This article was downloaded by: [Montana State University Bozeman]

On: 17 August 2014, At: 14:10

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Petroleum Science and Technology

Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/lpet20

The Development of a True Boiling Point

Distillation Apparatus
a

R. Hosein & R. A. Dawe

Petroleum Engineering Unit, Chemical Engineering Department ,

University of the West Indies , St. Augustine, Trinidad
Published online: 22 Mar 2011.

To cite this article: R. Hosein & R. A. Dawe (2011) The Development of a True Boiling
Point Distillation Apparatus, Petroleum Science and Technology, 29:9, 906-913, DOI:
10.1080/10916460903452017
To link to this article: http://dx.doi.org/10.1080/10916460903452017

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the
Content) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &
Conditions of access and use can be found at http://www.tandfonline.com/page/termsand-conditions

Petroleum Science and Technology, 29:906913, 2011

Copyright Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916460903452017

The Development of a True Boiling Point

Distillation Apparatus
R. HOSEIN1 AND R. A. DAWE1
Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

Petroleum Engineering Unit, Chemical Engineering Department,

University of the West Indies, St. Augustine, Trinidad
Abstract A new true boiling point distillation apparatus was designed, fabricated,
and tested as part of a larger research effort on characterization studies of condensate fluids. Mixtures from heptanes, C6 , to dodecanes, C12 , were separated under
atmospheric conditions and from tridecanes, C13 , to nonadecanes, C19 , under vacuum conditions. Benchmarking of the results from true boiling point analyses was
performed by high-precision gas chromatography. Such data are not only scarce but
those available indicate differences ranging from 20 to 30% mainly due to carryover of
volumes outside the boiling range. This work has shown a difference of less than 10%,
which indicates that this new true boiling point equipment is capable of producing
results suitable for conducting reservoir fluids characterization studies.
Keywords characterization, hydrocarbons, oil, Trinidad, true boiling point

Introduction
Mole percentage, boiling point, specific gravity, and molecular weight of pure components
and reservoir fluid hydrocarbon fractions are used in many correlations in the chemical
and petroleum industries. Studies (Bergman, 1976; Whitson, 1984) have shown that a
proper description for single carbon number (SCN) fractions (greater than C6 ) of a reservoir fluid is essential in performing reliable phase behavior calculations. Chromatographic
methods provide a reliable separation of reservoir fluids for identifying SCN fractions
and their respective mole percentages. The gas chromatograph (GC) uses small sample
volumes in the micro liter range; therefore, it is not possible to collect and determine
specific gravities and molecular weights of these fractions because larger volumes in the
liter range are required.
With a true boiling point (TBP) distillation apparatus, a reservoir sample can be
heated at the respective boiling points of the normal paraffins (Bergman, 1976; Katz and
Firoozabadi, 1978) and SCN fractions of sufficient quantity are obtained for measuring
these physical properties. Guidelines on the equipment required, equipment design, and
operating procedures are well documented as ASTM International standard D2892-84
(ASTM, 1984). Fractions up to C12 are obtained by heating under atmospheric pressure.
Fractions beyond C12 and to a maximum of C29 are heated under vacuum conditions,
because heating at reduced pressures lowers the boiling temperatures and thus prevents
cracking.
Address correspondence to Raffie Hosein, Petroleum Engineering Unit, Chemical Engineering
Department, University of the West Indies, St. Augustine, Trinidad. E-mail: Raffie.hosein@sta.
uwi.edu

906

Development of a TBP Distillation Apparatus

907

Determination of the phase behavior of Trinidads gas condensates was conducted

because of the development of the reserves (Ministry, 2008). Due to the high cost of
commercial units, a benchtop TBP unit was designed, assembled, and tested in order
to provide the necessary characterization data. This article gives details of equipment
design, calibration, operational procedures, and results of performance for this new TBP
apparatus.

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

TBP Distillation Apparatus

TBP distillation of reservoir liquid surface samples is a process employed to separate
the heavy components (beyond C6 ) into cuts corresponding to normal paraffin fractions,
usually carried out at known temperatures equivalent to the normal paraffin boiling points.
A schematic and photograph of the apparatus that was designed and assembled are
shown in Figures 1 and 2. Essentially, it follows that used by Bergman (1976; ASTM
1984). The equipment, mainly manufactured from glass, includes a distillation flask fitted
with a heating system to supply heat for boiling, a fractionating column comprising
a distillation column and reflux divider enclosed in a heating system to supply heat
to compensate for column losses, a condenser head with cooling supply capable of
maintaining a temperature below 40F, glass thermometers for measuring vapor and
charge temperatures, and graduated receivers. The sizes of the distillation flask and
column (details given below) were determined in accordance with the specifications
stated in ASTM method D-2892-84 (ASTM, 1984).

