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A Method of Testing the Pour Point of

Petroleum Products on a Refrigerated
Sloping Surface
V. F. Nikolaev

a b

, A. V. Egorov , I. V. Nikolaev & R. B. Sultanova

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan

Scientific Center of Russian Academy of Sciences, Kazan, Russia
b

Department of Technology of Basic Organic and Petrochemical

Synthesis, Kazan National Research Technological University, Kazan,
Russia
c

Champion Technologies, Russia and Caspian B.V. Moscow Branch,

Kazan, Russia
Version of record first published: 11 Jan 2013.

To cite this article: V. F. Nikolaev , A. V. Egorov , I. V. Nikolaev & R. B. Sultanova (2013): A Method
of Testing the Pour Point of Petroleum Products on a Refrigerated Sloping Surface, Petroleum Science
and Technology, 31:3, 276-283
To link to this article: http://dx.doi.org/10.1080/10916466.2010.547900

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Petroleum Science and Technology, 31:276283, 2013

Copyright Taylor & Francis Group, LLC
ISSN: 1091-6466 print/1532-2459 online
DOI: 10.1080/10916466.2010.547900

A Method of Testing the Pour Point of Petroleum

Products on a Refrigerated Sloping Surface
V. F. Nikolaev,1;2 A. V. Egorov,2 I. V. Nikolaev,3 and R. B. Sultanova2
1

A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center of

Russian Academy of Sciences, Kazan, Russia
2
Department of Technology of Basic Organic and Petrochemical Synthesis, Kazan National
Research Technological University, Kazan, Russia
3
Champion Technologies, Russia and Caspian B.V. Moscow Branch, Kazan, Russia

The method of testing pour points of pure substances and multicomponent hydrocarbon mixtures
basing on the analyses of the path lengths of passing of equal volumes of substances along the
tracking grooves on the refrigerated sloping metallic panel has been presented. Repeatability of the
method makes up 0:3C, which surpasses the repeatability of testing pour points by the known
international standards (ASTM D5853-95, ASTM D97-09, ISO 3016, GOST 20287-91) 57 times.
Operability of the method has been shown on the example of testing pour points of hexadecane,
octadecane, and paraffinic oil. It has been established that experimental curve plotted in coordinates
(length of sample passing path temperature), can be presented by the sum of two terms, the first of
which is described by hyperbola with asymptote at temperature, equal to the pour point of the sample,
which actually corresponds to the flow regime, and the second term is described by the parabola of
variable exponent and the contribution to drop rolling regime. Drop rolling has a greater contribution
into the experimental curve with the increase of the panel slope angle, and with the greater difference
between the temperature of the panel and the pour point of the sample.
Keywords: melting point, multicomponent mixture, oil, petroleum product, physicochemical property,
pour point, pure hydrocarbon

1. INTRODUCTION
Pour point is an important characteristic of pure substances. This physical characteristic (along with
viscosity) of a substance for multicomponent hydrocarbon mixtures, specifically oils, is the most
important indicator that defines expenditures of oil recovery enterprises connected with pipeline
transportation (Azevedo and Teixeira, 2003; Merino-Garcia and Correra, 2008; Deshmukh and
Bharambe, 2009). The higher is the pour point of oils, the greater is the expenditure for transport
and the more urgent is the necessity of using pour point depressants (Lakshmi et al., 1997). There
are known standard methods for estimating pour points of petroleum products (American Society
for Testing and Materials [ASTM] D5853-95 [American Society for Testing and Materials, 2009];
Address correspondence to Vyacheslav F. Nikolaev, Arbuzov Institute of Organic and Physical Chemistry of the Kazan
Scientific Center of Russian Academy of Sciences, 420088 Russia, Tatarstan, Kazan, ul. Akad. Arbuzova, 8. IOPC. E-mail:
nikolaev@iopc.ru

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TESTING POUR POINT OF PETROLEUM PRODUCTS

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ASTM D97-09 [American Society for Testing and Materials, 2009]; International Organization for
Standardization [ISO] 3016 [International Organization for Standardization] 1994; GOST 2028791 [Russian State Standard, 1992]). The essence of these methods consists in preheating of the
sample of the tested product with its subsequent refrigeration in specified rate up to the temperature
at which the sample sloped by 45 remains motionless for 1 min. The indicated temperature is
taken as the pour point. Repeatability and reproducibility of the listed above standard methods
are equal to 2 and 8 C, accordingly. The proposed method allows the improvement the analogous
parameters of estimating accuracy of tPPT more than 57 times.

