3Refinery Feedstocks

The basic raw material for refineries is petroleum or crude oil, even though in

some areas synthetic crude oils from other sources (Gilsonite, tar sands, etc.)

and natural gas liquids are included in the refinery feedstocks. The chemical

compositions of crude oils are surprisingly uniform even though their physical

characteristics vary widely. The elementary composition of crude oil usually falls

within the following ranges.

Element Percent by weight

Carbon 84–87

Hydrogen 11–14

Sulfur 0–3

Nitrogen 0–0.6

In the United States, crude oils are classified as paraffin base, naphthene

base, asphalt base, or mixed base. There are some crude oils in the Far East

which have up to 80% aromatic content, and these are known as aromatic-base

oils. The U.S. Bureau of Mines [1,2] has developed a system which classifies

the crude according to two key fractions obtained in distillation: No. 1 from 482

to 527°F (250 to 275°C) at atmospheric pressure and No. 2 from 527 to 572°F

(275 to 300°C) at 40 mmHg pressure. The gravity of these two fractions is used

to classify crude oils into types as shown below.

21

22 Chapter 3

Key fractions,•API

No. 1 No. 2

Paraffin 40 30

Paraffin, intermediate 40 20–30

Intermediate, paraffin 33–40 30

Intermediate 33–40 20–30

Intermediate, naphthene 33–40 20

Naphthene, intermediate 33 20–30

Naphthene �33 �20

The paraffinic and asphailic classifications in common use are based on the prop-

erties of the residuum left from nondestructive distillation and are more descrip-

tive to the refiner because they convey the nature of the products to be expected

and the processing necessary.

3.1 CRUDE OIL PROPERTIES

Crude petroleum is very complex and, except for the low-boiling components,

no attempt is made by the refiner to analyze for the pure components contained

in the crude oil. Relatively simple analytical tests are run on the crude and the

results of these are used with empirical correlations to evaluate the crude oils as

feedstocks for the particular refinery. Each crude is compared with the other feed-

stocks available and, based upon the operating cost and product realization, is

assigned a value. The more useful properties are discussed.

API Gravity

The density of petroleum oils is expressed in the United States in terms of API

gravity rather than specific gravity; it is related to specific gravity in such a fash-

ion that an increase in API gravity corresponds to a decrease in specific gravity.

The units of API gravity are °API and can be calculated from specific gravity

by the following:

°API �141.5

specific gravity� 131.5 (1)

In equation (1), specific gravity and API gravity refer to the weight per

unit volume at 60°F as compared to water at 60°F. Crude oil gravity may range

Refinery Feedstocks 23

from less than 10°API to over 50°API but most crudes fall in the 20 to 45°API

range. API gravity always refers to the liquid sample at 60°F (15.6°C). API gravi-

ties are not linear and, therefore, cannot be averaged. For example, a gallon of

30°API gravity hydrocarbons when mixed with a gallon of 40°API hydrocarbons

will not yield two gallons of 35°API hydrocarbons, but will give two gallons of

hydrocarbons with an API gravity different from 35°API. Specific gravities can

be averaged.

Sulfur Content, wt%

Sulfur content and API gravity are two properties which have had the greatest

influence on the value of crude oil, although nitrogen and metals contents are

increasing in importance. The sulfur content is expressed as percent sulfur by

weight and varies from less than 0.1% to greater than 5%. Crudes with greater

than 0.5% sulfur generally require more extensive processing than those with

lower sulfur content. Although the term ‘‘sour’’ crude initially had reference to

those crudes containing dissolved hydrogen sulfide independent of total sulfur

content, it has come to mean any crude oil with a sulfur content high enough to

require special processing. There is no sharp dividing line between sour and sweet

crudes, but 0.5% sulfur content is frequently used as the criterion.

Pour Point, °F (°C)

The pour point of the crude oil, in °F or °C, is a rough indicator of the relative

paraffinicity and aromaticity of the crude. The lower the pour point, the lower

the paraffin content and the greater the content of aromatics.

Carbon Residue, wt%

Carbon residue is determined by distillation to a coke residue in the absence of

air. The carbon residue is roughly related to the asphalt content of the crude and

to the quantity of the lubricating oil fraction that can be recovered. In most cases

the lower the carbon residue, the more valuable the crude. This is expressed in

terms of the weight percent carbon residue by either the Ramsbottom (RCR) or

Conradson (CCR) ASTM test procedures (D-524 and D-189).

Salt Content, lb/1000 bbl

If the salt content of the crude, when expressed as NaCl, is greater than 10 lb/

1000 bbl, it is generally necessary to desalt the crude before processing. If the

salt is not removed, severe corrosion problems may be encountered. If residua

are processed catalytically, desalting is desirable at even lower salt contents of

24 Chapter 3

the crude. Although it is not possible to have an accurate conversion unit between

lb/1000 bbl and ppm by weight because of the different densities of crude oils,

1 lb/1000 bbl is approximately 3 ppm.

