SPE 54006

Determination and Prediction of Wax Deposition from Kuwaiti Crude Oils

Adel M. Elsharkawy, SPE, Taher A. Al-Sahhaf, Mohamed A. Fahim, and Wafaa Al-Zabbai,
Kuwait University, P.O. Box 5969, Safat 13060, Kuwait

Introduction
Copyright 1999, Society of Petroleum Engineers, Inc.
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Abstract
Crude oils produced from the formations are transported and
processed at low temperatures where solid wax particles may
precipitate. These solid particles cause additional pressure
drop in production tubing, pipeline, and processing
equipment and eventually cause plugging. Great saving in
the cost of operating such equipment can be achieved from
accurate prediction of wax appearance temperature (WAT)
and the amount of wax formed at given conditions.
This paper reports measurements of wax content by acetone
precipitation techniques as well as measurements of wax
appearance temperature (WAT) by viscosity measurements
and differential scanning calorimetry (DSC) of eight
different stock-tank Kuwaiti crudes. Viscosity measurements
indicate that crude oils exhibit Newtonian behavior at
temperature above WAT and Non-Newtonian elsewhere.
Comparison of WAT measured by DSC and viscosity
indicates that the viscosity method overestimates the WAT.
Crude oil gravity measured, by digital density meter, and
molecular weight, by vapor pressure osmometer, were used
to characterize the plus fraction and predict WAT and
amount of wax formed at given condition by the
thermodynamic model. Comparison between predicted and
measured results shows that measured Wax appearance
temperature (WAT) by DSC compare very well with that
predicted from the model for most crudes. However, Wax
contents measured by modified UOP method 46-64 are not
in good agreement with that predicted by the thermodynamic
model.

Crude oils contain mixture of light and heavy hydrocarbons

that can be classified as paraffins, naphthenes and aromatics
as heavy as C60 or C70 in addition to polar and asphaltenes1-3.
The lighter parts of the crude oils keep the heavier parts,
wax and asphaltene, in solution. This solubility depends on
pressure, temperature and composition of crude oils. The
presence of light ends increase solubility of wax in crude oil.
Asphaltene acts as inhibitor for wax formation3. When the
temperature of crude oil drops as it occurs in production
tubing of oil wells and pipe lines, the solubility of the heavy
fractions may be sufficiently reduced to cause precipitation
of solid particles of wax and asphaltenes. Two types of wax
are commonly encountered in crude oils. The first is the
macrocrystalline wax composed of mainly straight-chain
paraffins (n-alkanes) with varying chain length (about C20 to
C50). The second is the microcrystalline or amorphous waxes
containing high portion of isoparafins (cycloalkanes) and
naphthenes with a molecular weight ranges from C30 to C60.
The presence of these solid particles causes a change of the
flow behavior of crude oil from Newtonian to nonNewtonian3,4 . Thus resulting in a marked increase in crude
oil viscosity and hence additional pressure drop which
increases consumption of pumping and decreases pipeline
and tubing efficiency because of potential plugging5-11.
Great saving in the cost of operating processing equipment,
pipeline and production tubing can be achieved from
accurate prediction of wax appearance temperature (WAT)
and the amount of wax formed at given conditions. Several
methods have been presented to the industry for coping with
wax related problems12-14. These methods fall in three
different categories; thermal, mechanical, and chemical. All
these methods have their disadvantages that they increase
operating expenses. Therefore, it is essential to be able to
predict amount and conditions of wax precipitation in order
to reduce operating expenses.
Several models have been presented in the literature for the
prediction of WAT and amount of wax formed at different
temperatures7,11,15-26. These models generally overestimate
the WAT11 and amount of wax formed below the cloud-point
Won16,17 used regular solution theory to
temperature22.
describe the non-idealities in oil and wax phases. Hansen et
al.15 applied polymer solution theory of Flory27 for the
description of oil phase while the wax phase was assumed to
be an ideal. The cloud points obtained using the model of
Won were somewhat higher than those

