Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Physical and Thermal Properties of Crude Oil and Its

Products

Introduction:

A petroleum Refinery is a collection of unit operation, such as fractionation

towers, pumps and heat exchangers. Analysis and design of these units
requires knowledge the thermodynamic and physical properties of the
petroleum fluids. Designing a crude Oil distillation tower requires
knowledge how hydrocarbon in crude oil are distributed on each tray of the
tower, that is vapor- liquid distribution and the densities of the mixture
…etc.; therefore the physical, chemical and thermal properties that must be
studying will be as follow:

1. Thermal Properties.
2. Mechanical Properties.
3. Some Electrical and Optical Properties.
4. Miscellaneous Properties.
1. Thermal Properties: These properties include:
A. Simple Thermal Properties
 Cloud point.
 Pour point.
 Freezing Point, and
 Melting point.
 Smoke point.
 Flash and fire point.
B. General Thermal Prosperities:
 Specific heat.
 Heat of Combustion.

1
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

 The heat Content or Enthalpy.

 The Latent Heat of Vaporization.
 Vapor Pressure and Boiling Points Corrections.
 Critical Properties.

C. Distillation Curves

2. Mechanical Properties: These properties can be listed as:

 Density and Coefficient of Thermal Expansion.

 Viscosity.
 Surface Tension.

3. Some Electrical and Optical Properties: These properties include:

 Conductivity.
 Statics Electrification.
 Refractive Index.
 Optical Activity.

4. Miscellaneous Properties: These properties include:

 Molecular Weight
 Aniline Point and Diesel Index.
 The hydrogen content (%H).
 The % Ash Content.
 Carbon Content%.
 Sulfur Content%.

1- Density, Specific Gravity, and API Gravity

Density is defined as mass per unit volume of a fluid. Density is a state

function and for a pure compound depends on both temperature and pressure

2
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

and is shown by ρ. Liquid densities decrease as temperature increases but the

effect of pressure on liquid densities at moderate pressures is usually
negligible.

Liquid density for hydrocarbons is usually reported in terms of specific

gravity (SG) or relative density defined as:

Since the standard conditions adopted by the petroleum industry are 60°F
(15.5°C) and 1 atm specific gravities of liquid hydrocarbons are normally
reported at these conditions. Water density at 60°F is 0.999 or almost 1
,g/cm3, thus

The American Petroleum Institute (API) defined the API gravity (degrees
API) to quantify the quality of petroleum products and crude oils. The API
gravity is defined as:

Crude Oils API = 10 – 50, crude oils can generally be classified according to
API as shown:

3
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

The definition of specific gravity for gases is somewhat different. The specific
gas )28.97(gravity of a gas is proportional to the ratio of molecular weight of
(Mg) to the molecular weight of air

Density and Specific gravity Scales:

Specific gravity of solid or liquid (SG) T1/T2 =

Specific gravity Scales(SG):

1. Twaddell Scale: this scale uses for measure specific gravity (SG) for
liquids heavier than water.

Twaddle (ᵒTW) = 200(SG (288.7k/288.7k) -1)

2. Baume Gravity Scales:

This scale uses for measure specific gravity (SG) for liquids
heavier than water:

ᵒ
Baume (ᵒBe) =

And for liquids lighter than water:

4
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

ᵒ
Baume (ᵒBe) =

American Petroleum Institute(API) Scale:

This scale uses for measure (API) for petroleum products.

ᵒ
API =

Brix Scale(Brix):
This scale uses for measure directly concentration of sugar
solutions

ᵒ
Brix =

2- Viscosity

The viscosity of oil is a measure of its resistance to internal flow and an

indication of its oiliness in the lubrication of surfaces. There are two types of
viscosity: dynamic and kinematics viscosity.

Kinematic viscosity (υ) = dynamic viscosity (μ) / density (ρ)

The unit of dynamic viscosity is poise (0.1 Pa.s). It is more commonly

expressed, particularly in ASTM standards, as centipoises (cP). While the
kinematics viscosity as centistokes –cSt (10−6 m2·s−1). The following
equations can be used to calculate the liquid viscosities of petroleum
fractions at atmospheric pressure and at temperatures of 37.8 C (100 F) and
98.9 C (210 F)

5
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Where; v100 and v210 are the kinematic viscosities at 100 and 210°F, in
centistokes. The viscosity can be measured by several instruments (U-tube
Viscometer, Saybolt Universal Viscosity (SSU), thermo-viscosity, Red wood
viscometer and Englar).

