New Correlation When Fitting Data of ASTM Distillation Curves, Dr. Khalid Farhod Chasib, TDM
New Correlation When Fitting Data of ASTM Distillation Curves, Dr. Khalid Farhod Chasib, TDM
New Correlation When Fitting Data of ASTM Distillation Curves, Dr. Khalid Farhod Chasib, TDM
ABSTRACT
The present work deals with fitting literature data of ASTM Distillation curves and
obtain a new correlation suitable to use in modeling when optimized the refining processes,
such as distillation, FCC, catalytic reforming, hydrotreating, etc.
The results showed that the values predicted by a new correlation are very good
agreement with data of literature and the range of mean overall deviation (%MOD) is (0.305-
0.585).
INTRODUCTION
Distillation curves provide a breadth of information about the crude oil or the
petroleum fuel. In certain respects, the boiling point distribution is representative of the
composition of the petroleum fraction. Therefore, in principle, by determining the presence
and volume percent of the components in a conventional hydrocarbon fuel solution, the
overall physical properties can be determined (1). P P
The simple distillation curve is the temperature as a function of the percent distilled in
a simple or Rayleigh type of distillation. This type of distillation is approximated by the
laboratory A.S.T.M. distillation which is widely used to characterize petroleum fractions. The
A.S.T.M. procedure gives some reflux and rectification, and the results are not exactly equal
to the simple batch distillation, although the difference is not large. The temperature normally
measured is the condensation temperature of the vapor flowing from the still to the condenser
(1)
P .
P
There are many types of standard distillation tests that determine the boiling point
distribution of petroleum fuels, the inter-conversion between which is well documented.
Some of the more common standard test methods for distillation of petroleum products
include: ASTM D86-96, which is performed under atmospheric pressure and is used for
determining the boiling point distribution of light petroleum fractions, such as naphtha,
kerosene, diesel, and light gas oil; micro-distillation; molecular distillation; fractional
distillation (typically using a spinning band still); ASTM D5236 distillation (typically using a
pot still); D1160 (for heavy petroleum fractions); ASTM D3710 (simulated distillation, which
is also known as the GC SimDist method, and uses gas chromatography to determine the true
boiling point, or TBP, of gasoline); ASTM D2887 (GC SimDist to determine the TBP of
petroleum fraction other than gasoline); ASTM D2892 (also known as 15/5 distillation, which
produces simulated TBP of petroleum fuels using a distillation column with 15 theoretical
plates and a reflux ratio of 5); ASTM D5236 Distillation (also known as the vacuum pot still
method, and is used for heavy hydrocarbon mixtures); ASTM D5307 (SimDist for
determining TBP of crude oil); ASTM D6352-98; and Hemple analysis for the distillation of a
large volume of fuel samples providing further detailed analysis of the produced distilled cuts.
ASTM D86-96 and D1160 may be combined together for determining the boiling point
distribution of wide boiling range materials, such as crude oils (2). P P
The ASTM distillation curve conducted on the whole crude. This type of distillation
curve is used however on a routine basis for plant and product quality control. This test is
carried out on crude oil fractions using a simple apparatus designed to boil the test liquid and
to condense the vapors as they are produced. Vapor temperatures are noted as the distillation
proceeds and are plotted against the distillate recovered. Because only one equilibrium stage
is used and no reflux is returned, the separation of components is poor and mixtures are
distilled (3).
