COMPOSITION AND CHARACTERISTICS

OF CRUDE PETROLEUM

Crude Oil Composition:

1. Chemical approach
1. S, salt, metals, nitrogen and so forth
2. Carbon residue (CCR)

2. Physical methods
1. Distillation
2. Density, specific gravity, and API gravity
3. Viscosity
4. Vapor pressure
5. Flash and fire points
6. Cloud and pour points
7. Color
8. Basic sediments and water (B.S.&W.)
9. Aniline point
10. Carbon residue
Crude Oil Composition:
1. Chemical composition
2. Physical properties
(a) API, RVP,
(b) Distillation: ASTM, TBP, EFV
TBP is true boiling point
EFV is equilibrium flash vaporization
(c) Correlations: Kw, IND
Kw is Watson characterization factor
IND is U.S. Bureau of Mines correlation index.

Crude Oil Comparisons and crude oil assay

1. The properties of crude oil
2. The fractions obtained: (a) their percentage yield and (b) properties

The basis of the assay is the distillation of a crude oil under specified
conditions in a batch laboratory distillation column, operated at high
efficiency [column with 14 plates and reflux ratio (RR)].
Composition of Petroleum
Crude

Element Percent by weight

Carbon 84 – 87
Hydrogen 11 – 14
Sulfur 0–3
Nitrogen 0 – 0.6
 Hydrocarbons Compounds
• Alkanes (Paraffins)
 Carbon atoms connected by single bond
 Other bonds saturated with hydrogen
CnH2n+2.
 Hydrocarbons Compounds
• Cycloparaffins (Naphthenes)
 Ringed paraffins (cycloparaffins)
 All bonds saturated with hydrogen
 Hydrocarbons Compounds
• Aromatics
 Six carbon ring (multiple bonding)
 All bonds are unsaturated
 Hydrocarbons Compounds
• Alkenes (Olefins)
 Usually not in crude oil
 Formed during processing
 At least two carbon atoms connected by double bond
C nH n.
Non – Hydrocarbon Compounds
• Sulfur Compounds
Non – Hydrocarbon Compounds
• Nitrogen Compounds
Non – Hydrocarbon Compounds
• Oxigen Compounds
Non – Hydrocarbon Compounds
• Metallic Compounds
Some of the more abundant are
 Sodium
 Calcium
 Magnesium
 Aluminum
 Iron
 Vanadium
 Nickel

Porphyrin
SG - specific gravity defined as the ratio of the density of the
crude oil to the density of water both at 15.6 °C (60 °F)

API gravity – American Petroleum Institute

< 10 API Very heavy crudes

10-30 API Heavy crudes
30-40 API Medium crudes
> 40 API Light crudes
Key fractions °API

No. 1: 250 – 270 °C

No. 2: 275 – 300 °C
1. Paraffinic: paraffinic hydrocarbons with a
relatively lower percentage of aromatics and
naphthenes
2. Naphthenic: cycloparaffins in a higher ratio and a
higher amount of asphalt than in paraffinic crudes
3. Asphaltic: fused aromatic compounds and
asphalt in higher amounts
Correlations: Kw, BMCI
(Tb ) (1/ 3)
Kw: Watson characterization factor Kw 
G

87,552
BMCI: U.S. Bureau of Mines correlation index BMCI   473,7G  456,8
Tb

(Tb ) : average boiling point ( R)

G : specific gravity (60  F)

Kw Crude type
<10 highly aromatic crude
~10,5-12,5 highly naphtenic crude
~12,5-13 highly paraffinic base
 Bulk Properties
• Sulfur Content
The sulfur content is expressed as a percentage of
sulfur by weight (or ppm), and varies from less than
0.1% to greater than 5%.

< 1wt.% Low-Sulfur or Sweet crude

> 1wt.% High-sulfur or Sour crude

Hydrogen sulfide (ppm): Toxic gas than can evolve

during storage or in the processing

LIGHT AND LOW SULFUR CRUDE ARE WORTH MORE

THAN HEAVY AND HIGH-SULFUR ONES
 Bulk Properties
• Pour point
It is a measure of how easy o difficult to pump the
crude oil, especially in cold weather.
It is the lowest temperature at which a crude oil will
flow or pour when it is chilled without disturbance at a
controlled rate.