Characterization Factors

There are several correlations between yield and the aromaticity and paraffinicity

of crude oils, but the two most widely used are the UOP or Watson ‘‘characteriza-

tion factor’’ (KW) and the U.S. Bureau of Mines ‘‘correlation index’’ (CI).

KW �T1/3

B

G(2)

CI �87,552

TB

� 473.7G � 456.8 (3)

where

TB � mean average boiling point, °R

G � specific gravity at 60°F.

The Watson characterization factor ranges from less than 10 for highly

aromatic materials to almost 15 for highly paraffinic compounds. Crude oils show

a narrower range of KW and vary from 10.5 for a highly naphthenic crude to 12.9

for a paraffinic base crude.

The correlation index is useful in evaluating individual fractions from crude

oils. The CI scale is based upon straight-chain paraffins having a CI value of 0

and benzene having a CI value of 100. The CI values are not quantitative, but

the lower the CI value, the greater the concentrations of paraffin hydrocarbons

in the fraction; and the higher the CI value, the greater the concentrations of

naphthenes and aromatics [3].

Nitrogen Content, wt%

A high nitrogen content is undesirable in crude oils because organic nitrogen

compounds cause severe poisoning of catalysts used in processing and cause

corrosion problems such as hydrogen blistering. Crudes containing nitrogen in

amounts above 0.25% by weight require special processing to remove the ni-

trogen.

Distillation Range

The boiling range of the crude gives an indication of the quantities of the various

products present. The most useful type of distillation is known as a true boiling

Refinery Feedstocks 25

Fig

ure

3.1

TB

Pcu

tpoin

tver

sus

AS

TM

end

poin

t.

26 Chapter 3

point (TBP) distillation and generally refers to a distillation performed in equip-

ment that accomplishes a reasonable degree of fractionation. There is no specific

test procedure called a TBP distillation, but the U.S. Bureau of Mines Hempel

and ASTM D-285 distillations are the tests most commonly used. Neither of

these specify either the number of theoretical plates or the reflux ratio used and,

as a result, there is a trend toward using the results of a 15:5 distillation (D-

2892) rather than the TBP. The 15:5 distillation is carried out using 15 theoretical

plates at a reflux ratio of 5:1.

The crude distillation range also has to be correlated with ASTM dis-

tillations because product specifications are generally based on the simple ASTM

distillation tests D-86 and D-1160. The TBP cut point for various fractions can

be approximated by use of Figure 3.1. A more detailed procedure for correlation

of ASTM and TBP distillations is given in the API Technical Data Book—Petro-

leum Refining published by the American Petroleum Institute, Washington, DC.

Metals Content, ppm

The metals content of crude oils can vary from a few parts per million to more

than 1000 ppm and, in spite of their relatively low concentrations, are of consider-

able importance [4]. Minute quantities of some of these metals (nickel, vanadium,

and copper) can severely affect the activities of catalysts and result in a lower-

value product distribution. Vanadium concentrations above 2 ppm in fuel oils

can lead to severe corrosion to turbine blades and deterioration of refractory fur-

nace linings and stacks [2].

Distillation concentrates the metallic constituents of crude in the residues,

but some of the organometallic compounds are actually volatilized at refinery

distillation temperatures and appear in the higher-boiling distillates [5].

The metallic content may be reduced by solvent extraction with propane

or similar solvents as the organometallic compounds are precipitated with the

asphaltenes and resins.

3.2 COMPOSITION OF PETROLEUM

Crude oils and high-boiling crude oil fractions are composed of many members

of a relatively few homologous series of hydrocarbons [6]. The composition of

the total mixture, in terms of elementary composition, does not vary a great deal,

but small differences in composition can greatly affect the physical properties

and the processing required to produce salable products. Petroleum is essentially

a mixture of hydrocarbons, and even the non-hydrocarbon elements are generally

present as components of complex molecules predominantly hydrocarbon in char-

acter, but containing small quantities of oxygen, sulfur, nitrogen, vanadium,

Refinery Feedstocks 27

nickel, and chromium [4]. The hydrocarbons present in crude petroleum are clas-

sified into three general types: paraffins, naphthenes, and aromatics. In addition,

there is a fourth type, olefins, that is formed during processing by the dehydroge-

nation of paraffins and naphthenes.

Paraffins

The paraffin series of hydrocarbons is characterized by the rule that the carbon

atoms are connected by a single bond and the other bonds are saturated with

hydrogen atoms. The general formula for paraffins is CnH2n�2.

