160 tests are reasonably rapid batch laboratory distillations involving the equivalent of approximately one equilibrium stage and no reflux except for that caused by heat losses. Apparatus typical of the D 86 test is shown in Fig. 13-81 and consists of a heated 100-mL or 125-mL Engler flask containing a calibrated thermometer of suitable range to measure the temperature of the vapor at the inlet to the condensing tube, an inclined brass condenser in a cooling bath using a suitable coolant, and a graduated cylinder for collecting the distillate. A stem correction is not applied to the temperature reading. Related tests using similar apparatuses are the D 216 test for natural gasoline and the Engler distillation.

In the widely used ASTM D 86 test, 100 mL of sample is charged to the flask and heated at a sufficient rate to produce the first drop of distillate from the lower end of the condenser tube in from 5 to 15 min, depending on the nature of the sample. The temperature of the vapor at that instant is recorded as the initial boiling point (IBP). Heating is continued at a rate such that the time from the IBP to 5 volume percent recovered of the sample in the cylinder is 60 to 75 s. Again, vapor temperature is recorded. Then, successive vapor temperatures are recorded for from 10 to 90 percent recovered in intervals of 10, and at 95 percent recovered, with the heating rate adjusted so that 4 to 5 mL are collected per minute. At 95 percent recovered, the burner flame is increased if necessary to achieve a maximum vapor temperature referred to as the end point (EP) in from 3 to 5 additional min. The percent recovery is reported as the maximum percent recovered in the cylinder. Any residue remaining in the flask is reported as percent residue, and percent loss is reported as the difference between 100 mL and the sum of the percent recovery and percent residue. If the atmosphere test pressure P is other than 101.3 kPa (760 torr), temperature readings may be adjusted to that pressure by the Sidney Young equation, which for degrees Fahrenheit is

Another pressure correction for percent loss can also be applied, as described in the ASTM test method.

Results of a typical ASTM distillation test for an automotive gasoline are given in Table 13-26, in which temperatures have already been corrected to a pressure of 101.3 kPa (760 torr). It is generally assumed that percent loss corresponds to volatile noncondensables that are distilled off at the beginning of the test. In that case, the percent recovered values in Table 13-26 do not correspond to percent evaporated values, which are of greater scientific value. Therefore, it is common to adjust the reported temperatures according to a linear interpolation procedure given in the ASTM test method to obtain corrected temperatures in terms of percent evaporated at the standard intervals as included in Table 13-26. In the example, the corrections are not large because the loss is only 1.5 volume percent.

Although most crude petroleum can be heated to 600°F (316°C) without noticeable cracking, when ASTM temperatures exceed 475°F (246°C), fumes may be evolved, indicating decomposition, which may cause thermometer readings to be low. In that case, the following correction attributed to S. T. Hadden may be applied:

where T = measured temperature, °F

At 500 and 600°F (260 and 316°C), the corrections are 6 and 18°F (3.3 and 10°C) respectively.

As discussed by Nelson (op. cit.), virtually no fractionation occurs in an ASTM distillation. Thus, components in the mixture do distill one by one in the order of their boiling points but as mixtures of successively higher boiling points. The IBP, EP, and intermediate points have little theoretical significance, and, in fact, components boiling below the IBP and above the EP are present in the sample. Never-

TABLE 13-25 Laboratory Distillation Tests

Test name

Reference

Main applicability

ASTM (atmospheric)

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