The pour point of the whole crude or oil fractions

boiling above 232°C (450°F) is determined by the
standard test ASTM D97.
 Bulk Properties
• Flash Point
The flash point of a liquid hydrocarbon or an oil
fraction indicates its fire and explosion potential.
It is the lowest temperature at which sufficient vapor is
produced above the liquid to form a mixture with air
that a spontaneous ignition can occur if a spark is
present.

One of the standard test methods for the flash point is

ASTM D3278.
 Bulk Properties
• Freeze Point
It is the temperature at which the hydrocarbon liquid
solidifies at atmospheric pressure.

It’s an important property for kerosene and jet fuels,

because of the very low temperatures encountered at
high altitudes in jet planes.

One of the standard test methods for the freeze point

is ASTM D4790.
 Bulk Properties
• Smoke Point
The smoke point refers to the height of a smokeless
flame of fuel in millimeters beyond which smoking
takes places. The standard test methods for the
freeze point is ASTM D1322.

• Aniline Point
It represents the minimum temperature for complete
miscibility of equal volumes of aniline and petroleum
oil.
It is an important property of diesel fuels, and is
measured by ASTM D611.
 Bulk Properties
• Cloud Point
It refers to the temperature at which solidifiable
components (waxes) present in the oil sample begin
to crystallize or separate from solution under a
method of prescribed chilling.
It’s an important specification of middle distillate fuels,
as determined by ASTM D2500.

• The acid number

The acid number results from ASTM test method
D3339-11 that determines the organic acidity of a
refinery stream.
 Bulk Properties
• Conradson carbon residue (CCR)
It measures the coke-forming tendencies of oil. It’s
expressed as the weight percentage of the original
sample.
A related measure of the carbon residue is called
Ramsbottom carbon residue. The CCR results from
ASTM test D189.

• Refractive index
It represents the ratio of the velocity of light in a
vacuum to that in the oil. It’s determintated by ASTM
D1218.
 Bulk Properties
• Viscosity
Resistance of a liquid to flow
“pumpability” of oil
• Ash content
Is an indication of the contents of metal and salts in a
sample.

Crude sample is burned in air  ash: material

unburned
Metal oxides, stable salts and silicon oxides
Reid Vapor Pressure (RVP)
Is a measure of the vapor pressure exerted by oil or
by light products at 100 ºF.
 Bulk Properties
• Metals
As, Ni, Pb, V (ppm)
Poisson for process catalysts
• Nitrogen
It is the weight of total nitrogen determined in a liquid
hydrocarbon (ppm)
Contribute negatively to process catalysts
• Salt content
PTB (pounds of salt by thousand barrels of oil)
Corrosion problems (top-tower zone and the
overhead condensers)
 Bulk Properties
Asfaltenos & SARA
 Petroleum
products

Crude Oil Comparison

and
Crude Oil Assay
1. The properties of crude oil
2. The fractions obtained
(a) Percentage yield
(b) Properties
 Crude Assay
A typical crude assay includes two types of
information for an oil sample:
1. Bulk Properties
2. Fractional Properties
Since the properties and composition of crude
change over time, Kaes suggests that assay
data should not be two years older tan the
process data used to build process simulation.
 Fractional Properties
• Octane Number
It’s a measure of the knocking characteristics of a fuel
in a laboratory gasoline engine according to ASTM
D2700.
0 Heptane
70 30%Heptane 70%isooctane
100 2-2-4-trimethylpentane
• Motor Octane Number (MON)
It’s reflects the engine performance at highway
conditions with highway conditions with high speeds
(900rpm).
 Fractional Properties
• Research Octane Numbers (RON)
It’s corresponds to the low-speed city driving (600 rpm).

RON is typically higher than MON because of engine

test efficiencies. The posted octane number is an
average of MON and RON.

• Cetane Index
It’s a number calculated from the average boiling point
and gravity of a petroleum fraction in the diesel fuel
boiling range. It is stimates according to ASTM D976.
 Boiling point curve
A key result from a distillation test is the boiling
point curve, that is, the boiling point of the oil
fraction versus the fraction of oil vaporized.

• Initial boiling point (IBP): it’s defined as the

temperature at which the first drop of liquid
leaves the condenser tube of the distillation
apparatus.

• End point(EP): it’s the highest temperature

recorded in the test.
 Distillation Test
The true boiling point (TBP) distillation of a
crude oil or petroleum fractions results from
using:
- The U.S. Bureau of Mines Hemple method
- ASTM test D-285
Neither of these methods specifies the number
of theoretical stages or the molar reflux ratio.