Figure 1. Schematic of the TBP distillation apparatus.

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

908

R. Hosein and R. A. Dawe

Figure 2. TBP distillation apparatus.

Design Considerations
Distillation Flask
The standard practice (Bergman, 1976; ASTM, 1984) is to select a distillation flask at
least 50% larger than the volume of the charge. Because a condensate volume of 200 cc
is suitable for the characterization process, a flask of capacity 500 cc was used. This
flask contained two side arms. One side arm was used as a thermo-well, which contained
a thermometer to determine the temperature of the charge, and the other, which was
plugged during runs, was used for charging the sample into the flask.
Heating System
The flask was heated by a 300-W electrothermal heating mantle capable of heating to a
maximum temperature of 662F. The heating mantle covered the lower half of the flask
and the upper half was insulated to reduce heat losses. Heat input was manually adjusted
using a built-in variable transformer to provide the quickest boiling and cooling.
Fractionating Column
The column used was 920 mm long with 40 mm internal diameter and was packed with
ceramic beads. This packing was corrosion resistant and provided a large surface area
for the ascending vapor and constrained the liquid to travel uniformly with avoidance of
streaming through the packing or down the column walls. This allowed mixing of vapor
and liquid to take place at each stage and improved separation of the more volatile from
the less volatile components.
The column was wrapped with electrical heating tape and insulated. The objective
was to render it adiabatic, in an effort to ensure reproducible temperature gradients
throughout its length, thus enhancing reproducibility of results. The ends of the column
were fitted with quick-fit ground joints for rapid attachment to the distillation flask at

Development of a TBP Distillation Apparatus

909

the bottom and an adaptor with two side arms at the top. One side arm contained a
thermometer for measuring vapor temperature, and the other contained the reflux divider
and a condenser.
Condensers

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

A refrigerated bath was set up to allow cold water at a maximum temperature of 40F
to flow into the condenser. The condenser above the column was 300 mm long and had
sufficient capacity to condense all vapors heavier than pentane, C5 . A second condenser
was installed just above the product receivers to ensure that the light fractions remained
in the liquid state.
Product Receivers
The product receivers ranged in capacity from 10 to 50 cc depending on the distillate
output expected. These were factory graduated and permitted reading of volumes to the
nearest 0.1 cc. The receivers were enclosed by an ice jacket to prevent any evaporation
of light fractions during collection of distillates.
Distillation under Reduced Pressure
Distillation under vacuum was achieved by connecting a vacuum pump and gauge at the
open end near the three-way valve. The vacuum system had the capacity to draw down
the pressure in the receivers from atmospheric to 2 mmHg in less than 30 sec to avoid
upsetting the equilibrium of the system during emptying of the receivers under vacuum.
The procedures established for component separation were as follows: the refrigerated bath was turned on and cold water below 40 F circulated through the inlet and outlet
of the condensers. A mixture of volume 200 cc was carefully poured into the distillation
flask and pieces of ceramic chips were added to control bumping. Heat was applied to
the flask at a predetermined rate using a variable transformer so that it took between 20
to 50 min for vapors to reach the top of the column.
Components were separated by heating at their respective boiling points (Bergman,
1976; Katz and Firoozabadi, 1978), shown in Table 1. In order to prevent cracking,
components heavier than C12 were heated under vacuum at reduced boiling temperatures.
For each component, the column was allowed to operate at total reflux for about 15 min
(Bergman, 1976). The reflux needle was then manually opened to allow a distillation rate
of between 15 and 25 cc per hour (Bergman, 1976). The distillate collected was removed
and the volume of each cut was recorded.

Performance Testing
Separation of Pure Components
The approach taken to assess the performance of the TBP equipment was to prepare
hydrocarbon mixtures from measured volumes of pure paraffin components, separate
them at their respective boiling points, and compare the distilled volumes with the initial
measured volumes. These volumes were accurately measured to 0.1 cc using a burette.
The components were separated by boiling the mixtures and taking cuts at the known pure
hydrocarbon boiling points (of the most common isomer; ASTM, 1984) and the volumes

910

R. Hosein and R. A. Dawe

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

Table 1
Comparison of volume of components in sample 3 and volume of distillate collected

Component

SCN

Heptane
Octane
Nonane
Decane
Undecane
Dodecane
TOTAL

C7
C8
C9
C10
C11
C12

Temperature
applied, F

Vacuum
pressure
applied,
mm Hg

210.1
259.1
304.4
346.4
385.5

0
0
0
0
0

Vol. of
comp. in
mixture, cc

Vol. of
distillate
collected, cc

30
40
30
20
20
60
200

30.5
38.8
29.8
20.7
20.1
58.4
198.3

% Diff.
1.67
3.00
0.67
3.50
0.50
2.67
0.85

obtained were compared to those before mixing. Because of vaporliquid equilibrium

through the phase rule, the fractions will not be pure but will contain some percentage
of additional components.