ADEL M. ELSHARKAWY, TAHER AL-SAHHAF, MOHAMED A. FAHIM AND WAFAA AL-ZABBAI

measured. Countinho et al. 24,25 proposed a model in which

the solid state is described by local composition. Ungerer et
al.26 hypothesis that each component of the heavy fraction of
crude oil can crystallize pure wax leading to several solid
wax phases.
Finally Pedersen18,28 has presented a
thermodynamic model based on equation of state to predict
the wax formation at different conditions. Results reported
by Pedersen28 shows that the model successfully matches the
experimental data for wax deposition for the North Sea
crudes. Hamouda et al.2 reported that wax deposited in
pipeline at higher temperature than those measured in
laboratory where pipeline wall roughness and/or the
presence of nucleation sites, such as solid, corrosion
products etc., plays great role for depositing wax from
undersaturated fluids. Models accounting for molecular
diffusion and shear dispersion were also presented to predict
wax formation under dynamic conditions 2,5,29.
Determination of quantity of wax precipitated at different
temperature depends on the definition of wax and method of
measurement30-33. Differential scanning calorimetry (DSC),
polarized microscopy, low-resolution pulsed nuclear
magnetic resonance (NMR), and viscosity measurements
have been used to determine wax appearance temperature for
north sea crude oils. DSC and NMR have been used to
determine the amount of wax precipitation from crude oil at
different temperatures. Acetone precipitation technique has
also been used to determine total amount of wax29.
This paper is aimed at Characterizing the Kuwaiti crudes,
measuring the temperature at which solid wax phase starts to
crystallize (WAT) and total wax content, and using the
measured data to predict amount of wax precipitated at
various pressures and temperatures.

A modification of the thermodynamic model of Pedersen28

has been used to predict the wax appearance temperature and
the amount of wax formed at a given temperature.
At thermodynamic equilibrium between a liquid (oil) and a
solid (wax) phase, the fugacity, fiL, of component i in the
liquid phase equals the fugacity, fiS, of component i in the
solid phase:
fiL =

fiS

xiL iLp

(3)

Where xiS is the solid phase mole fraction of component i

and fioS the standard state fugacity of component i. The solid
standard state fugacity is related to the liquid standard state
fugacity as follows:

f oS
ln i oL
fi

G i f = RT

(4)

where Gif is the molar change in Gibbs free energy

associated with the transition of pure component i from
liquid to solid forms at the temperature and pressure of the
system, R is the gas constant and T is the temperature. To
calculate Gif the following general thermodynamic relation
is used:
G =

H-TS

(5)

where H stands for change in enthalpy and S for change

in entropy. Neglecting any differences between the liquid
and solid phase heat capacities, Gif may be expressed using
Eq. 5 as follows:
Gif

Hif - TSif

(6)

where Hif is the enthalpy and Sif the entropy of fusion of

component i at the normal melting point. Again neglecting
any differences between the liquid and solid state heat
capacities, the entropy of fusion may be expressed in terms
of the enthalpy of fusion as follows:

H i f

(7)

Ti f

where Tif is the melting temperature of component i. By

combining Eqs. 4, 6 and 7 the following expression may be
derived for the solid standard state fugacity of component i:

fi

oS

= fi

oL

H i f
exp
RT

T
1 f
T
i

(8)

(1)

When a cubic equation of state is used for the liquid phase it

is practical to express the liquid phase fugacities in terms of
fugacity coefficients:
fiL =

f i S = x iS f i oS

S i f =

Thermodynamic model

SPE 54006

(2)

In this expression xiL is the liquid phase mole fraction of

component i, iL the liquid phase fugacity coefficient of
component i and p is the pressure. For an ideal solid phase
mixture, the solid phase fugacity of component i can be
expressed as follows:

The liquid standard state fugacity of component i may be

expressed as follows:

f ooL = ioL p

(9)

where ioL is the liquid phase fugacity coefficient of pure i at

the system temperature and pressure. Inserting Eq. (8) into
Eq. (9) gives:

- H if
f i oS = ioL p exp
RT

T
1 f
Ti

(10)

