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Module 3: Liquid Fossil Fuel (Petroleum)

Lecture 17: Evaluation of crude

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Keywords: Evaluation, characterization factor, TBP, ASTM, EFV

3.2 Evaluation of crude

The assessment of a crude oil mainly involves the chemical evaluation of crude oil feedstocks by

petroleum testing laboratories. Each crude oil type has unique characteristics and no crude oil is

identical to the other. The results of crude oil assay testing provide extensive and detailed

analytical data for a particular crude oil which are necessary for refinery. In practice it is difficult

and very expensive to carry out full laboratory analysis of every type of crude oil at the refinery.

This has resulted in development of a number of computing methods that can predict the

properties of petroleum fractions by routine laboratory analyses. For application of these

methods, information about distillation characteristics, density, sulfur content, viscosity etc. of

petroleum fractions are required.

According to U.S Bureau of Mines, eight bases of crude oil are designated depending on the

distillation characteristics. The characteristics of a crude oil is expressed according to key

fraction no. 1, which boils at 482 to 5270F at atmospheric pressure and key fraction no. 2, which

boils at 527 to 5720F at 40 mm pressure in a standard Hemple distillation apparatus and

condition. Table 1. shows different crude oil bases with their characterization factors and API

gravity. The bases of the crude oil are designated as paraffin, paraffin-intermediate, paraffin-

naphthene etc, depending on the nature of the low boiling and high boiling fractions of crude.

For example, in paraffin-naphthene base, the first word of the base name, such as ‘paraffin’

denotes the nature of the low boiling fraction and the second word, ‘naphthene’ indicates the

nature of the higher boiling fraction of the crude oil.

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Characterisation factor of a crude oil, defined by Universal Oil Product (U.O.P) is expressed as

Where, K is the characterization factor, TB is the molal average boiling point in oR and S is the

specific gravity at 600F. Bases of crude oil can be indicated primarily by this factor. Paraffin

base crude oils show the range of characterization factor as 12.9 to 12.15, for intermediate base

crude oils the range is 12.1 to 11.5 and for naphthene base crude oil it is 11.45 to 10.5. These

ranges are determined based on the properties of crude oil, such as, viscosity, aniline point,

molecular weight, critical temperature, percentage of hydrocarbon etc.

Table 1. Different bases of crude oil with their properties

Base of crude oil API gravity at 600 F Approx. U.O.P

characterization factor

Low boiling High boiling Key fraction 1 Key fraction 2 Low High
part part  boiling boiling 

Paraffin 40+ 30+ 12.2 + 12.2 +

Paraffin Intermediate 40+ 20 to 30 12.2 + 11.4 to 12.0

Paraffin Naphthene 40+ 20- 12.2 + 11.4-

Intermediate Paraffin 33 to 40 30+ 11.5 to12.0 12.2+

Intermediate 33 to 40 20 to 30 11.4 to12.1 11.4 to 12.1

Intermediate Naphthene 33 to 40 20- 11.4 to12.1 11.4-

Naphthene Intermediate 33- 20 to 30 11.5- 11.4 to 12.1

Naphthene Paraffin 33- 30+ 11.5- 12.2+

Naphthene 33- 20-  11.4- 11.4-

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A crude oil is termed as ‘sour’ crude when it contains dissolved hydrogen sulfide in it, 0.05 cu ft

of hydrogen sulfide per 100 gallon of crude oil. At this level, the crude oil becomes dangerously

toxic. The crude oils which contain disulfides, mercaptans, thiophenes in a sufficient amount, are

said to be ‘high sulfur’ crude. Sometimes ‘high sulfur’ crude oils are erroneously termed as sour

crude. Such as, high sulfur crude oils of California, Venezuela and Mexico do not contain any

dissolved hydrogen sulfide in them; hence they should not be termed as sour crude.

The vaporization characteristics of petroleum mixtures are determined by a batch distillation

curve where percentage distilled is plotted against respective temperature at which it is distilled.

