CHAPTER 3

CRUDE OILS, HYDROCARBONS,

AND REFINERY PRODUCTS.

Petroleum Supply/Demand Picture

The U.S. has become increasingly dependent on imported crude
oil. Crude oil imports exceeded 50% of crude charged to U.S.
refineries in 1993 and are still increasing (Fig. 31).1 As a result
largely of stringent environmental regulations, the number of oper-
ating refineries in the U.S. has decreased from 303 in 1981 with a
combined crude charge capacity of 18.5 million barrels per day, to
161 in 1999 with a charge capacity of 15.3 million barrels per day.2
During this period, the number of refineries operating in the
non-communist world increased from 440 to 535 and the capacity
of U.S. refineries decreased from about 44% of the non-commu-
nist capacity to about 26%.3
Also, during this same period, the demand for refined
petroleum products in the U.S. increased from less than 16 million
barrels per day to more than 18 million barrels per day. With neg-
ligible increase in the importation of products, this increase in
demand has been met essentially by increasing refinery utilization
from 70% of capacity to more than 95% (Fig. 32) and by increas-
ing severity of operations (increasing conversion of residual oils to
lighter oils).4 See the following tabulation:

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 PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 31 Percent Imported Crude Oil Charged to U.S. Refineries

Fig. 32 Percent Utilization Rate (U.S. Refineries)

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

Product Yields as Percent of Crude Charged 5

Year Gasoline Jet Fuel Distillate Residual Oil
1988 55.2 10.9 23.5 10.4
1998 56.6 11.2 24.5 5.9

It is evident from the above that the slight increases in lighter products
have resulted from destruction of residual oil. Demand for residual fuel oil
decreased as a result of environmental constraints and the increased avail-
ability of competitively-priced natural gas.

Nature of Crude Oils

Crude oils are complex mixtures of hundreds of different species of chemical
compounds. Most of these compounds are hydrocarbons, principally paraf-
fins (alkanes), naphthenes (cycloparaffins), aromatics, or combinations of
these, such as alkyl naphthenes, alkyl aromatics, and polycyclic compounds.
Another type of hydrocarbon found in refinery productsas a result of chem-
ical reaction during processingis the olefin (alkene). It is generally assumed
olefins are not present in crude oil, that olefins reported in a crude assay arise
due to decomposition during the distillation of the crude.
In addition, a number of elements (other than carbon and hydrogen)
appear in crude oils. Principal among these is sulfur in the form of free
(elemental) sulfur, hydrogen sulfide (H2S), mercaptan (RSH), thiophene,
etc. Sulfur is very troublesome in petroleum products, causing corrosion,
producing sulfur dioxide (which is toxic and is the main component of acid
rain) when burned, and in the form of H2S is an insidious poison. In suffi-
ciently high concentration, H2S paralyzes the olfactory nerves so that its vic-
tim is unaware of its presence. Sulfur is also a poison to some catalysts. The
petroleum industry is a large producer of sulfur as a product from treating
operations that convert H2 S to elemental sulfur.
Nitrogen is another undesirable element occurring in crude oil since it,
too, is a poison to some catalysts. Other catalyst poisons include arsenic,
vanadium, and nickel. Vanadium can also cause corrosion and in the form
of V2O5 acts as a flux that can cause furnace refractories to flow.

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PETROLEUM REFINERY P ROCESS ECONOMICS