By combining eqs. (3) and (10) the following expression is

SPE 54006

DETERMINATION AND PREDICTION OF WAX DEPOSITION FROM KUWAIT CRUDE OILS

derived for the solid phase fugacity of component i:

- H if
f i S = xis ioL p exp
RT

T
1 f
Ti

z =z
s
i

(11)

ioL may be found using equation of state on pure component

i at the temperature and pressure of the system. If the
equation of state is the same as that used to describe the
liquid-vapor equilibrium this ensures a consistent
representation of the liquid phase with respect to the types of
phase equilibria (vapor-liquid and liquid-solid).
what
remains is to decide what components are to be considered
to be potentially wax forming and how to estimate hfi and
Tfi and Vsi of these components.
To be able to account for the possible formation of wax
phase, it is necessary to have a procedure for estimating the
melting temperature, enthalpy of diffusion, and the molar
volume. For the defined fractions these properties are well
documented in the literature. However, for the plus fraction
(C7+), correlation has been used.
Enthalpy of fusion, hfi in cal/mol of component i, and
melting temperature Tfi in Kelvin are calculated using the
following expressions16:

hi f = 0.1426Ti f ( MWi )

(12)

Where MWi is the molecular weight. The melting

temperature Tfi can be predicted by the following equation:

Ti f = 374.5 + 0.02617 MW 20172 / MWi

(13)

Liquid and solid molar volume, Vi (cm3/mol), of componenti are calculated from the following experssion28;
Vi L = MW i /( 0 .8155 + 0 .6272 x10 4 MW i 13 .06 / MW i ) (14)

The wax forming components of the plus fraction seem to be

mainly n-paraffins19. Based on this fact the solubility
parameters can be expressed as a function of molecular
weight of normal paraffins as follows:

il = 6.993 + 0.781 0.049 2 10.235 / (15)

Where

= ln(MWi )

To split the C7+ fraction into several pseudo-components

forming the wax, a procedure is required. In this study,
Pedersen et.al34 procedure is used. The plus fraction is
divided into several pseudo-components with carbon number
fraction up to C80. The mole fraction zis of potentially wax
forming part of pseudo-component is calculated from the
following experssion28.

total
i

i ip

1 ( A + B.MWi )
p

(16)

Where MWi is the molecular weight in g/mol and i the

density in g/cm3 at standard condition of components i, and
A, B and C are constants (0.8824, 5.353 x 10-4, and 0.1144
respectively).

ip is the density at standard condition of a

normal paraffins with the same molecular weight as pseudocomponent i, calculated from the following expression28:

ip = 0.3915 + 0.0675 ln MWi

(17)

Experimental
The wax appearance temperature (WAT) and the amount of
wax formed at a given temperature have been measured for
eight stock-tank crude oils from major producing oil fields in
Kuwait. The compositional analyses of these samples are
given in Table 1. These wax measurements were carried out
by the viscosity method and differential scanning calorimetry
(DSC). Details of these measurements are discussed below.

Viscosity measurements
The capillary viscometer was calibrated using standard
calibration fluid. The maximum error in viscosity
measurements was calculated as 0.13% for a very viscous
fluid having a viscosity of 1200 cp as shown in Table 2.
Before any viscosity measurements were carried out, the
stock-tank oil sample was first heated to 80 C to insure that
all wax particles are dissolved. The sample was later
charged to an appropriate capillary viscometer and cooled to
the desired temperature. The time required to flow a
standard volume through a selected capillary tube of given
size was calculated and the oil viscosity is determined. At
each temperature, an average of three runs was recorded and
the test is repeated at 10 C intervals from 80 to 10 C. The
repeatability of viscosity measurements was calculated to be
about 1%.

