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Lecture 3:

Evaluation of crude oil

Department of Chemical Engineering, National Institute of Technology, Calicut


Evaluation of Crude oil
Evaluation of crude oil is important for refiner because it gives the following types of
information:
1. Base and general properties of the crude oil.
2. Presence of impurities such as sulfur, salt, and emulsions which cause general
difficulties in processing.
3. Operating or design data. Primarily this necessitates curves of temperature and
gravity vs. per cent distilled.
a. Fractionating or true boiling point distillation curve.
b. Equilibrium or flash-vaporization curve.
c. API or specific gravity curve of each fraction distilled.
4. Curves of the properties of the fractions vs. percent distilled (mid per cent
curves) or the average properties of a series of fractions vs. Percentage
yield (yield curve) by which common realization of yields can be prepared.

Department of Chemical Engineering, National Institute of Technology, Calicut


Types of Distillation Curve: Crude Oil

1- True Boiling point (TBP) Distillation.


2- ASTM Distillation.
3- Equilibrium Flash Vaporization (EFV).

Department of Chemical Engineering, National Institute of Technology, Calicut


True Boiling point (TBP) Distillation

• firstly, under
atmospheric pressure
until 300°C (1%
distilled very 2 min)

• secondly under
vacuum pressure (to
prevent cracking
process and to
reduce the boiling
point) at 40mmHg (1%
distilled every 3-5
min)

• the vapor press.


temp. is plotted vs.
distilled(%) to get TBP
curve

Department of Chemical Engineering, National Institute of Technology, Calicut


ASTM Distillation

• It is a simple distillation
carried out with standard
ASTM flasks 100,200,500 ml
flasks.
• The data obtained is similar
to TBP data.
• No reflux is provided.
• Rapid batch distillation
employing no trays or reflux
between the still pot and
condensation

Department of Chemical Engineering, National Institute of Technology, Calicut


ASTM Distillation

• ASTM method D86 (atm. Press.): Gasoline, Kerosene, gas oil and
similar light and middle distillates.

• ASTM method D1160 (max. temp. 400oC, min.1mmHg): For heavy


petroleum fractions which tend to decompose at atm pressure

Department of Chemical Engineering, National Institute of Technology, Calicut


ASTM and TBM Distillation
• TBP/ASTM distillation curves: are the most important characterization
properties of the crude/intermediate/product streams.
• Both TBP, ASTM distillation curves are measured at 1 atm pressure.
• In both these cases, the boiling points of various volume fractions are
being measured.
• TBP curve is measured using batch distillation apparatus consisting with
15 stages and reflux ratio of 5.
• ASTM Curve: is more common because it is simple to determine in the
laboratory.
• TBP Curve: is the most useful.
• the ASTM distillation is measured in a single stage apparatus without any
reflux.
Department of Chemical Engineering, National Institute of Technology, Calicut
ASTM and TBM Distillation

Riazi and Daubert (1980)

Department of Chemical Engineering, National Institute of Technology, Calicut


Equilibrium or Flash Vaporization (EFV) Distillation

Department of Chemical Engineering, National Institute of Technology, Calicut


Cut points
TBP cut points for crude oil distillate fractions
Distillate Product Boiling Range

Butanes and Lighter


o o
Light SR Naphtha 90 - 190 F (32-88 C)
o o
Heavy Naphtha 190 - 380 F (88 - 193 C)

o o
Kerosene 380 - 520 F (193 - 271 C)

o o
Light Gas Oil 520 - 610 F (271 - 321 C)

o o
Heavy Gas Oil 610 - 800 F (321 - 425 C)

o o
Light Vacuum Gas Oil 800 - 950 F (425 - 510 C)

o o
Heavy Vacuum Gas Oil 950 - 1050 F (510 - 564 C)

o o
Vacuum Residue > 1050 F (>565 C)

Department of Chemical Engineering, National Institute of Technology, Calicut


Department of Chemical Engineering, National Institute of Technology, Calicut
Crude distillation curve

Department of Chemical Engineering, National Institute of Technology, Calicut


Gravity-mid-percent curves

• The properties are found to be different


for each drop or fraction of the material
distilled.
• The rate at which these properties
change from drop to drop may plot as
mid per cent curves.
• the specific gravity or viscosity of a
fraction is an average of the properties
of the many drops that constitute the
fraction.
• the average property is equal to the
property at the mid-point of the fraction.