2. EXPERIMENTAL
2.1. Description of the Device and Measuring Procedure
In the given work a method has been proposed for determining the pour points of pure substances,
multicomponent hydrocarbon mixtures, including oils and petroleum products, and other viscose
process liquids by analyzing the lengths of passing trajectories of the equal volumes of samples
along the tracking grooves of metallic panel, refrigerated in specified rate (0.05 /min). For the
first time the device was described in Nikolaev et al. (2006), and its modification in Nikolaev et al.
(2011). The major part of the device is the thermostatically controlled metal panel (duralumin
D16T [Al 92.5%, Cu 4%, Mg 1.5%, Mn 0.5%, admixtures 1.5%]; Figure 1) with the regulated
slope angle with 17 tracking grooves, which serve for placing liquid samples and watching their
subsequent passing. Distance between the centers of tracking grooves in the device used in
the given work made up 9.0 mm, the width of the grooves is 8.4 mm. The device has a flap
thermostatically controlled lid 2, transparent lid 3 with the scale for measuring the lengths of
sample passing, handle 4 for discrete adjustment of angle ( D 0 ; 15; 30; : : : 75; 90) of panel
slope, bottom 5, and hose 6 for feeding cooling agent (heat carrier) from thermostat or cryostat.

FIGURE 1 Device for testing the pour point of pure hydrocarbons, oils, petroleum products, and viscose process
liquids. The used numerations in the text.

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V. F. NIKOLAEV ET AL.

The procedure of carrying out the experiment consists in performing the following operations.
Thermostatically controlled metal panel 1 is adjusted in slanting position (1575). The initial
temperature of the thermostatically controlled panel 1 and the thermostatically controlled flap lid
2 is adjusted by supplying the cooling agent (heat carrier) from cryostat having the temperature
by 15 C higher than the presumptive pour point of the tested sample. Control over the panel
temperature is maintained with the help of digital electronic thermometer (e.g., LT-300, LCC,
Termex, Tomsk, Russia, Testo-106, Testo AG, Lenzkrich, Germany), the sensor of which is placed
into one of the tracking grooves of thermostatically controlled panel 1. Cryostat is switched on
to refrigeration. While refrigerating the sloping thermostatically controlled panel 1 the batcher
placed at a right angle to the panel surface performs the consecutive dosing of the testing liquid
samples of pure substance of the equal volumes (e.g., 0.2 mL) of oil, petroleum product, or other
process liquid), preheated to 50C (by analogy with ASTM D5853-95, ASTM D97-09, ISO 3016,
or GOST 2028791) and refrigerated prior to dosing to 35C. When the dosing of the samples is
completed in the temperature range overlapping the region of prospective pour point of the sample,
the sloping thermostatically controlled panel is transferred to horizontal position; thermostatically
controlled lid 2 is diverted into lateral position; transparent lid 3 with the scale is installed on
thermostatically controlled panel 1, and the lengths of trajectories of sample passing are measured
.L/. Dozing of the first liquid sample is conducted at the higher temperature than that of the
pour point, the passing way coming out of the limits of tracking groove. When the sample on
the first groove starts showing the signs of crystallization the dozing of samples on the other
paths is renewed with the interval of 0.050.10C. Most informative are the paths the passing
lengths of which they terminate at the lower half of the refrigerated panel. If the pour point of
the tested sample is close to room temperature, there is no need for covering the panel 1 with
thermostatically controlled lid 2. It is sufficient just to cover it with transparent lid 3, serving at
the same time as heat insulation screen, as well as the ruler for measuring lengths of trajectories.
2.2. Factors Effecting the Length of Sample Passing Trajectories
In order to optimize the conditions of the experiment on testing pour points and for minimizing
the experimental errors the effects of some factors on the lengths of trajectories of hydrocarbon
passing along the tracking grooves have been studied. Among these factors the following ones
have been supposed to be the most important: volume of sample dosing (VDOS , cm3 ), temperature
of preheating temperature of samples (tPRH , C), dosing temperature (tDOS , C), temperature of
refrigerated panel (t, C), and angle of slope of the panel (, ).
As the tested substances there were used the pure hexadecane (TU 6-09-3659-74) and octadecane (TU 6-09-3005-78) with the purity specification pure, and with the content of basic
substance 98%.
Effect of the dosing volume on the length of passing was studied with the use of hydrocarbon
of hexadecane. Dosing was performed by single-channel batcher DPOP-1-100-1000 (dosing error
11.5%) manufactured by ZAO (JSC Termo Fisher Scientific, St. Petersburg, Russia). The
surface of the thermostatically controlled panel was previously cleaned with petroleum ether
(fraction 4070C) and degreased with acetone. The dosed volume of samples varied in the interval
0.10.3 mL with the step of 0.033 mL, the permanent temperature of the panel was maintained
with the help of liquid thermostat MLW UH-16 (veb MLW prufgerate-werk, Medingen Freital,
Germany) and made up 9.0 C, the sloping angle of the panel made up D 45. Simultaneously
two parallel experiments were carried out (on paths No. 18 and 1017). On the basis of their
results, the mean values of passing lengths have been calculated and diagram of dependence of
L on VDOS has been plotted (Figure 2). From Figure 2 it is seen that with the increase of dosing
volume the length of sample passing grows practically linearly. It is only natural, too, that at
V D 0, L D 0. In subsequent experiments the optimal volume of dosing was taken to be 0.2 mL.