Theoretically, a true boiling point (TBP) distillation is that where a very close separation is made

so that each component in the mixture is separated at its own boiling point and the quantity

present in the original mixture. Fig. 1 represents the TBP curve of a mixture containing two

components A and B which are present in the volume percent 30 and 70 respectively and their

boiling points are tA and tB respectively (tA< tB).

Fig. 1. True boiling point (TBP) distillation of a two component mixture

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The stepwise plot shows the theoretical TBP plot with perfect fractionation while smooth curve

represents the actual curve with imperfect fractionation i.e incomplete separation of the two

components.

Vaporisation characteristics of petroleum fractions are determined by means of a simple

distillation with a little fractionation. This distillation is done by following the methods and

apparatus designated by ASTM (American Society for Testing and Materials). This type of

distillation is called ASTM distillation and the method of this distillation is termed as ‘ASTM

D158’ in ASTM standard. In this method 100 or 200 ml sample is distilled in a batch mode in

specified condition and apparatus. Fig. 2a and 2b show typical ASTM distillation curve for three

components compared to the typical TBP curve for the same three components and the same

curve for a complex system respectively.

(a) (b)

Fig. 2. (a) Comparison of TBP and ASTM distillation curves for a three component
mixture (b) for a complex system

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Equilibrium flash vaporization (EFV) is a type of separation of components of a petroleum

mixture where, the mixture under pressure is suddenly vaporized or flashed in a still and the

mixture is separated into a vapour and a liquid portion which remain at equilibrium. In fact, this

type of flash is observed in the refinery when crude oil containing appreciable amount of light

components under pressure is piped to separators at lower pressure and allowed to vaporize

suddenly through a pressure reducing valve. If a number of samples of the same composition are

flashed at the same pressure but at different temperatures between the bubble point and dew

point temperatures of the feed, an EFV curve can be generated.

Fig. 3 shows the comparison of the slopes of TBP, ASTM and EFV. It has been shown that 10-

70% slope of EFV> 10-70% slope of ASTM> 10-70% slope of TBP.

Fig. 3. Comparison of the slopes of TBP, ASTM and EFV distillation curves

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The physical properties of petroleum oil vary gradually throughout the range of compounds by

which the oil is constituted. Distillation is a means of arranging these compounds in accordance

to their boiling points. The properties such as, viscosity, specific gravity, colour etc are found to

vary at each drop or fraction of the mixture distilled. The rate at which these properties change

can be shown by mid-percent curve. Actually, the viscosity or specific gravity of a petroleum

fraction is an average of that property of many drops which constitute the fraction. The concept

of mid-percent curve is that, if each drop is equally different from the last drop and it’s

succeeding one, then the property of the whole fraction is determined by the property of the drop

which comes at exactly 50% distilled. This would be the condition when a mid-percent curve is a

straight line. Although mid-percent curves are never exactly straight line, but they may be

straight for a short range of percent distilled and this short range, the average property of the

fraction is exactly the same as that of mid-percent fraction. There are some properties which are

not additive, such as, viscosity, API gravity, colour, flash point etc., for which this mid-percent

curve is not suitable. But the properties which are additive, such as, specific gravity, aniline

point, percent sulfur etc. can be utilized nicely in mid-percent curve to determine the average

property of the whole fraction. Although viscosity is not an additive property, but it has been

seen that, for a wide fraction of oil, the average viscosity is almost exactly the same as that of the

mid-point fraction.

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Reference:

1. Petroleum refinery engineering, W. L. Nelson, 4th edition, McGraw-Hill Book Company,

1987.

2. Distillation, M. Van Winkle, McGraw-Hill Book Company, 1967.

3. Evaluation of crude oil quality, D. Stratiev, R.Dinkov, K. Petkov, K. Stanulov, Petroleum &

Coal, ISSN 1337-7027, 52(1) 35-43, 2010.

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