P P
(4, 5)
The molecular distillation process P P introduces a potential technique for attainment
of liquid volume percentage in relation to temperature for the distilled fractions. In Batistella
(6)
P , it can be verified the robustness of this method since it enables operation at low
P
temperatures, short residence times, being ideal for working with high molecular weight and
(7)
thermally sensitive compounds P . In the petroleum case, avoids thermal cracking, allowing,
P
thus, the development of a methodology for determination the real TBP curve. The molecular
distillation technique has being reported. It is necessary, however, establish a relationship
(8, 9)
between the operating conditions of the molecular distiller and the TBP curve P . In
P
(10)
Batistella et al. P , data of temperature and percentage of distillate from molecular distiller,
P
obtained experimentally, were used in the TBP curve extension, and a new correlation
(FRAMOL correlation) was presented (11): P P
−4 −6
TBP = 456.4 + 0.1677×T DM + 1.64⋅10 ×T DM + 4.13⋅10 ×T DM
2 3
(1)
In the past five decades the researchers tried to calculate the properties of crude oil or
the petroleum fuel by making a mathematical model, which is a function of composition and
some constants, which fits the experimental data. This mathematical model is not supported
by any theoretical base. With the development of computer and computer programs the use of
analytical expressions to interpolate, extrapolate and even predict thermodynamic information
has become of increasing importance for process design and for modeling of process
operation (13). P P
Ψ
β
−
V = 1 − e α ×100 (2)
where V is the volume percent distilled at temperature T and α and β are constants and
determined from the data of ASTM distillation curve, Ψ is the dimensionless temperature
defined as:
T −T i
Ψ= (3)
T f −T i
where Ti and Tf are the initial and final boiling point temperatures of ASTM distillation
MAXIMUM-LIKELIHOOD PRINCIPLE
The estimation of parameters in theoretical and semi-empirical mathematical models
from experimental data is an important requirement in many fields of science and
engineering. In the maximum-likelihood analysis, it is assumed that all measured data are
subject to random errors. If each experiment were replicated, the average value for each
replicated experimental point would approach some true value. Usually the distribution of a
measured variable about its true value is approximated by the normal distribution,
characterized by an associated variance. The variances are ideally obtained from replicated
experiments, but they may be estimated from experience associated with a particular type of
experimental apparatus. It is customary to assume that the random errors in different
experiments are uncorrelated (14). P P
For each experiment, the true values of the measured variables are related by one or
more constraints. Because the number of data points exceeds the number of parameters to be
estimated, all constraint equations are not exactly satisfied for all experimental measurements.
Exact agreement between theory and experiment is not achieved due to random and
systematic errors in the data and to “lack of fit” of the model to the data. Optimum parameters
and true values corresponding to the experimental measurements must be found by
satisfaction of an appropriate statistical criterion (14).
P P
DETERMINATION OF CONSTANTS
Constants α and β are calculated such that Eq.2 fits the literature data P
(1,2)
P of ASTM
distillation. The properties of the crude oils and petroleum fractions used are shown in Table
(1). To obtain the best fitting that describe the ASTM curves, the sum of square of errors for
prediction should be minimum. Let T 1 , T 2 , …, T n and V 1 , V 2 , …, V n be the data of ASTM
R R R R R R R R R R R R
distillation test. The values of α and β should minimize the following function:
2
Ψ
β
−
n
∑
lit . calcd
Mi −Mi
lit .
CONCLUSIONS
The properties of natural petroleum and petroleum products make use of the ASTM
distillation analyses very useful for petroleum characterization, design and operation of
refinery units, the classification of petroleum, the development of petroleum property
correlations and it has been used worldwide.
Optimum values of constants α and β are significantly different for each case (Figs. 2
to 7). Eq. 2 has been successfully integrated in model of FCC Unit for blending ASTM
distillation curves of fresh feed, recycle LCO and recycle HCO for the total feed to the
reactor.
REFERENCES
[1] W. C. Lyons, (1996), Standard Handbook of Petroleum and Natural Gas Engineering,
Gulf Publishing Company.
[2] J. G. SPEIGHT, (2002), Handbook of Petroleum Product Analysis, John Wiley & Sons,
Inc., Hoboken, New Jersey.
[3] R. J. HENGSTEBECK., (2001), PETROLEUM PROCESSING, Principles and
Applications, the McGraw-Hill Book Company, Inc.
[4] Wolf, F. R. E Maciel, M. R. W., (2001), Project nº 1, UNICAMP / FUNCAMP /
FNDCT/CTPETRO / PETROBRAS / FINEP.
[5] Wolf, F. R. E Maciel, M. R. W, (2004), Project nº 2, UNICAMP / FUNCAMP /
FNDCT/CTPETRO / PETROBRAS / FINEP.
[6] Batistella, C. B., (1999), PHD Thesis (in Portuguese), UNICAMP, SP, Brazil.
[7] Batistella, C. B. E Maciel, M. R. W., (1998), Comput. Chem. Eng., v. 22, S53-S60.
[8] Burrows, G,(1960), Molecular Distillation. Oxf. Univ. Press (Oxford) .
[9] Boduszynski, M.M E Altgelt, K.H., (1994), Composition end Analysis of Heavy
Petroleum Fractions. Marcel Dekker, Inc.,NY.
[10] Batistella, C. B., Sbaite, P., Wolf Maciel, M.R., Maciel Filho, R., Winter, A., Gomes,
A., Medina, L., Kunert, R, (2005), Heavy Petroleum Fractions Characterization: A New
Approach Through Molecular Distillation, 2nd Mercosul Congress on Chemical Engineering
P P
& 4th Mercosul Congress on Process Systems Engineering (ENPROMER 2005), Costa Verde
– RJ, Brazil..