TBP Distillation of Condensate Samples

Separation of Mixtures
The procedures followed for the condensate samples were similar to that described above.
The condensate samples were first flashed at atmospheric conditions (70F and 14.7 psia).
Each cut was obtained by collecting the fraction when the top column temperature was
1.0 F above the boiling point of the normal paraffin hydrocarbon concerned (Bergman,
1976; ASTM, 1984). The boiling range (and transformer settings for this system) and
corresponding pressure (ASTM, 1984; Hosein, 2004) defines the paraffin and associated
isomer volume for the SCN fractions (C7 to C19 ). The volumes of the SCN fractions and
the residue (C20C) were recorded and compared with those derived from chromatographic
analysis (wt% was converted to volume using a basis of 200 cc). The procedures for
obtaining the SCN boiling point and SCN composition are stated in the Appendix (Hosein
and Dawe, 2011).

Results and Discussion

Separation of Pure Components
Seven samples were prepared by mixing known volumes of pure components. By using
appropriate boiling points (ASTM, 1984), the components were separated and the respective volumes obtained were compared to those before mixing (Hosein, 2004) as shown
in Tables 1 and 2 for samples 3 and 7, respectively. For all seven samples an acceptable
difference of less than 6% was obtained for both atmospheric and vacuum distillation
(Hosein, 2004). This difference can be attributed to:
 carryover of components outside the boiling range,
 loss of material of less than 2% due to wetting and vaporization, and
 impurities in the known components (98% purity).

Development of a TBP Distillation Apparatus

911

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

Table 2
Comparison of volume of components in sample 7 and volume of distillate collected

Component

SCN

Temperature
applied, F

Heptane
Octane
Nonane
Decane
Undecane
Dodecane
Tridecane
Tetradecane
Pentadecane
Hexadecane
Heptadecane
Octadecane
Nonadecne
TOTAL

C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19

210.1
259.1
304.4
346.4
385.5
295
325
354
383
297
322
343
365

Vacuum
pressure
applied,
mm Hg
0
0
0
0
0
100
100
100
100
10
10
10
10

Vol. of
comp. in
mixture, cc

Vol. of
distillate
collected, cc

30
40
30
20
20
10
10
10
10
5
5
5
5
200

30.4
40.9
28.4
19.2
19.6
10.4
10.2
9.5
9.6
4.9
5.2
5.1
4.8
198.2

% Diff.
1.33
2.25
5.33
4.00
2.00
4.00
2.00
5.00
4.00
2.00
4.00
2.00
4.00
0.90

Separation of Mixtures
Seven condensate samples were separated into SCN fractions using the new TBP apparatus and compositions obtained from C7 to C19 were compared with those derived by GC
analysis (Hosein, 2004; Hosein and McCain, 2009) as shown in Table 3 for samples PL3
and PL7. For all seven samples an acceptable difference of less than 10% was obtained
(Hosein, 2004). This difference is mainly due to carryover of components outside the
boiling range and can vary between individual TBP tests. These results indicate that
our equipment performed accurately and the data could be used for reservoir fluids
characterization studies. TBP and GC analysis conducted by Bergman (1976) indicated
differences as high as 25%, whereas similar comparison by Osjord et al. (1985) indicated
differences as high as 15%. Because GC fractions are sharply cut, Osjord et al. (1985)
attributed this difference as due to a 2030% overlap in TBP fractions outside the defined
boiling range depending on operational conditions and a 0.52% loss of material, which
is common during TBP distillation.
The difference between the total volumes measured before and after distillation (0.5
1.5%) was within the range of 0.52.0% as published by Osjord et al. (1985). This latter
is expected due to some losses by evaporation and wetting of the vessels. These results
indicate that the equipment is quite adequate for separating mixtures and reproducing
results within acceptable experimental errors.
Apart from the limited data published by Bergman (1976) and Osjord et al. (1985), no
other data were found in the open literature for further comparison. The 12 TBP studies
conducted by Bergman (1976) were limited to distillation at atmospheric conditions, and
fractions up to a maximum of C14 were obtained. The study conducted by Osjord et al.
(1985) included vacuum distillation, and fractions up to C19 were obtained. However,
their study was limited to one data set. As such, this work has covered new grounds