Differential scanning
measurements

calorimetry

(DSC)

Wax appearance temperature (WAT) during cooling and

wax dissolution temperature (WDT) during heating was
performed using scanning calorimeter (Mettler Toledo TA
4000 system). DSC was chosen for measuring the amount
of wax because it is superior to Nuclear Magnetic
Resonnance (NMR). NMR is not very sensitive for low
amount of wax , i.e. less than 5%. While, DSC is faster and
more accurate for low amount of wax11. The differential
scanning calorimeter was calibrated using Indium and
normal paraffins. These materials were chosen because they
have known melting temperatures and enthalpies of fusion,
see Table 3. Published data for the melting temperature and
melting enthalpy for Indium was used to

ADEL M. ELSHARKAWY, TAHER AL-SAHHAF, MOHAMED A. FAHIM AND WAFAA AL-ZABBAI

6- The sample was placed into a deep freeze at 20oC to

30o oC and allowed to come to temperature for about 2
hours.
7- The following items were pre-cooled to 20oC: Buchner
porcelain filtering funnel, Whatman No. 934 glass fiber
filters, vacuum flask, and a mixture of three parts
acetone plus one part ether.
8- Before filtering the cold sample/solvent mixture, the
filter was seated in the filter funnel by wetting the filter
with the cold solvent mixture and evacuating the
assembled apparatus. The sample was filtered by
pouring it slowly into the funnel, using the stirring rod
as a guide. The stirring rod, bottle, and filter cake were
washed well with the cold solvent mixture. The vacuum
was disconnect, the filter was removed with a forceps,
and place it in the original tarred bottle. The wax
crystals on the filter funnel and the stirring rod were
washed into the bottle with toluene.
9- The toluene was evaporated to dryness, then the bottle
was re-weighed. The difference between the tare and
the final bottle weight, less the weight of the filter used,
is the weight of the wax crystals contained in the
original 5-g sample.

program the DSC to draw the baseline. Difference in melting

temperature (mp) and enthalpies of fusion (H) for normal
alkanes between literature data and measured ones were in
the order of 0.33 to -4.16 C and -15.88 to 2.4 J/gm,
respectively. Based on these results, a correction factor of -2
C was used to correct crystallization onset temperature and
dissolution temperature measured by DSC for crude oils.
Before any measurements, crude oil sample is heated to a
temperature of 80 C for 60 minutes and shaken thoroughly
to insure that all wax crystals have been dissolved. The oil is
later transferred to a tarred sample capsule and weighed.
The filled and closed sample is heated and shaken again to
70 C. Aluminum capsule of 40 L capacity was used for
sample measurements and references. During the cooling
process, the sample was cooled at a rate of 10 C/min. from
70 C to -140 C using liquid nitrogen. At the end of each
run, the sample compartment was purged with nitrogen gas.
The crystallization onset temperature was determined as the
onset of the exothermal peak corresponding to the liquidsolid transition. Under heating condition, the sample was
heated from -140 to 80C at a rate of 10 C/min. The
dissolution temperature on heating was taken as the
temperature at which the solid-liquid exotherm reaches the
baseline.
The accuracy of DSC measurements were
calculated to be about 2C.

Results and Discussion

Characterization of the C7+ fraction

WAT from viscosity measurements

Average molecular weight of the stock-tank oil samples was

measured by vapor pressure osmometer (model Knauer
A0280).
The osmometer was calibrated using various
concentration of benzene in chloroform. A digital frequency
density-meter (model DMA 48) was used to measure the
sample density. The density of the oils were measured at
15.6 C before heating the sample to 80 C and the density
gravity and the molecular weight were measured again at
15.6C after heating the sample to 70 at C. These
measurements are reported in Table 4.

Wax content
The wax content is determined by modified UOP method
46-6429 that is based on precipitation of wax by acetone. We
modified the method to remove fine grain sands, sediments,
and asphaltene from crude oil as follows:
1- Crude oil samples were heated to 70 oC to insure
complete dissolution of all solid phases.
2- The oil was then mixed with pentane (1:40, vol/vol), left
overnight, and filter to remove asphaltene and other
sediments.
3- A representative sample, weigh a 5 gm for example, was
taken into a tarred bottle of suitable size.
4- A given volume of petroleum ether (35 cm3) was added
to the sample and stirred until the sample is thoroughly
dissolved.
5- A given volume of acetone (about 110 cm3 ) was added
and stired well.