Department of Chemical Engineering, National Institute of Technology, Calicut


True boiling point (TBP)

Physical property for which it is


Average Boiling Point
distinct.
Used for liquid viscosity, Specific
Volume Average
gravity.
Weight Average Critical properties i.e., temperature
Characterization factor, Thermal
Molal Average
Expansion of liquid.
Molecular weight, Sp. gravity, Heat of
Mean Average
combustion, Sp. heat etc.
For additive properties, viscosities are
Cubic Average additive when expressed on cubic
average.
Note: For narrow boiling cuts (TBP slope less than 2) all above mentioned
boiling points tend to equal.

Department of Chemical Engineering, National Institute of Technology, Calicut


True boiling point (TBP)

1:Vol. Avg. - Based on the boiling temperature of different


cuts (VABP)

Used for distinguishing physical property like Liquid Viscosity,


Specific Gravity.

For short cut Boiling Point (having short B.P), VABP =T50%

Department of Chemical Engineering, National Institute of Technology, Calicut


True boiling point (TBP)
2. Weight Average Boiling point- For Critical Temperature.

% calculation based on weight.

(Characterization factor, Thermal expansion of liquid, based


upon boiling temperature at different mole fraction.)

3. Molal average

t1, t2, t3 are at respective mole fraction. X1, X2, X3 are mole fraction

Department of Chemical Engineering, National Institute of Technology, Calicut


True boiling point (TBP)

Mean Average Boiling Point


(For Estimating Mol.wt, Sp. Gravity, Sp.heat of fraction.)

Mean Avg B.P=(Molal avg. B.P + Cubic avg. B.P)/2

Cubic avg. B.P

Va= Vol. Fraction

Department of Chemical Engineering, National Institute of Technology, Calicut


Average Boiling Point for a Fraction (summary)

Volume average boling point

Mass average boiling point

Molar average boiling point

Cubic average boiling point

Mean average boiling point

Interconversion of Boiling points


• Calculate slope of distillation curve of a fraction.
• The methods for finding the slope for ASTM/TBP/EFV is same
• TBP Slope = (t70%– t10%)/60 where 70% and 10% are volumetric boiling points.

Department of Chemical Engineering, National Institute of Technology, Calicut


Molal Avg BP

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Mean AVG BP

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Conversion of TBP slope to ASTM on
EFV slope

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Conversion of TBP slope to ASTM on
EFV slope

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Relationship between ASTM and TBP 50 volume points

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Crude oil properties

These are required for estimating property of cut ranges in the manual method.
 Mid percent API Gravity (density ) is drawn along with TBP
 Mid percent Mol. Wt. is drawn along with TBP

Evaluation of crude properties


 Calculate Mean average boiling point from TBP slope and correction factor (From
graph)
MABP = VABP- Correction factor
 Calculate Characterisation factor (Kw) and API gravity for fractions.
 Kw is assumed constant for whole crude and its fraction.
 50% BOILING POINTS OF ASTM : Calculated from the slope of TBP Curve of a
crude and its 50% B.P.