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TESTING POUR POINT OF PETROLEUM PRODUCTS

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FIGURE 2 Dependence of the passing length of hexadecane on the sample volume (conditions: D 45 , dosing
temperature tDOS D 25 C).

Effect of sample dosing temperature before withdrawing it into the batcher has been studied
on octadecane under the following experimental conditions: temperature of the panel t D 26:2C,
volume of dosing VDOS D 0:2 mL, angle of the panel slope D 45. With the increase of
the preheating temperature of the sample there takes place the regular growth of sample passing
length, but these changes are not essential, they make up about 0.13 cm/ . Dependences of the
passing lengths on the angle of slope of the panel are given in Section 2.3.

2.3. Testing Pour Point of Hydrocarbon Samples

In the experiment there were used hexadecane and octadecane. In accordance with literary
data (Mackay et al., 2006) these hydrocarbons have the following melting points 18.12 C and
28.2 C, respectively. Thermostatically controlled panel was previously cleaned with petroleum
ether (fraction 4070C) and degreased with acetone. The experiment was carried out under
the following conditions: preheating temperature tPRH D 50 C, dosing temperature tDOS , dosing
volume VDOS D 0:2 mL, angle of panel slope varied from 15 to 75 with the step 15 , panel
temperature t was lowered from 20.0 to 12.0C with the rate of 0.05 /min. A thermostatically
controlled lid was not used and was in the reclined position, since the temperature of thermostatically controlled panel was close to the room temperature. Using the obtained data the curve of
dependence of L on t has been plotted (Figure 3).
With the panel temperature lowering below the pour point of the sample by 0.51.5, there
takes place the natural shortening of passing length (Figure 3). However, on decreasing the panel
temperature much lower than pour points of the sample by 1.5 and lower the flow regime starts
to transfer into the drop rolling regime, which leads to the smooth path length increase and the
appearance of minimum on the dependence L D f .t/. This minimum is most distinctly manifested
at large angles of panel slope . > 45 /. The region of the diagram where drop rolling takes
place turns out less informative as to the pour point, that is why in the subsequent experiments
on testing the pour point we have used the angle of panel slope D 30.

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V. F. NIKOLAEV ET AL.

FIGURE 3 Diagram of dependence of passing length of hexadecane at different angles of panel slope on the
panel temperature: preheating temperature .tPRH / D 50 C, dosing temperature .tDOS / D 35 C.

On processing the data of experimental curves L D f .t/ several variants of quantitative

estimation of pour points have been discussed. As the first method there has been used the
method of tangent crossing, plotted to two branches of the experimental curve. However, this
method is subjective, ambiguous, and leads to understated values of pour points. As an alternative
method of tangents there can be used the method of estimating pour points on temperature of
maximum curvature of the dependence L D f .t/; however, it also gives understated results.
The most accurate, as we see it, is the asymptotic method, in which experimental curve L D
f .t/ is described by the equation:
L D A=.tPPT

t/ C B
.tPPT

t/C ;