SPE 54006

Figure (1) shows plot of viscosity versus temperature for one

of the eight crude oil samples before-mentioned. These plots
show that at high temperature viscosity is a linear function of
temperature and crude oil flow behavior is Newtonian. At
lower temperature, viscosity versus temperature plot is
deviating from linearity. This deviation is caused by
precipitation of solid particles of wax and hence a change of
flow behavior to non-Newtonian. The intersection of the
straight line portion to the curve of viscosity vs temperature
plot is used to define the WAT. The viscosity-temperature in
the Newtonian range can be considered as a simple
exponential Arrhenius equation, as reported by Pedersen4 as;
= A eEa / RT
Where is the Newtonian dynamic viscosity, Ea is viewed
as an activation energy of viscous flow, A is a constant, R is
the Universal gas constant, and T is the temperature.
Realizing the fact that oil viscosity obeys the exponential
Arrhenius equation until solid particles of wax starts to
precipitate, wax precipitation temperature can be concluded
from viscosity temperature plot Figure (1). The accuracy of
determining the WAT from viscosity-temperature plot
depends greatly on how distinctive is the intersection of the
straight lines.

SPE 54006

DETERMINATION AND PREDICTION OF WAX DEPOSITION FROM KUWAIT CRUDE OILS

DSC Measurements
WAT and WAD
Figure (2) and (3) show DSC results during cooling and
heating temperature scanning, respectively, for one of the
eight crude oil samples in the temperature range of -140 to
70 C. Figure (2) is a typical thermograms showing the
endothermal peak during heating, the exothermal peak
during cooling, the glass transition temperature, Tg, and the
processing baseline. Most DSC curves show sharp spike of
the endothermal peak and/or exothermal peak for Kuwaiti
crudes, except crude oil sample E. The exothermal peak
corresponds to the crystallization and hence precipitation of
solid particles of wax during cooling process. The
endothermal peak corresponds to dissolution or melting of
all wax crystals during heating process. DSC curve of oil E
shows the baseline intersecting the exotherm. Similar
phenomenon was reported by Hansen et al.31 for their oil 4.
Table (5) shows the wax appearance temperature (WAT),
sometimes refered to as the onset crystallization temperature,
the wax dissolution temperature (WDT), and the glass
transition temperature (Tg) for the Kuwaiti crudes that are
described in this paper. Wax appearance temperature (WAT)
is taken as the temperature at which the first crystal of wax
appears. On DSC curve it is taken as the onset temperature
of exthothermal peak. During cooling process the solvating
power of the oil matrix decreases resulting in precipitation of
solid particles of wax. The Kuwaiti crudes described in this
study have a WAT ranging from 32 C to 38 C. Further
cooling of the crude oil sample in the range of -100 C to 150 C result in crystallization of the oil matrix into solid
material like glass. This transition is marked by increase in
viscosity and decrease in heat capacity. The temperature at
which this transition occurs is defined as glass transition
temperature Tg. Crude oil considered in this study has a
glass transition temperature ranging from -106 C to -148
C. Above Tg a wax Crystal and liquid oil matrix exist.
Below, Tg only a crystalline wax phase and glassy oil matrix
exist. Our experimental results show no correlation between
Tg and WAT or between Tg and wax content. This is in
agreement with Hansen et al.31.
It is clear from Table (5) that the dissolution temperature
(WDT) is always 10 C to 29 C higher than the wax
precipitation temperature (WAT). Rnningsen et al.4
reported that WDT is 5 C to 28 C higher than WAT for
North Sea crudes. The difference between WAT and WDT
might be caused by undercooling and overheating that result
in non-equilibrium condition during fast temperature
scanning (10C/min.). To avoid this, Hansen et al.31
recommended using very low temperature scanning. In this
study, however, it was found that the low temperature
scanning reduces the DSC sensitivity. Another reason for
the difference between WAT and WDT might be the way the
processing baseline is drawn.

Wax dissolution temperature is taken as the temperature at

which all the precipitated wax has been dissolved into the oil
matrix during the heating process, as shown in Figures (3). It
is the temperature corresponding to the endothermal peak on
the DSC curve during heating temperature scanning. The
crude oils described in this study have a WDT ranging from
42 C to 67 C.