Compounds containing oxygen, notably naphthenic acids, are corrosive,

particularly when the process temperature is 430F to 750F and the stream
velocity is high, as in nozzles, transfer lines, and return bends.
Finally, one other problem material is salt (primarily chlorides, sulfates
and carbonates of sodium, calcium, and magnesium) that occurs in crude
in the form of fine droplets of brine or minute particles of salt. The salt
content of a crude is expressed as pounds of salt (NaCl equivalent) per
thousand barrels of crude. Salt by itself is bad enough, causing corrosion
and depositing in equipmentparticularly on heat transfer surfaces.
However, in combination with H2S and H2O a vicious corrosion cycle
occurs on carbon steel and even stainless steel. Later in the book, we shall
see how the refiner deals with these and some other problems.
There has been an understandable tendency among refiners (with a free
choice) to select from the crudes available, those with the lower amounts of
these difficult materials. As a result, the reserves of more desirable crudes
decline while the reserves of less desirable crudes grow. On average, crude
oils available for import are heavier and contain more of these contami-
nants than do domestic crudes. As the U.S. has become more dependent on
imported crude, these effects have been reflected in the quality of the aver-
age crude refined in the U.S., progressively heavier and containing more
sulfur and the other undesirables (Figs. 33 and 34).6

Properties of Hydrocarbons
The many hydrocarbons in crude oil vary widely in physical and chemical
properties. It is these differences that determine the ways in which they are
processed in the refinery and finally the ways in which finished products
from the refinery are employed.
Figure 35 demonstrates the close correlation of the boiling point (BP)
of a hydrocarbon with its number of carbon atoms per molecule for differ-
ent series of hydrocarbons. This permits the use of the number of carbon
atoms as a parameter in lieu of BP.7
Figure 36, containing data calculated by author, shows how the weight
ratio of carbon to hydrogen (C/H) varies with number of carbon atoms for
different series of hydrocarbons. The primary purpose of this graph is to

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

Fig. 33 API Gravity of Crude to U.S. Refineries

Fig. 34 Sulfur Content of Crude Charged

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PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 35 Boiling Point vs. No. of Carbons

Fig. 36 C/H Ratio vs. No. of Hydrocarbons

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

show the marked difference in C/H between the alkylbenzenes and the
other hydrocarbons. This will be referred to later in our discussion of
processing.
One familiar characteristic of petroleum products (and thus of hydro-
carbons) is their combustibility. Figure 37 shows the close correlation
between the flash point of a hydrocarbon and its number of carbons atoms.8
This should not come as a surprise in view of the close correlation between
BP and Cs, since the flash point is the temperature at which sufficient vapor
is generated to support combustion when ignited.
The upper and lower explosive limits of normal paraffins (as represen-
tative of the various series) are plotted against Cs in Figure 38.7,8,9 The area
between the lines is the explosive range. Below the lower limit, the mixture
is too lean to flashabove, too rich.
The autoignition temperature (AIT) is the temperature at which a
vapor will ignite spontaneously (in the absence of a flame). The anomalous
behavior of aromatics with respect to AIT is demonstrated in Figure 39

Fig. 37 Flash Points of Some Hydrocarbons

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PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 38 Flammability of Normal Paraffins

Fig. 39 Autoignition Temperature, F

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

showing that the other hydrocarbons have significantly lower AITs for the
same number of Cs.8,9 It should be noted that a gasoline or naphtha could
ignite spontaneously on coming into contact with a 600F surface.
The specific gravity of crude oil and petroleum products is generally
expressed as degrees API (American Petroleum Institute), which is defined
by the following equation:

141.5
API = 131.5
sp. gr.

where the specific gravity is the ratio of the density of the material at 60F
to the density of water at that same temperature. The gravity of water at
60F is 10 API.
A calculated value that has been used widely as a parameter for corre-
lating properties of petroleum products is the Watson characterization fac-
tor or K factor. The defining equation is:

MeABP 1/3
K =
sp. gr.

where MeABP is the mean average BP of the fraction in degrees Rankine.

MeABP is the arithmetic average of the molal average BP (MABP) and the
weight average BP (WABP). A correlation of WABP, MABP, MeABP, and
cubic average BP in terms of the volumetric average boiling point (VABP)
and the slope of the ASTM distillation was presented by Watson and
Nelson.10
Figure 310 is a plot of K factors for petroleum fractions calculated
using the above equation. Figure 311 shows the variation of K with the
number of carbon atoms for the different series of hydrocarbons.7 Figure
312 shows cetane number vs. number of carbon atoms for various series
of hydrocarbons. Cetane number is defined in chapter 5 under the discus-
sion of diesel fuel characteristics.
Oftentimes the engineer has the distillation and gravity of a material
but needs additional property information. Fortunately, the properties of
petroleum fractions and the interrelationships between these properties
have been investigated extensively. Some of these relationships have been