The simplest paraffin is methane, CH4, followed by the homologous series

of ethane, propane, normal and isobutane, normal, iso-, and neopentane, etc. (Fig.

3.2). When the number of carbon atoms in the molecule is greater than three,

several hydrocarbons may exist which contain the same number of carbon and

hydrogen atoms but have different structures. This is because carbon is capable

not only of chain formation, but also of forming single- or double-branched

chains which give rise to isomers that have significantly different properties. For

example, the motor octane number of n-octane is �17 and that of isooctane

(2,2,4-trimethyl pentane) is 100.

Figure 3.2 Paraffins in crude oil.

28 Chapter 3

The number of possible isomers increases in geometric progression as the

number of carbon atoms increases. There are two paraffin isomers of butane,

three of pentane, 17 structural isomers of octane and, by the time the number of

carbon atoms has increased to 18, there are 60,533 isomers of cetane. Crude oil

contains molecules with up to 70 carbon atoms, and the number of possible paraf-

finic hydrocarbons is very high.

Olefins

Olefins do not naturally occur in crude oils but are formed during the processing.

They are very similar in structure to paraffins but at least two of the carbon atoms

are joined by double bonds. The general formula is CnH2n. Olefins are generally

undesirable in finished products because the double bonds are reactive and the

compounds are more easily oxidized and polymerized to form gums and var-

nishes. In gasoline boiling-range fractions, some olefins are desirable because

Figure 3.3 Naphthenes in crude oil.

Refinery Feedstocks 29

olefins have higher research octane numbers than paraffin compounds with the

same number of carbon atoms. Olefins containing five carbon atoms have high

reaction rates with compounds in the atmosphere that form pollutants and, even

though they have high research octane numbers, are considered generally undesir-

able.

Some diolefins (containing two double bonds) are also formed during pro-

cessing, but they react very rapidly with olefins to form high-molecular-weight

polymers consisting of many simple unsaturated molecules joined together. Di-

olefins are very undesirable in products because they are so reactive they poly-

merize and form filter and equipment plugging compounds.

Naphthenes (Cycloparaffins)

Cycloparaffin hydrocarbons in which all of the available bonds of the carbon

atoms are saturated with hydrogen are called naphthenes. There are many types

Figure 3.4 Aromatic hydrocarbons in crude oil.

30 Chapter 3

of naphthenes present in crude oil, but, except for the lower-molecular-weight

compounds such as cyclopentane and cyclohexane, are generally not handled as

individual compounds. They are classified according to boiling range and their

properties determined with the help of correlation factors such as the KW factor

or CI. Some typical naphthenic compounds are shown in Figure 3.3.

Aromatics

The aromatic series of hydrocarbons is chemically and physically very different

from the paraffins and cycloparaffins (naphthenes). Aromatic hydrocarbons con-

tain a benzene ring which is unsaturated but very stable and frequently behaves

as a saturated compound. Some typical aromatic compounds are shown in

Figure 3.4.

The cyclic hydrocarbons, both naphthenic and aromatic, can add paraffin

side chains in place of some of the hydrogen attached to the ring carbons and form

a mixed structure. These mixed types have many of the chemical and physical

characteristics of both of the parent compounds, but generally are classified ac-

cording to the parent cyclic compound.

3.3 CRUDES SUITABLE FOR ASPHALT MANUFACTURE

It is not possible to predict with 100% accuracy whether or not a particular crude

will produce specification asphalts without actually separating the asphalts from

the crude and running the tests. There are, however, certain characteristics of

crude oils that indicate if they are possible sources of asphalt. If the crude oil

contains a residue [750°F (399°C)] mean average boiling point having a Watson

characterization factor of less than 11.8 and the gravity is below 35°API, it is

usually suitable for asphalt manufacture [7]. If, however, the difference between

the characterization factors for the 750°F and 550°F fraction is greater than 0.15,

the residue may contain too much wax to meet most asphalt specifications.

3.4 CRUDE DISTILLATION CURVES

When a refining company evaluates its own crude oils to determine the most

desirable processing sequence to obtain the required products, its own labora-

tories will provide data concerning the distillation and processing of the oil and

its fractions [8]. In many cases, information not readily available is desired con-

cerning the processing qualities of crude oils. In such instances, true boiling point

(TBP) and gravity-midpercent curves can be developed from U.S. Bureau of

Mines crude petroleum analysis data sheets (Fig. 3.5).

Refinery Feedstocks 31

Figure 3.5 U.S. Bureau of Mines crude petroleum analysis.