Enthalpy of precipitation and melting

Table (5) also shows measured enthalpy of precipitation and
enthalpy of dissolution for the eight crude oil samples. The
total energy released during cooling or heating process is
proportional to the area between the base line and the
exothermal peak or endothermal peak, respectively. Kuwaiti
crudes have enthalpy of precipitation ranging from 47.5 j/g
to 66.3 j/g and melting enthalpy from 60.5 j/g to 78.6 j/g.
Generally, the dissolution enthalpy is higher than the
corresponding enthalpy of
precipitation.
Differences
between enthalpy of precipitation or dissolution may reflect
the differences in oil composition (i.e. molecular weight and
molecular structure) and to their waxy content. Linear
relationship between transition enthalpies and paraffin
content has been observed31 . Our results do no show that
relationship.

Comparison of measured and predicted results

Table (6) shows comparison between WAT from viscosity
measurements, DSC measurements, and that predicted from
the thermodynamic model. The WAT from viscosity
measurements is 2 to 8 C higher than that WAT from DSC
measurements for all Kuwaiti crudes, except crude oil C.
Other investigators found similar differences between WAT
from viscosity and DSC. Measured WAT by DSC
compares with those predicted by the thermodynamic
models. Maximum difference between predicted and
measured WAT by DSC was in the order of 7 C. Figure (4)
shows comparison between measured and predicted WAT
and wax content for one of the eight crude oils considered in
this paper. Wax appearance temperature (WAT) compare
very well with that predicted from the model for most
crudes. However, Wax contents measured by modified UOP
method 46-64 and that predicted by the thermodynamic
model are not in good agreement. This might be due to
entrapment of liquid in solid residue.
Some investigators have found correlation between WAT,
pour point and wax content. WAT increases with increasing
the wax content. However, results reported by Rnningsen
et al. 4 showed no correlation between minimum pour point
and wt.% wax at minimum pour point. Our results show no
correlation between WAT and wax content.

Conclusions
In this study, eight stock-tank crude oil samples from major
producing oil fields in Kuwait have been characterized. The
characterization includes measurements of crude oil

ADEL M. ELSHARKAWY, TAHER AL-SAHHAF, MOHAMED A. FAHIM AND WAFAA AL-ZABBAI

viscosity to estimate wax appearance temperature. It also

comprises DSC measurements of wax appearance
temperature (WAT), wax dissolution temperature (WDT),
enthalpy of precipitation and dissolution, glass transition
temperature and total wax content.
Our measurements indicate that the wax dissolution
temperature is somewhat higher than the wax appearance
temperature for all of the crudes. No correlation was found
between glass transition temperature and total wax content
of the crude. However, enthalpy of precipitation of wax
during cooling is always lower than the corresponding
dissolution enthalpy during heating process. Comparison of
wax appearance temperature from viscosity measurements
and DSC indicates that the former is always higher. Thus, it
is more appropriate to use WAT from viscosity
measurements for designing of pipe lines and production
equipment.
Wax appearance temperature and amount of wax as a
function of temperature predicted from the thermodynamic
model compares well with our measurements for most
crudes.