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PETROLEUM REFINERY P ROCESS ECONOMICS

Fig. 310 K Factors for Petroleum Fractions in terms of Boiling Point and API Gravity

Fig. 311 K Factor vs. No. of Carbon Atoms

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

Fig. 312 Cetane Numbers of Some Hydrocarbons

presented in the form of graphs or nomographs, to be found in various

references, such as the graphs provided by American Society for Testing
Materials (ASTM) in chapter 5 showing sensitivities of various series of
hydrocarbons and the graphs in chapter 30 showing some relationships for
jet fuels. The API Data Book contains numerous property correlations.
The early refiners produced their finished products directly from crude
oil by distillation aloneand not very good distillation at that. Except
for some residual fuel oil, the products were quite different from those
produced in today's very complex refinery. With strict environmental
regulations in effect and crudes higher sulfur content, products from crude
distillation today require further (sometimes multi-step) processing to
produce acceptable finished products.

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PETROLEUM REFINERY P ROCESS ECONOMICS

Refinery Products
Of the multitude of products produced by the refiner today, only those listed
below are considered in this work. They are listed in order of increasing
boiling temperatures, since distillation is the primary means employed for
separating refinery products. The values are general and are included only
for comparative purposes.

Boiling Range, F Av. MW No. Cs

LPG -4431 4458 34
Gasoline 31400 100110 411
Kerosene, Jet fuel 380520 160190 1015
Diesel fuel 520650 245 1520
Atmos. gas oil 650800 320 2025
Atmos. Resid 800+ 25+
Vacuum gas oil 8001,000 430 2550
Vacuum resid 1,000+ 800+ 50+
Petroleum coke 2,000+ 2,500+ 200+

Such specialty products (of relatively low amounts) as lubes, greases,

carbon black, petrochemical feedstock, etc., are not considered.
Initially, the refiner distilled crude oil to produce kerosene in competition
with coal oil. After the explosion of several oil lamps, it was realized that a
quantity of lower boiling material would need to be removed before recov-
ering kerosene. This material began to be used in the horseless carriage. As
the number of automobiles grew, the demand for gasoline grew. In a short
while, gasoline became the major product produced by the refiner.
At first, product quality demands were made primarily by the auto-
mobile manufacturers. More recently, competition between refiners and
marketers became a factor as well. Still more recently, the government in
the form of the EPA and state regulatory agencies has become the primary
factor forcing changes on the refiner.

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 CHAPTER 3 CRUDE OILS, HYDROCARBONS, AND REFINERY PRODUCTS

Notes
1. Forecast and Review, Oil & Gas Journal, in January each
year plus EIA, Table A5, Annual U.S. Petroleum Supply
and Demand, October, 1997
2. Midyear Forecast, Oil & Gas Journal, in July each year
3. Annual Refinery Survey, Oil & Gas Journal, in December
each year
4. Midyear Forecast, Oil & Gas Journal, in July each year
5. Worldwide Refining, Oil & Gas Journal, in December each
year plus EIA, Table 19, Percent Refinery Yield of
Petroleum Products by PAD and Refining Districts, each
year
6. Swain, E.J., Oil & Gas Journal, September 9, 1991, pp. 59-
61 plus October 5, 1998, ff 43
7. American Petroleum Institute, API Technical Data Book
Petroleum Refining, 1987
8. Dean, J.A., Lange's Handbook of Chemistry, 13th ed.,
McGraw-Hill Book Company, New York, 1985
9. Hercules Incorporated, Data Guides, Tech-Notes and
Service-Notes, Hazard Evaluation & Risk Control Services,
Rocket Center, W. Va, 1987
10. Watson, K.M., and Nelson, E.F., Industrial and Engineering
Chemistry, vol. 25, 1933, p. 880

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