Thermo.Vis. = 15 + 148.5 kinematic Vis. = 46 SSU - 1183

The comparison of viscosity by different instruments is shown in Figure 1.

Ex.1 Calculate the kinematic viscosities for oil which has a MeABP of 320 °C
and API gravity of 34.

Sol.:

The boiling point is 593.15 K or 1067.7 R. the specific gravity is 0.855 and
the Watson K factor is 11.95. v100= 5.777 cSt and v210 = 1.906 cSt

6
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Fig.1. Comparison of viscosity by different instruments.(Viscosity must

be at the same T.)

3- Pour Point

The pour point is defined as the lowest temperature at which the sample will
flow and is a rough indicator of the relative paraffinicity and aromaticity of
the crude. A lower pour point means that the paraffin content is low and
greater content of aromatics. To estimate the pour point of petroleum
fractions from viscosity, molecular weight, and specific gravity, the
following form is used for this purpose:

Where; Tp is the pour point (ASTM D 97) in kelvin, M is the molecular

weight, and v38(100) is the kinematic viscosity at 37.8 °C (100°F) in cSt. This

7
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

equation was developed with data on pour points of more than 300 petroleum
fractions with molecular weights ranging from 140 to 800 and API gravities
from 13 to 50.

4- 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).

Crude distilled (%) at 1100°F= 100 – 3*CCR, CCR is the Carbon residue
for whole crude oil

5- 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 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.

6- 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%.

8
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Crudes with greater than 0.5% sulfur generally require more extensive
processing than those with lower sulfur content.

7- Flash point

Flash point TF, for a hydrocarbon or a fuel is the minimum temperature at

which vapor pressure of the hydrocarbon is sufficient to produce the vapor
needed for spontaneous ignition of the hydrocarbon with the air with the
presence of an external source, i.e., spark or flame. From this definition, it is
clear that hydrocarbons with higher vapor pressures (lighter compounds)
have lower flash points. Generally flash point increases with an increase in
boiling point. Flash point is an important parameter for safety considerations,
especially during storage and transportation of volatile petroleum products
(i.e., LPG, light naphtha, gasoline) in a high-temperature environment.

The flash point can be estimated using the following equation:

Where T10 is normal boiling point for petroleum fractions at 10 vol%

distillation temperature. Both temperatures (T10 and flash point (TF) in
Kelvin).

Ex.2: A kerosene product with boiling range of 175-260 °C from Mexican

crude oil has the API gravity of 43.6 and T10 is 499.9K. Estimate its flash
point and compare with the experimental value of 59 °C.

Solution:

By using the last equation, TF = 60.4 °C, which is in good agreement with
the experimental value of 59 °C.

9
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

8- Fire Point

The fire point is the lowest temperature at which the application of test flame
causes the material to ignite and burn at least for 5 seconds under specified
conditions of the test.

9- Refractive Index
The refractive index is a readily measured property that can be used as an
input parameter for other correlations. It is defined as the speed of light in
vacuum with respect to the speed of light in the medium. Since refractive
indices of petroleum fractions are not always known, it is important to

predict the refractive index.

10- Freezing Point:

Petroleum fractions are mostly liquids at ambient conditions. However,
heavy oils contain heavy compounds such as waxes or asphaltenes. These
compounds tend to solidify at low temperatures, thus restricting flow. The
freezing point is the temperature at which the hydrocarbon liquid solidifies
at atmospheric pressure. It is one of the important property specifications
for kerosene and jet fuels due to the very low temperatures encountered at
high altitudes in jet planes. One of the standard tests is ASTM D4790 and
ASTM D16.

11- Cloud Point

Cloud point refers to the temperature below which wax in diesel or biowax
in biodiesels form a cloudy appearance. The presence of solidified waxes
thickens the oil and clogs fuel filters and injectors in engines. The wax also
accumulates on cold surfaces (e.g. pipeline or heat exchanger fouling) and

10
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

forms an emulsion with water. Therefore, cloud point indicates the tendency
of the oil to plug filters or small orifices at cold operating temperatures.

12- Melting Point

Ii is the temperature at which petroleum wax stars in flow as the wax is

heated under standard conditions.

13- Octane number

An octane number is a measure of the knocking tendency of gasoline fuels in

spark ignition engines. The ability of a fuel to resist auto-ignition during
compression and prior to the spark ignition gives it a high octane number.
Two octane tests can be performed for gasoline. The motor octane number
(MON) indicates engine performance at high way conditions with high
speeds (900 rpm). On the other hand, the research octane number is
indicative of low-speed city driving (600 rpm).