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SPE 54006

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SPE 54006

DETERMINATION AND PREDICTION OF WAX DEPOSITION FROM KUWAIT CRUDE OILS

20- Niper, T. C., Thermodynamic modeling for organic solid

precipitation, Paper SPE 24851, presented at the 67th Ann.
Tech. Conf. & Exhibit. of the Soc. Pet. Eng., Washington,
DC, October 4-7, 1992.
21- Chung, T-H., Thermodynamic modeling for organic
solid precipitation. Paper SPE 24851 presented at the 67th
Ann. Tech. Conf. Exhibt., Washington D. C., Oct. 4-7, 1992.
22- Lira-Galeana, C, and Firoozabadi, A., Thermodynamics
of wax precipitation in petroleum mixtures. AIChE Journal,
Vol. 42, No. 1, 1996, 329-248.
23-Majeed, A., Bringedal, B., Overa, S. Model Calculates
wax deposition for N. Sea Oils. Oil & Gas J., 1990, (6)18,
63-69.
24- countinho, J.A.P., Andersen, S. I., and Stenby, E. H.,
Evaluation of activity coefficient models in prediction of
alkane solid-loquid equlilibria, Fluid phase Equilibria, (103),
1995, 23-39.
25- countinho, J.A.P., Knudsen, K., and Andersen, S. I., A
local compostion model for paraffinic solid solution,
Chemical engineering Science, vol. 51, No. 12, 1996, 32733282.
26- Ungerer, P., Faissat, Leibovic, C., Zhou, H., Behar, E.,
and Moracchini, G., high pressure-high temperature
reservoir fluids: investigation of synthetic condensate gases
containing a solid hydrocarbon, . Fluid phase Equilibria,
(111), 1995, 287-311.
27- Flory, P. J., Principle of polymer chemistery, Cornell

Univ. Press, Ithaca, NY, 1953.

28 -Pedersen, K. S. Prediction of cluid point temeprature
and amount of wax precipitation. SPE Prod. & facilities,
Feb. 1995, 46-49.
29 -Burger, E. D., Perkins, T. K., Straggler, j. H., Studies of
wax deposition in the Trans Alaska pipeline, JPT, 1981, (6),
1075-1086.
30- Claudy, p., Letoffe, J. M., Chague, B., Orrier, J., Crude
oils and their distillates: characterization by differential
scanning calorimetry, Fuel, (67), 1, 1988, 58-61.
31-Hansen, A. B., Larsen, E., Pedersen, W. B., Nielsen A.
B., Rnningsen, H. P., Wax precipitation from North Sea
crude oils. 3. precipitation and dissolution of wax studied by
differential scanning calorimetry. Energy & fuel, 1991,(5),
914-923.
32- Letoffe, J. M, Claudy, P. , Kok, M. V., Garcin, M.,
Volle, J. L., Crude oils: characterization of waxes
precipitated on cooling by d.s.c. and thermomicroscopy,
Fuel, Vol. 74, No. 6, 1995, 810-817.
33- Pedersen, W. B., Hansen, A. B., Larsen E., Nielsen, A.,
Rnningsen, H. P., Wax precipitation from North Sea crude
oils. 2. solid-phase content as function of temperature
determined by pulsed NMR. Energy & fuel, 1991, (5), 908913.
34- Pedersen, K.S., Thomssen, P., and Fredenslund, Aa.:
Characterization of gas condensate mixtures, Advances in
thermodynamics, 1989, 1, 137-52.