ASTM D2892: The 15 : 5 distillation uses 15

theoretical stages and a molar reflux ratio of 5.
 Distillation Test
• Oil fractions tend to decompose or crack at a
temperature of approximately 650 °F (344 °C) at
one atmosphere. Thus, the pressure of TBP
distillation is gradually reduced to as low as 40
mmHg.

• TBP distillation typically takes much time and labor.

In practice, we carry out the distillation test of oil
fractions using other less costly ASTM methods and
convert the resulting boiling point curve to TBP
curve using correlations, as given in the API
Technical Data Book-Petroleum Refining.
 Distillation Tests
• ASTM D86: Distillation of an oil fraction takes
place at laboratory room temperature and
pressure.
• ASTM D1160: Distillation of an oil fraction is
applicable to high-boiling oil samples. The
simple is distilled at a reduced pressure,
typically at 10 mmHg, to inhibit cracking.
• ASTM D2887: It’s a popular chromatographic
procedure that separates the hydrocarbons in
a boiling-point order.
Curvas de destilación.

500

TBP
450
Temperatura (°F)

400
ASTM D86

350

300

250
0% 20% 40% 60% 80% 100%

Destilado (%vol.)
Figura [5]. Curvas de destilación TBP y ASTM D86
.
Curvas de destilación.

Figura [6a]. Curvas de destilación TBP

.
Curvas de destilación (productos)

Figura [6b]. Curvas de destilación TBP

.
Curvas de destilación (Teórico vs. Práctica)

Figura [6c]. Curvas de destilación TBP

.
 Curvas de destilación.

PUNTO DE EBULLICIÓN PROMEDIO DE UNA MEZCLA DE

HIDROACARBUROS

Por tratarse de una mezcla de alta complejidad, el AVP o Punto de

ebullición promedio es definido en relación a la temperatura ebullición
y propiedades como la fracción molar, volumétrica o másica de los
establecidos ..

• Factor de caracterización de Watson promedio:

 Curvas de destilación.

Tabla [7]. Técnicas empleadas en la determinación del punto de ebullición promedio.

MÉTODO ECUACIÓN VARIABLES EMPLEADAS

Volumétrico
(R o °F)
Molal
Molal
Másico
Másico
Cúbico

Cúbico
Media de la
Media
Media de la
Media
 Curvas de destilación.

Curvas disponibles Curvas deseadas

MÉTODO DE CONVERSIÓN
PRESIÓN PRESIÓN
TIPO TIPO
MM Hg MM Hg

ASTM D2887 (SD) 760 4 ASTM 86 760

ASTM D 86 760 1 TPB 760
ASTM D1160 10 2 TPB 10
ASTM D1160 10 2.5 TPB 760
ASTM D1160 10 2.5.1 ASTM 86 760
TPB 10 5 TPB 760
ASTM D2887 760 3 TPB 760
ASTM D1160 1 5.2.5 TPB 760
ASTM D1160 1 5.2.5.1 ASTM 86 760
ASTM D1160 100 5.2.5 TPB 760
ASTM D1160 100 5.2.5.1 ASTM 86 760

Fuente: Api API Technical Databook

Curvas de destilación.

Figura [7]. Conversión entre curvas de destilación

 Pseudocomponentes.

ALGORITMO PARA LA DETERMINACIÓN DE LOS

PSEUDOCOMPONENTES

1. Convertir ASTMD86 / D1160 / D2887 en curva TBP si curva TBP

no está disponible.

2. En caso de no contar con la totalidad de la TBP extrapolar los

datos conocidos.

3. Cortar el intervalo de ebullición en el número de pseudo

componentes que se deseen obtener.

4. Estimar la distribución de la densidad de pseudocomponentes

aunque sólo este disponible la densidad aparente.
 Pseudocomponentes.

CONVERSIÓN ENTRE CURVAS DE DESTILACIÓN.