RON of a fuel may be estimated from the pseudocomponent techniques in

the following form:

Where; x is the volume fraction of different hydrocarbon families i.e., n-

paraffins (NP), isoparaffins (IP), olefins (O), naphthenes (N), and aromatics
(A). RONNp, RONIp, RONo, RONN, and RONA are the values of RON of
pseudocomponents from n-paraffin, isoparaffins, olefins, naphthenes, and
aromatics families whose boiling points are the same as the mid boiling point

11
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

or the ASTM D86 temperature at 50% point of the fraction and can be
determined from Figure

Figure 2: Research octane number of different families of hydrocarbons.

There is another graphical relation for estimation of RON of naphthas in

terms of Kw characterization factor or paraffin content (wt%) and mid
boiling point as given in Figures below

Figure 3: Research octane number of naphthas

12
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Figure 4: Research octane number versus paraffin content

RON for these various hydrocarbon groups have been correlated to normal
boiling point, Tb in the following form:

…………………… (2)

Where RON is the clear research octane number and T = (Tb -273.15)/100 in
which Tb is the boiling point in kelvin. Based on the data taken from the
API-TDB, the coefficients a - e were determined and are given in Table
below:

13
‫‪Chapter Three: Physical and Thermal Properties of Crude Oil and its Products‬‬ ‫‪Petroleum Refining‬‬

‫‪Coefficients of eq. 2 for estimation of RON‬‬

‫العدد األكوتان ي(‪:)Octane Number, ON‬‬

‫هو مؤشر لما قد يحصل في محرك السيارة من قرقعة (‪ )Knocking‬اثناء االحتراق‬
‫وهذه الظاهرة مضرة بالمحرك و تقلل من كفاءة االحتراق و يجب تجنبها النها تدفع‬
‫بالمكابس ضد حركتها االعتيادية و قد تؤدي الى تحطيم االجزاء الميكانيكية للمحرك‪.‬‬
‫حدوث القرقعة لها عالقة مباشرة بالتركيب الكيميائي للبنزين و الذي يحدد بالعدد‬
‫االوكتاني الذي تم كشفه عام ‪ 6291‬من قبل العالم كراهار اوكار‪ .‬الخواص االحتراقية‬
‫الي مركب من المركبات التي توجد في خليط البنزين تقدر عن طريق المقارنة مع نسب‬
‫معينة من خليط اآليزو أوكتان ذو العدد االوكتاني (‪ )611‬و الهبتان االعتيادي الذي عدد‬
‫االوكتان له (‪.)1‬و الذي له خواص احتراقي ة رديئة‪ ,‬لذلك يكون العدد االوكتاني للوقود‬
‫تحت االختبار عددا مساويا للنسبة المؤية لآليزو اوكتان في خليط االيزواوكتان والهبتان‬
‫االعتيادي الذي يعطي خواصا احتراقية مشابهة بالضبط للخواص االحتراقية للوقود تحت‬
‫االختبار و بنفس نسبة االنضغاطية‪.‬‬

‫و العدد االوكتاني يتوقف على التركيب الجزيئي للهايدروكاربونات‪ ,‬فالبرافينات‬

‫(‪ )N-Paraffine‬تكون قليلة العدد االوكتاني بصورة عامة مقارنة مع‬ ‫المستقيمة‬
‫غيرها من المركبات الهايروكاربونية و منها البرافينات المتفرعة ويعود السبب الى‬
‫كونها مشبعة وذلك مما يجعل ذرات الكاربون فيها سهلة المنال لالحتراق و هذا يسبب‬

‫‪14‬‬
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

‫ كما ان العدد االوكتاني لهذه البارافينات‬,‫بدوره االحتراق اللحضي (الذاتي) اي القرقعة‬

.‫المستقيمة يقل كلما ازداد طول السلسلة‬

‫) فكلما ازداد تفرع السلسلة كلما ازداد العدد‬Iso-Paraffin( ‫أما البرافينات المتفرعة‬
‫ اي ان ذرات الكاربون الموجودة في مثل هذه الجزيئات تصبح اقل تأثيرا‬,‫االوكتاني‬
.)9( ‫لالحتراق من البرافينات االعتيادية و هذا بدوره يجعل االحتراق بطيئا و منتظما‬

Ex.3: A naphtha sample from an Australian crude oil has the following
characteristics: boiling point range 15.5 – 70°C specific gravity 0.6501, n-
paraffins 49.33%, isoparaffins41.45%, naphthenes 9.14%, aromatics 0.08%,
clear RON 69.6, and MON 66.2. a) Estimate RON from the
pseudocomponent method using experimental composition, b) Estimate
RON from Fig.4, and c) Estimate RON from Fig.4