32 Chapter 3

The U.S. Bureau of Mines has carried out Hempel distillations on thousands

of crude oil samples from wells in all major producing fields. Although the degree

of fractionation in a Hempel assay is less than that in a 15:5 distillation, the

results are sufficiently similar that they can be used without correction. If desired,

correction factors developed by Nelson [9] can be applied.

The major deficiency in a Bureau of Mines assay is the lack of information

concerning the low-boiling components. The materials not condensed by water-

cooled condensers are reported as ‘‘distillation loss.’’ An estimate of the compo-

sition of the butane and lighter components is frequently added to the low-boiling

end of the TBP curve to compensate for the loss during distillation.

Figure 3.6 Boiling point at 760 mmHg versus boiling point at 40 mmHg.

Refinery Feedstocks 33

Fig

ure

3.7

Cru

de

dis

till

atio

ncu

rve.

34 Chapter 3

The Bureau of Mines analysis is reported in two parts: the first is the portion

of the distillation performed at atmospheric pressure and up to 527°F (275°C)

end point, the second at 40 mmHg total pressure to 572°F (300°C) end point. The

portion of the distillation at reduced pressure is necessary to prevent excessive pot

temperatures, which cause cracking of the crude oil.

The distillation temperatures reported in the analysis must be corrected to

760 mmHg pressure. Generally, those reported in the atmospheric distillation

section need not be corrected, but if carried out at high elevations it may also

Figure 3.8 TBP and gravity-midpercent curves. Hastings Field, Texas crude: gravity,

31.7°API; sulfur, 0.15 wt%.

Refinery Feedstocks 35

be necessary to correct these. The distillation temperatures at 40 mmHg pressure

can be converted to 760 mmHg by use of charts developed by Esso Research and

Engineering Company [6]. Figure 3.6 shows the relationships between boiling

temperatures at 40 mmHg and 760 mmHg pressure.

The 572°F (300°C) end point at 40 mmHg pressure corresponds to 790°F

(421°C) at 760 mmHg. Refinery crude oil distillation practices take overhead

streams with end points from 950 to 1050°F (510 to 566°C) at 760 mmHg. Esti-

mates of the shape of the TBP curve above 790°F (421°C) can be obtained by

plotting the distillation temperature versus percentage distilled on probability

graph paper and extrapolating to 1100°F (593°C) [11]. (See Fig. 3.7.) The data

points above 790°F (421°C) can be transferred to the TBP curve.

The gravity mid-percent curve is plotted on the same chart with the TBP

curve. The gravity should be plotted on the average volume percent of the frac-

tion, as the gravity is the average of the gravities from the first to the last drops

in the fraction. For narrow cuts, a straight-line relationship can be assumed and

the gravity used as that of the mid-percent of the fraction.

Smooth curves are drawn for both the TBP and gravity mid-percent curves.

Figure 3.8 illustrates these curves for the crude oil reported in Figure 3.5.

PROBLEMS

1. Develop a TBP and gravity-midpercent curve for one of the crude oils

given in Appendix D.

2. Using the TBP and gravity curves from problem 1, calculate the Wat-

son characterization factors for the fractions having mean average boil-

ing points of 550°F (288°C) and 750°F (399°C). Is it probable this

crude oil will produce a satisfactory quality asphalt?

3. Using the U.S. Bureau of Mines method for classifying crude oils from

the gravities of the 482 to 527°F (250 to 275°C) and 527 to 572°F

(275 to 300°C) fractions, classify the crude oil used in problem 1 ac-

cording to type.

NOTES

1. J. R. Dosher, Chem. Eng. 77(8), 96–112 (1970).

2. W. A. Gruse and D. R. Stevens, Chemical Technology of Petroleum, 3rd Ed.

(McGraw-Hill Book Company, New York, 1960), p. 16.

3. Ibid., p. 13.

4. M. C. K. Jones and R. L. Hardy, Ind. Eng. Chem. 44, 2615 (1952).

5. E. C. Lane and E. L. Garton, U. S. Bureau of Mines, Rept. Inves. 3279 (1935).

36 Chapter 3

6. J. B. Maxwell and L. S. Bonnell, Derivation and Precision of a New Vapor Pressure

Correlation for Petroleum Hydrocarbons, presented before the Division of Petro-

leum Chemistry, American Chemical Society, Sep. 1955.

7. W. L. Nelson, Oil Gas J. 68(44), 92–96 (1970).

8. W. L. Nelson, Petroleum Refinery Engineering, 4th Ed. (McGraw-Hill Book Com-

pany, New York, 1958), p. 114.

9. W. L. Nelson, Oil Gas J. 66(13), 125–126 (1968).

10. H. M. Smith, U. S. Bureau of Mines, Tech. Paper 610 (1940).

11. R. A. Woodle and W. B. Chandlev, Ind. Eng. Chem. 44, 2591 (1952).