(1)

where L is length of passing (cm), A is the parameter of equation (cm
), tPPT is the asymptotic
estimation of pour points ( C or K) of the tested liquid, and t is the temperature of the panel (C or
K). The equation consists of two terms, the first term constituting the hyperbolic function, which
describes, strictly speaking, the flow, while the second one constitutes parabola of the degree C,
describing the contribution into drop rolling (C 1/. Contribution of drop rolling B
.tPPT t/C
turns to 0 at t D tPPT , which seems to be valid.
In Figure 4 decomposition of experimental curve L D f .t/ to components is shown schematically.
In Table 1 for hexadecane (Figure 3) and octadecane (Figure 5) there can be seen that asymptotic
estimation of pour points for all angles of panel slope remain constant with the accuracy up to 0.24
(hexadecane) and 0.17 (octadecane). This fact points out that the used asymptotic temperature is
the true temperature of phase transfer of the studied hydrocarbons with specification pure.
Figure 6 shows the results of testing pour points of paraffin oil (Stavropol, Russia). The tested
oil sample has the next content (wt%): asphaltenes 1.1, wax 23.9, resin 3.5, density (at 15 C)
0.8362 g/mL, pour point (ASTM 585395) 28 C. Determination of pour point temperature was

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TESTING POUR POINT OF PETROLEUM PRODUCTS

281

FIGURE 4 Decomposition of experimental curve L D f .t / for hexadecane on the contributions of flow regime
and drop rolling regime.

TABLE 1
Coefficients and Equation Statistics (1) for Hexadecane
and Octadecane
Hexadecane
Parameter
A15
tPPT15
B15
C15
R=S15
A30
tPPT30
B30
C30
R=S30
A45
tPPT45
B45
C45
R=S45
A60
tPPT60
B60
C60
R=S60
A75
tPPT75
B75
C75
R=S75
tPPT . C

Estimate

Octadecane
SE

22.51
2.26
17.82
0.08
0.91
0.67
0.88
0.38
0.9998/0.20
24.47
1.10
17.24
0.04
1.36
0.32
1.05
0.14
0.9999/0.07
30.36
4.50
17.50
0.16
0.55
0.63
1.81
0.67
0.9977/0.48
22.60
3.79
17.67
0.15
2.40
1.25
0.98
0.29
0.9983/0.33
11.29
2.25
17.31
0.10
8.24
1.67
0.55
0.12
0.9972/0.42
17.505 0.244

Estimate

SE

14.22
1.26
27.36
0.07
1.86
0.58
0.81
0.19
0.9996/0.17
19.50
3.44
27.39
0.13
3.07
1.76
0.82
0.37
0.9994/0.30
10.49
1.78
27.02
0.08
7.17
1.38
0.43
0.14
0.9996/0.20
12.22
0.80
27.07
0.04
6.18
0.68
0.92
0.10
0.9999/0.12
18.50
2.84
27.28
0.12
3.25
1.50
1.19
0.34
0.9985/0.31
27.23 0.17

Note. R=S D correlation coefficient/standard deviation; D variable;

tPRH D 50 C; tDOS D 35 C; VDOS D 0:2 mL.

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V. F. NIKOLAEV ET AL.

FIGURE 5 Dependence of the length of passing trajectory of octadecane samples (0.2 mL) along the sloped
refrigerated panel on the angle of the sloped panel and its temperature t .

spent in following experimental conditions: D 30, tPRH 50C, tDOS D 35 C, VDOS D 0:2 mL.
At statistical processing of experimental points on Eq. (1) the following coefficients have been
received: A 15.63, tPPT 28:50C, B 3.36, C 0.62, R/S 0.9984/0.16.
It is seen that the accuracy of estimation of pour points of oil with the use of Eq. (1) has the
same order as the accuracy of determining pour points of pure hydrocarbons.

FIGURE 6

Dependence of the flow path of paraffin oil sample (Stavropol, Russia) on the temperature of panel.

TESTING POUR POINT OF PETROLEUM PRODUCTS

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3. CONCLUSION
A new method has been proposed for testing pour (melting) points of pure substances and
multicomponent hydrocarbon mixtures, oils, and petroleum products, which surpasses the known
international standards in repeatability and reproducibility. The method can be used as an express
method for estimating the efficiency of pour point depressant to oils and petroleum products by
means of pour point depression, as well as in the food processing industry for testing the quality
of animal and vegetative fats.

ACKNOWLEDGMENTS
The authors express sincere gratitude to the workers of the machine shop at the A. E. Arbuzov
Institute: A. I. Kozlov and L. E. Levina, who made the pilot device and gave valuable advice that
helped to improve its construction.

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