Tabla [8]. Procedimiento 3A1.1 ASTMD86 - TBP

ASTM D86 TBP
i Vol% Distilled (°F) (°F) a b
6 0 320,00 30,06 57,50 259,10 7,40 0,60244
5 10 350,06 29,88 55,88 316,61 4,90 0,71644
4 30 379,94 24,12 38,77 372,49 3,0305 0,80076
3
3 50
50 404,06
404,06 28,98
28,98 39,97
39,97 411,25
411,25 2,53 0,82002
2
2 70
70 433,04
433,04 36,00
36,00 45,51
45,51 451,23
451,23 3,0419 0,75497
1
1 90
90 469,04
469,04 10,98
10,98 6,31
6,31 496,74
496,74 0,11798 1,6606
-- 100
100 480,02
480,02 -- -- 503,04
503,04

=a (T < 50%):

(T > 50%)
 Pseudocomponentes.

DETERMINACIÓN DE PSEUDOCOMPONENTES

TBP Curve @ 760 mmHg

%Vol T (°F) Para cada corte (pseudocomponente):
0 310,2 1) Elegir el %vol.
10 341,4
30 369,8 2) Determinar la temperatura media de
50 387,4 ebullición de cada corte.
70 406,4
90 433,4 3) Calcular la gravedad específica.
100 480,6 4) Determinar la fracción másica y el %wt.
5) Calcular el peso molecular.
Gravedad Específica 0,7475
Valor inicial MeABP (°F) 387,4 6) Determinar el %molar.
Factor Watson Kw 12,625521
Pseudocomponentes.

Tabla [9]. Pseudocomponentes generados a partir de los datos TBP.

Inicial Final Mitad T (°F) SGi Wi %Wt MW %Mol
0 5 2,5 318,66 0,729 3,64E-02 4,861 133,269 5,733
5 10 7,5 334,52 0,733 3,67E-02 4,893 138,602 5,550
10 15 12,5 347,29 0,737 3,69E-02 4,919 142,999 5,408
15 20 17,5 356,42 0,740 3,70E-02 4,938 146,203 5,309
20 25 22,5 362,87 0,742 3,71E-02 4,951 148,499 5,241
25 30 27,5 367,69 0,744 3,72E-02 4,961 150,228 5,190
30 35 32,5 371,87 0,745 3,72E-02 4,969 151,741 5,147
35 40 37,5 376,02 0,746 3,73E-02 4,977 153,252 5,105
40 45 42,5 380,31 0,747 3,74E-02 4,986 154,829 5,062
45 50 47,5 384,92 0,749 3,74E-02 4,995 156,535 5,016
50 55 52,5 390,00 0,750 3,75E-02 5,005 158,429 4,966
55 60 57,5 395,36 0,752 3,76E-02 5,015 160,444 4,914
60 65 62,5 400,45 0,753 3,77E-02 5,025 162,378 4,865
65 70 67,5 404,73 0,754 3,77E-02 5,034 164,018 4,824
70 75 72,5 407,73 0,755 3,78E-02 5,039 165,170 4,796
75 80 77,5 410,48 0,756 3,78E-02 5,045 166,235 4,770
80 85 82,5 415,57 0,758 3,79E-02 5,054 168,220 4,723
85 90 87,5 425,66 0,761 3,80E-02 5,074 172,204 4,631
90 95 92,5 443,24 0,766 3,83E-02 5,107 179,316 4,477
95 100 97,5 467,40 0,772 3,86E-02 5,152 189,451 4,275
 Pseudocomponentes.

• Capacidad calorífica Gas ideal • Capacidad calorífica

(Lee-Kesler). líquidos

Recomendado por API

 Pseudocomponentes.

CORRELACIONES PROPUESTAS POR LEE-KESLER

Presión crítica

Gravedad específica
Temperatura de ebullición del corte.

Temperatura crítica
 Pseudocomponentes.

Peso molecular

Factor acéntrico

si

si
 Pseudocomponentes.

• Volumen molar de la fase líquida

•Ecuación estándar Spencer-Danner

Donde:
 Pseudocomponentes.

• Calor de Vaporización
1.Riedel 2.Chen&Vettere

1.

2.

A PB normal A cualquier T

• Presión de vapor (Lee-Kesler)

 Tratamiento de una corriente de crudo

Deben tenerse en cuenta dos

requisitos:
• Usar un numero suficiente de
pseudocomponentes.
• Tener una buena calidad de
información de ensayos del residuo
atmosférico.

Figura [13]. Curva de destilación TBP y

generación de Pseudocomponentes.

Pseudocomponentes típicos y mejorados

generados por un simulador para una
corriente de residuo atmosférico
The density of
distillate fractions
ther mid-boiling
points