912

R. Hosein and R. A. Dawe

Table 3
Volume of SCN fraction from GC and TBP analysis of condensate samples

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

Sample PL3
SCN Fraction

GC

TBP

C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20C
TOTAL

22.0
33.0
20.4
17.8
13.6
10.1
11.8
10.5
9.6
7.6
6.8
5.8
4.8
26.3
200.0

23.1
32.3
20.5
16.1
13.0
10.3
11.0
10.1
10.5
7.0
7.0
5.4
5.1
25.3
196.6

Sample PL7
% Diff.
5.1
2.2
0.4
9.6
3.9
2.1
7.0
4.2
9.5
8.8
3.6
6.9
8.2
3.9
1.7

GC

TBP

38.4
31.5
32.6
24.0
16.3
12.3
11.7
9.6
6.7
4.7
3.5
3.0
1.9
3.8
200.0

40.1
29.1
29.5
23.5
17.8
12.4
12.2
8.8
6.8
5.1
3.6
2.7
2.0
3.7
197.3

% Diff.
4.3
7.8
9.6
1.7
9.4
1.1
3.9
8.4
2.3
9.5
2.6
9.8
3.4
2.2
1.3

in demonstrating the accuracy to be derived from TBP studies with reservoir fluids and
providing a larger data set for future comparison studies.

Conclusions
 The new TBP distillation apparatus can accurately perform reservoir fluid characterization studies up to C20C.
 The cooling system was adequate for condensing essentially all vapors.
 The equipment was properly calibrated to ensure optimum separation, and by following the experimental guidelines outlined, the equipment is capable of separating
components from a known mixture with a reproducibility of less than 6%, which is
superior to that found in the literature.
 The fractionating column was carefully designed to ensure that there was a uniform
temperature gradient throughout its length and separation of the more volatiles from
the less volatile components.
 A loss of volume in the range of 0.52.0% is to be expected due to wetting and
vaporization.
 No such tests were found in the literature with a commercial apparatus for any
meaningful comparison.

Acknowledgments
The authors thank the Campus Research and Publication Fund Committee of the University of the West Indies for providing financial support for this research project.

Development of a TBP Distillation Apparatus

913

Downloaded by [Montana State University Bozeman] at 14:10 17 August 2014

References
ASTM International. (1984). D2892-84. Standard test method for distillation of crude petroleum.
In Annual Book of ASTM Standards, Vol. 05.03, Philadelphia, PA: ASTM, pp. 826860.
Bergman, D. F. (1976). Predicting the phase behaviour of natural gas in pipelines. Ph.D. Dissertation, Ann Arbor, MI: University of Michigan.
Hosein, R. (2004). Phase behaviour of Trinidad gas condensates. Ph.D. Thesis, The University of
The West Indies, St. Augustine, Trinidad.
Hosein, R., and Dawe, R. A. 2011. TBP and chromatographic data for gas condensate characterisation. J. Pet. Sci. Eng. 75:283288.
Hosein, R., and McCain, W., Jr. (2009). Extended analysis for gas condensate systems. SPE
Reservoir Evaluation Engineering 12:159166.
Katz, D. L., and Firoozabadi, A. (1978). Predicting phase behaviour of condensate/crude oil systems
using methane interaction coefficients. J. Petrol. Tech. 30:16491655.
Ministry. (2008). Trinidad and Tobago Gas Reserves Audit Report. Trinidad and Tobago: Ministry
of Energy Library.
Osjord, E. H., Ronningsen, H. P., and Tau, L. (1985). Distribution of weight, density and molecular
weight in crude oil derived from computerised capillary GC analysis. J. High Resolut. Chrom.
8:683690.
Whitson, C. H. (1984). Effect of C7+ properties on equation-of-state predictions. SPE J. 24:685
696.

Appendix
Obtaining SCN Boiling Point
The weight average boiling points for the SCN fractions were determined as outlined by
Bergman (1976). The first task was to have a chromatographic chart of the sample. The
second was to plot the boiling points of the n-paraffins present and read the temperature
corresponding to the midpoint (i.e., 50% of the total counts for the entire group) from
the plot obtained (Hosein, 2004). The average boiling points of the SCN fractions for
the local samples were found to be similar to those obtained by Katz and Firoozabadi
(1978; Hosein and Dawe, 2011).
Obtaining SCN Composition
Chromatographic analysis shows that the normal paraffin peaks are considerably higher
than the isomers of comparable volatility. Due to this feature, the normal paraffin peaks
serve as convenient markers for obtaining the area count of each SCN fraction from
chromatograms. For example, the area count for the C8 fraction was obtained by summing
the areas under the peaks from the end of the C7 peak to the end of the C8 peak (i.e.,
where the ends of these two peaks are nearest to the baseline). The mole percentage (or
wt%) was obtained by multiplying area count by response factor for this peak (Hosein,
2004).