[11] Winter, A., Batistella, C.B., Wolf Maciel, M.R., Maciel Filho, R., Lopes, M. S. Medina,
L.C., A True Boiling Point Curve Through Molecular Distillation Using FRAMOL
Correlation, Internet resources available at
(http://www.nt.ntnu.no/users/skoge/prost/proceedings/icheap8-
U
pres07/icheap8webpapers/109%20Winter.pdf) U
[12] Randy B., Ian B. , (2006), Sensitivity of Oil Fate Model Predictions to Oil Property
Inputs, Can. J Chem. Engng,83, 3.
[13] Owen, K. and Coley, T. , (1995), “Automotive Fuels Reference Book”, 2nd ed., P P
GREEK LITTERS
α Constant of new Correlation (-)
β Constant of new Correlation (-)
Ψ Dimensionless Temperature (-)
SUBSCRIPT
i Initial Temperature
f Final Temperature
R
DM R Molecular Distiller
Table 1 The properties of the crude oils and petroleum fractions
Table 2 Optimum values of constants α and β and percentage of Mean Overall Deviation
F = ∑ 1 − e ×100 − V i
α
i =1
Using maximum-likelihood principle
optimization technique
550
500
Temperature C
o
450
400
Literature data
350 New Correlation
300
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
220
200
180
Temperature C
o
160
140
Literature data
120 New Correlation
100
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
340
320
300
Temperature C
o
280
260
240
180
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
550
500
450
Temperature C
o
400
350
Literature data
300 New Correlation
250
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
Fig 5 ASTM distillation curve for mixed product of LCO and slurry from FCC unit
900
850
800
750
700
650
600
Temperature C
550
o
500
450
400
350
300
250
200 Literature data
150 New Correlation
100
50
0
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
900
850
800
750
700
650
600
Temperature C
550
o
500
450
400
350
300
250
200 Literature data
150 New Correlation
100
50
0
0 10 20 30 40 50 60 70 80 90 100
Volume distilled %
اﻟﺨﻼﺼﺔ
(ASTMﻟﻠﺤﺼوﻝ اﻟﺒﺤث اﻟﺤﺎﻟﻲ ﻴﺘﻌﺎﻤﻝ ﻤﻊ ﺘﻤﺜﻴﻝ اﻟﺒﻴﺎﻨﺎت اﻟﻤوﺠودة ﻓﻲ اﻷدﺒﻴﺎت ﻟﻤﻨﺤﻨﻴﺎت اﻟﺘﻘطﻴر اﻟﻘﻴﺎﺴﻴﺔ )
ﻋﻠﻰ ﻋﻼﻗﺔ ﺠدﻴدة ﻤﻨﺎﺴﺒﺔ ﻟﻸﺴﺘﺨدام ﻓﻲ ﻨﻤذﺠﺔ اﻟﻤودﻴﻼت ﻋﻨد أﺨﺘﻴﺎر أﻓﻀﻝ ظروف ﺘﺸﻐﻴﻝ ﻟﻌﻤﻠﻴﺎت اﻟﺘﻛرﻴر ﻤﺜﻝ ﻋﻤﻠﻴﺎت
اﻟﺘﻘطﻴر و ﻋﻤﻠﻴﺎت اﻟﺘﻛﺴﻴر ﺒﺎﺴﺘﺨدام اﻟﻌﺎﻤﻝ اﻟﻤﺴﺎﻋد ﻋﻠﻰ ﺸﻛﻝ ﺤﺸوة طﺎﻓﻴﺔ واﻟﺘﻬذﻴب ﺒﺎﻟﻌﺎﻤﻝ اﻟﻤﺴﺎﻋد و اﻟﻤﻌﺎﻤﻠﺔ
اﻟﻨﺘﺎﺌﺞ ﺒﻴﻨت ان اﻟﻘﻴم اﻟﺘﻲ ﺘم اﻟﺤﺼوﻝ ﻋﻠﻴﻬﺎ ﺒواﺴطﺔ اﻟﻌﻼﻗﺔ اﻟﺠدﻴدة ﻤﺘواﻓﻘﺔ ﺒﺼورة ﺠﻴدة ﺠداً.ﻤﻊ اﻟﺒﻴﺎﻨﺎت ﻤن
اﻷدﺒﻴﺎت وان ﻤدى ﻤﻌدﻝ اﻷﻨﺤراف اﻟﻛﻠﻲ ﻟﻠﻨﺘﺎﺌﺞ ) (%MODﻫو ) .(0.585 - 0.305