Solution:

For this fraction: Tb = (15.5 + 70)/2 = 42.8°C= Tb= 315.9K., SG = 0.6501,

xp = 0.4933, xw = 0.4145, xN = 0.0914, xA =0.008:

a) RON can be estimated from Eq.(1) through pseudocomponent method

using RON values for pure hydrocarbons calculated from Eq. (2) and Table
above with Tb= 315.9K. Results of calculation are (RON)np =54.63,

15
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

(RON)Ip = (90.94 + 104.83 + 88 + 87.05)/4 = 92.7, (RON)N = 55.57, and

(RON)A =125.39. In calculation of (RON)w, an average value for RON of 4
families in Table above is calculated. From eq.2, clear RON can be
calculated as:

In comparison with the reported value of 69.6 the error is 70.55 - 69.6 =
0.95.

b) To use Fig.3 we need Tb = 42.8°C =109°F and Kw, which is calculated as

Kw = 12.75.

Since the Kw is outside the range of values in Fig.3, accurate reading is not
possible, but from value of the boiling point it is obvious that the RON from
extrapolation of the curves is above 70.

c) To use Fig. 4 we need total paraffins which is % = 49.33 + 41.45 = 90.78 and
Tb = 109°F. In this case Tb is outside the range of values on the curves, but with
extrapolation a value of about 66 can be read. The error is about = 3.6.

14- Aniline Point

The lowest temperature at which an equal volume mixture of the petroleum

oil and aniline are miscible is the aniline point. Since aniline is an aromatic
compound, petroleum fractions with high aromatic content will be miscible
in aniline at ambient conditions.

Aniline point can be estimated using the following relation:

16
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Where; AP is in C Tb is the mid boiling point in kelvin and API is API

gravity.

15- Cetane number

The cetane number measures the ability for auto ignition and is essentially
the opposite of the octane number. The cetane number is the percentage of
pure cetane (n-hexadecane) in a blend of cetane and alpha methyl naphtha-
lene which matches the ignition quality of a diesel fuel sample. This quality
is specified for middle distillate fuels.

Since determination of cetane number is difficult and costly, ASTM D976

(IP 218) proposed a method of calculation. Calculated number is called
calculated cetane index (CCI) and can be determined from the following
relation:

WhereT50 is the ASTM D 86 temperature at 50% point in °F Another

characteristic of diesel fuels is called diesel index (DI) defined as:

which is a function of API gravity and aniline point in C.

:)Cetane Number, CN(‫العدد السيان ي‬

‫ كوهكو معتكوس العدد‬.‫هكو مؤشر على سرعة احاراق كوقكود الديزل كو اال ظغنط الالزم لالشاعنل‬
‫ كولتن ليس‬،‫ هكو عنمل مهم في احديد كوعية كوقكود الديزل‬CN‫ كو‬, ‫االكوتان ي للب زين من حيث المبدأ‬
‫ خصنئص‬،‫ كوالازييت‬،‫ كوالتثنفة‬،‫الكوحيد كواشمل قينسنت أخرى من كوعية الديزل مثل محاكوى الطنقة‬

17
‫‪Chapter Three: Physical and Thermal Properties of Crude Oil and its Products‬‬ ‫‪Petroleum Refining‬‬

‫الادفق البنرد كوالتبريت‪ .‬كوهذا الرقم يقنس بنل سبة إلى خليط الهيتسنديتنن الذي له قيمة العدد السيان ي‬
‫‪ 011 = CN‬مع الفن مثل فثنلين كو الذي له قيمة العدد السيان ي ‪ .1 = CN‬عمكومن محرتنت كوقكود‬
‫الديزل اعمل جيدا مع العدد السيان ي منبين ‪ . 55-01‬الكوقكود الذي يملك عدد سيان ي قليل يملك فارة‬
‫اشاعنل طكويلة كو يحانج كوقت اطكول التامنل عملية االحاراق‪ ،‬لذا محرتنت كوقكود الديزل عنلية‬
‫السرعة اعمل بتفنءة عنلية مع الكوقكود ذكو العدد السيان ي العنلي‪ .‬الشتل أد نه يبين الفرق بي العدد‬
‫االكوتان ي كو العدد السيان ي من حيث مبدأ العمل‪.‬‬

‫‪H.W. Compare between Octane Number and Cetane Number related to:‬‬

‫‪ Chemical Composition.‬‬

‫‪ Function.‬‬
‫‪ Typical Values.‬‬
‫‪ Fuel and Types of Engines.‬‬
‫‪ Methods of Measuring.‬‬
‫‪ Additives.‬‬

‫‪18‬‬
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

16- Smoke Point

The smoke point is a test measures the burning qualities of kerosene and jet
fuel. It is defined as the maximum height in mm, of a smokeless flame of
fuel. The smoke point (SP) can be calculated using the following equation:

Where AP is the aniline point in °C and SG is the specific gravity at 15.5°C.