8
54006

ADEL M. ELSHARKAWY, TAHER AL-SHAHAF, MOHAMED A. FAHIM AND WAFAA AL-ZABBAI

SPE

Table 1- compositional data for Middle East Crudes

Oil

N2
CO2
H 2S
C1
C2
C3
i-C4
n-C4
i-C5
n-C5
C6
C7

0.00
0.03
0.13
0.02
0.34
1.62
0.81
3.28
2.19
4.10
7.19
80.29

0.00
0.05
0.19
0.02
0.51
2.32
1.06
4.09
2.35
4.46
7.37
77.58

0.00
0.10
0.06
0.00
0.73
2.72
0.72
3.59
1.85
3.36
5.92
80.96

0.00
0.01
0.00
0.00
0.38
3.11
0.81
4.71
1.47
3.87
7.90
77.74

0.00
0.06
0.00
1.40
0.28
0.64
0.37
2.33
2.09
3.69
7.02
82.12

0.00
0.02
0.00
0.02
0.46
1.52
0.61
2.43
2.09
3.67
8.03
81.15

0.00
0.04
0.00
0.00
0.81
2.17
0.74
2.32
1.58
2.95
8.24
81.15

Table (2) Calibration data for capillary viscometer

Fluid #
1
2
3
4
5
6
7

Reported
viscosity, cp
1200
992
475
95.9
48
9.8
4.5

Following
time, sec
632.43
361.68
344.12
373.43
472.10
593.62
524.93

Tube
No.
600
450
400
300
200
100
75

Tube
constant
19
2.745
1.381
0.2575
0.1017
0.01651
0.00857

Measured
Viscosity, cp
12016
992.8
475.2
96.2
48.01
9.80
4.50

Eror
%
0.13
0.08
0.04
0.31
0.02
0.01
0.00

Table 3- DSC measurements on normal paraffins and Indium

standard
sample

published data

DSC measurements

n-C6

melting
Temp., C
-95.32a

melting
enthalpy, J/g
151.78 c

gradient,
C/min
-10

Range
, C
30-120

onset,
C
-99

H,
J/g
160.4

3.68

n-C7
n-C8
n-C16
n-C24
Indium
Indium

-90.85a
-56.77 a
18.158 b
50.6
156.6
156.6

140.21 c
181.65 d
235.6

-10
-10
-10
-10
+10
+10

30-120
30-100
30-30
30-120
30-180
30-180

-89
-57
14
53.2
157.8
157.9

156.1
194.8
238.5
263.3
27.1
27.4

-1.58
0.33
-4.158
-2.6
1.2
1.3

28.5
28.5

T, C

(H),
J/g
-8.62
-15.88
-13.23
-2.9
1.4
1.1

Daubert, T.E., Danner, R.P., Technical data-book-petroleum refinning, 4th edition, American petroleum institute, Washington, D. C. (Extant 1987).
Finke, h. L., Gross, M. E., waddington, G., Huffman, h. M., Low temperature thermal data for the nine normal parrafin hydrocarbons from octan to
hexadecane, J. Amer. Chem. Soc., 76, 333 (1954).
c
Thermodynamic Research center, Selected values of properties of hydrocarbon and retaled compounds American Petroleum Institute research project
44, texas A&M University, College Station, Tx, loose-leaf data sheeet, (extant) 1980).
d
Stull, D. R., Westrum, E. F., jr., sinke, G. C., the chemical thermodynamics of organic compounds john willey and Sons, NY (1969).
b

SPE 54006

DETERMINATION AND PREDICTION OF WAX DEPOSITION FROM KUWAIT CRUDE OILS

Table 4- Characterization of Kuwaiti crudes

Oil

A
B
C
D
E
F
G
H

before
heating
density @
15.6 C
0.8370
0.8860
0.8617
0.8724
0.9660
0.9070
0.8559
0.8791

after heating
density @
15.6 C
0.8859
0.8964
0.8810
0.8752
0.9495
0.9084
0.8851
0.9026

Wax %

molecular
weight
279
301
288
238
419
324
297
320

5.54
9.67
6.50
3.63
14.69
5.02
6.41
7.10

Table 5- DSC measurements on Kuwaiti crudes

oil

WAT

A
B
C
D
E
F
G
H

C
36
38
33
38
36
37
32
33

enthalpy of
precipitation
mj
j/g
1219 66.3
885
61.0
647
58.3
1165 66.2
1285 60.3
978
47.5
850
59.4
802
51.1

WDT
C
51
67
60
53
50
56
42
45

enthalpy of
dissolution
mj
j/g
1419
77.1
1140
78.6
784
70.7
1276
72.5
1413
66.3
1246
60.5
928
64.9
976
62.2

glass trans
temperature
. C
-148
-132
-127
-138
-111
-106
-145
-133

Table 6- Measurements and prediction of wax appearance temperature (WAT),

Dissolution temperature (WDT) and wax content

Oil
A
B
C
D
E
F
G
H

Viscosity
method
WAT
C
36
33
37
43
38
45
36
39

DSC method
WAT
C
36
38
34
38
36
37
32
33

WDT
C
51
67
60
53
50
56
42
45

predicted
WAT
C
37.3
38.8
39.8
31.0
39.4
39.5
40.2
40.0

Wax
%
5.68
5.06
6.41
5.35
1.65
4.17
6.16
4.63

UOP 46-64
modified
wax
%
5.54
9.67
6.50
3.63
14.69
5.02
6.41
7.10