Department of Chemical Engineering, National Institute of Technology, Calicut


Estimation of EFV Distillation Curve

Estimation of the straight line EFV curve:


1. Estimate of t 50% of ASTM/ TBP using:
Estimate the 10 to 70% slope of ASTM/TBP using
TBP Slope = (t70%– t10%)/60
Use Fig. to convert slope (ASTM/TBP) to slope of EFV
2. Estimate t 50% of EFV from Fig.
t 50%EVF= t50% TBP− ΔT
3. Draw a straight line through t50% EFV with slop of EFV
4. t 0% ( bubble point )=t 50% EFV – slope FVE*(50)
5 . t 100% (dew point)= t 50% of EFV +slope EFV*(50)

Department of Chemical Engineering, National Institute of Technology, Calicut


Example
Whole crude oil TBT data (API gravity 36.3)

Vol.% 5 10 20 30 40 50 60 70 80 85
TBP 62 144 255 344 437 531 623 717 819 897
Temp (F)

• SP.Gr.For whole crude = 141.5/ (131.5+ API)


• Sp. Gr. = 0.84 (for the crude oil)
• Volume average boiling point VABP for whole crude = (t20+t50 + t 80)/3
VABP =[ ( 255+ 531+819)/3 ]= 535 oF
• TBP Slope =[ (t70- t10)/ 60 ] = (717-144)/60 = [9.6 oF/%]
• Correction Factor (from graph ) = 70 oF
• Mean Average Boiling Point ( MABP) = 535 - 70 = 465 oF
• ΔT = 66oF using t50 TBT
• t 50%EVF= t50% TBP− ΔT =531-66= 465oF
• The slope of EFVC= 6.5oF
Department of Chemical Engineering, National Institute of Technology, Calicut
Example

Department of Chemical Engineering, National Institute of Technology, Calicut


Example

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Pseudo-Components

• The petroleum fractions - as a mixture of discrete pseudo-components


with defined boiling point ranges or cut points on the TBP distillation
curve.
• Each pseudo-component corresponds to several unknown actual
compounds (e.g. paraffins, naphthenes and aromatics) which boil in a
given temperature range.
• Usually each pseudo-component - an average normal boiling point,
specific gravity and molecular weight.
• The number of such pseudo-components depends on the boiling point
range of the whole petroleum fraction.
• This number is a trade off between producing a smooth calculated
property curve and having too many components which both leads to
excessive computation time
Department of Chemical Engineering, National Institute of Technology, Calicut
Pseudo-Components
The following cut-point ranges are reasonable for most refining calculations

A general guideline for determining the number of pseudo-components is


as follows

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Pseudo-Components

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Example

Compute the specific gravity of a 41.4 API (0.8183 spg) mixed base
crude oil from the spg mid percent

Department of Chemical Engineering, National Institute of Technology, Calicut


Example

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Pseudo-Components: problem
A petroleum cut has the following ASTM D86 Distillation data:

Divide the TBP curve of the petroleum cut into 20 pseudo-components. Calculate
the liquid volume percentage of each pseudo-component

Department of Chemical Engineering, National Institute of Technology, Calicut


Pseudo-Components
• The end boiling point (EBP) of the cut is 218.2°C
• The Initial boiling point (IBP) is -5.4°C
• No of cuts =20
• Temperature interval for each pseudo-component =(218.2+5.4)/20 = 11.2°C
• The EBP of the first cut = IBP+Interval = -5.4+11.2 = 5.8°C
• The average boiling point (NBP) of first component = (IBP+EBP) /2 = (-
5.4+5.8)/ 2=0.2°C
• The volume % at the end of first cut = 2.84 ( from TBP curve)
• The EBP of the second cut= 5.8+11.2 = 17°C
• The average boiling point (NBP) of second component = (5.8+17)/2 = 11.4°C
• The volume % at the end of second cut = 6.19 ( from TBP curve)
• Cut volume for second cut = 6.19-2.84= 3.35

Department of Chemical Engineering, National Institute of Technology, Calicut


Pseudo-Components

Department of Chemical Engineering, National Institute of Technology, Calicut


Homework

Department of Chemical Engineering, National Institute of Technology, Calicut


Homework

For a given crude oil;


1- Draw a TBP curve,
2- Evaluate the crude,
3- Find the value of Kw if API=43,
4- Draw a EFV on the same Figure,

Department of Chemical Engineering, National Institute of Technology, Calicut

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