Equation above estimates SP according to the IP test method. To estimate SP
from the ASTM D1322 test method, 0.7 mm should be subtracted from the
calculated IP smoke point.

Ex.4: A Nigerian kerosene has an API gravity of 41.2, aniline point of

55.6°C. Estimate the smoke point of this fuel and compare with the experimental
value of 20 mm.

Solution:

From API gravity, SG = 0.819, AP=55.6°C, the calculated SP is SP = 20

mm. The ASTM smoke point is then 19.3 mm which is in very good
agreement with the experimental value of 20 with deviation of -0.7 mm.

17- Freezing Point

Petroleum fractions are mostly liquids at ambient conditions. However,

heavy oils contain heavy compounds such as waxes or asphaltenes. These
compounds tend to solidify at low temperatures, thus restricting flow. The
freezing point is the temperature at which the hydrocarbon liquid solidifies at
atmospheric pressure. It is one of the important property specifications for
kerosene and jet fuels due to the very low temperatures encountered at high
altitudes in jet planes.

19
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

18- Reid Vapor Pressure (RVP)

Is a common measure of the volatility of gasoline. It is defined as the absolute

vapor pressure exerted by a liquid at 100 °F (37.8 °C) as determined by the
test method ASTM-D-323. The matter of vapor pressure is important relating
to the function and operation of gasoline powered, especially carbureted,
vehicles. High levels of vaporization are desirable for winter starting and
operation and lower levels are desirable in avoiding vapor lock during summer
heat. Fuel cannot be pumped when there is vapor in the fuel line (summer) and
winter starting will be more difficult when liquid gasoline in the combustion
chambers has not vaporized. Thus, oil refineries manipulate the Reid Vapor
Pressure seasonally specifically to maintain gasoline engine reliability. RVP
data on 52 different petroleum products (light and heavy naphthas, gasolines,
and kerosenes) from the Oil and Gas Journal data bank have been used to
develop a simple relation for prediction of RVP in terms of boiling point and
specific gravity in the following form:

Where; Tb is the mid boiling point and Tc is the pseudocritical temperature

of the fraction in kelvin. Pc is the pseudocritical pressure and RVP is the
Reid vapor pressure in bars.

20
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

Ex.5: Estimate RVP of a gasoline sample has molecular weight of 86 and

API gravity of 86 and Tb=388K, Tc=501.2K, Pc=28.82bar.

Solution:

Tr = 0.6205, X = 1.3364, and Y = -3.7235. Thus we calculate RVP = 0.696

bar or 10.1 psia. The experimental value is 11.1 psia

19- Molecular Weight

Molecular weight (M) is perhaps the most important characterization

parameter for petroleum fractions and many physical properties may be
calculated from this parameter. M can be predicted by using the following
equation:

This equation can be applied to hydrocarbons with molecular weight ranging

from 70 to 700, which is nearly equivalent to boiling point range of 300-850
K (90-1050°F) and the API gravity range of 14.4-39. For heavy petroleum
fractions based on the molecular weight of heavy fractions in the range of
200-800:

The three input parameters are kinematic viscosities (in cSt) at 38 and 98.9°C
(100 and 210 °F shown by v38(100) and v99(210), respectively, and the specific
gravity (SG) at 15.5°C.

21
Chapter Three: Physical and Thermal Properties of Crude Oil and its Products Petroleum Refining

20- 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 point (TBP) distillation and generally refers to a distillation
performed in equipment that accomplishes a reasonable degree of
fractionation.

21- Color

The color of oil serves as an indication of the thoroughness of the refining

process. True, oils of different boiling range and from different crude oils
may have different colors; but, other things being comparable, the color
indicates the degree of refining that the material has undergone. Distilled
products that are discolored are an indication of :

1) Thermal decomposition

2) The entrainment of dark-colored tarry material, or

3) Materials that are inherently dark in color.

Discoloration by decomposition is due to the use too high temperatures, and

discoloration by entrainment is usually due to "throughputs" above the
maximum capacity of the equipment.

22