SPE 80267

Cloud Point and Wax Deposition Measurement Techniques

Kosta J. Leontaritis*, SPE, AsphWax Inc. and John D. Leontaritis Kosta Oil Field Technologies Inc.
*Corresponding author
Copyright 2003, Society of Petroleum Engineers Inc.

This paper was prepared for presentation at the SPE International Symposium on Oilfield
Chemistry held in Houston, Texas, U.S.A., 58 February 2003.

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Abstract
Paraffin-waxes present in crude oils, at some thermodynamic
states, exhibit the phenomenon of crystallization. The onset of
wax crystallization temperature of stock tank oil at
atmospheric pressure is known as the cloud point. In this
paper, cloud point data are presented for several synthetic
mixtures and crude oils. The cloud point data have been
obtained via three different techniques: Near-Infra-Red (NIR)
light attenuation, Dynamic Filtration Cloud Point (DFCP), and
ASTM-D2500. For the transparent mixtures, the ASTM-
D2500 method is being used as the standard against which the
other two techniques are compared to. The data show that all
three techniques are consistent with each other, although their
precision is different. Because of its simplicity, higher
precision, and wide applicability to all kinds of fluids and
thermodynamic conditions, the NIR light attenuation
technique is recommended.

Furthermore, cloud point and wax deposition data from a
variation of the DFCP technique are presented from various
crude oils from around the world. Some of these oils contain
natural asphaltene dispersants and wax crystal modifiers and
as a result, although these oils contain substantial amounts of
asphaltene and wax molecules, they remain stable at most
thermodynamic conditions encountered during their
production. Two cases of these special oils are presented
here.

Introduction
Naturally occurring hydrocarbons in the earths crust contain
varying amounts of certain molecules generally called
asphaltenes and waxes. Asphaltenes exhibit a behavior at
some thermodynamic states called flocculation. That is,
asphaltene particles or micelles present in crude oils aggregate
or flocculate into larger aggregates or flocks. The locus of all
thermodynamic points in a P-T-x phase diagram at which
flocculation occurs is called the Asphaltene Deposition
Envelope (ADE). Asphaltene deposition can occur only at
thermodynamic conditions within the ADE, hence, the word
deposition in the name. Paraffin waxes present in crude oils,
on the other hand, at some thermodynamic states, exhibit the
phenomenon of crystallization. The locus of all
thermodynamic points in a P-T-x phase diagram at which wax
crystallization occurs is called the Wax Deposition Envelope
(WDE). As with asphaltenes, wax deposition can occur only at
thermodynamic conditions within the WDE, hence, the word
deposition in the name. The onset of wax crystallization
temperature of stock tank oil at atmospheric pressure is known
as the cloud point. Paraffin waxes are rather a-polar molecules
and their interactions are expected to be van der Waals or
London dispersion type, whereas asphaltene molecules are
polar in nature and, as a result, are expected to have polar,
hydrogen bond type, or associative type molecular
interactions. Asphaltene flocculation and wax crystallization
are two mechanisms via which organic deposition takes place
from crude oils. In crude oils, the probable shapes of the
thermodynamic envelopes that are manifestations of these two
mechanisms of organic deposition from the various reservoir
fluids have been defined recently.
1


Wax deposition is a serious field problem encountered during
crude oil production that causes plugging of pipelines, well
tubings, and surface and process equipment.
2-3
Wax crystals
change the flow behavior of crude oil from Newtonian to non-
Newtonian.
4-6
The wax crystals lead to higher viscosity, with
increased energy consumption for pumping and a decreased
pumping capacity. Wax deposition increases the pipeline
roughness, which results in an increase in pressure drop. The
other effect is to reduce the effective cross sectional area of
the pipe. The deposits also cause subsurface and surface
equipment plugging and malfunction, especially when oil
mixtures are transported across Arctic regions or cold
oceans.
6-7
Wax deposition leads to more frequent pigging
requirements. If the deposits get too thick, they reduce the
capacity of the pipeline and cause the pigs to get stuck. Wax
deposition in well tubings and process equipment may lead to
more frequent shutdowns and operational problems. Also,
some investigators report that wax deposition can result in
severe formation damage.
8-10
If the temperature of the fluid in
the formation falls below the cloud point, wax precipitates and
may deposit in the formation pores, partially blocking or
plugging the fluid flow channels and thus restricting the flow.

2 K. J. Leontaritis AND J. D. Leontaritis SPE 80267
The lighter components of crude oil help to keep the heavier
components in solution. These higher molecular weight solids
precipitate whenever anything occurs that decreases the
carrying capacity of the fluid solvent. Crude oil is a mixture
of a wide range of hydrocarbons. The carbon number
distribution of the paraffins varies from one crude oil to
another. The solubility of a specific n-paraffin in a crude oil is
a strong function of its carbon number and system
temperature. Temperature is a major driving force for the
paraffin solid-liquid phase equilibria and the subsequent
separation of the two phases. The two major parameters that
affect the solubility of wax in oil are the temperature and
composition of the oil.
9
Pressure has a lesser effect. The
precipitation of wax is sometimes irreversible in that the wax,
once removed from solution, is very difficult to re-dissolve,
even after original formation temperatures are restored.
8


Precipitation of wax from petroleum fluids is considered to be
a thermodynamic molecular saturation phenomenon.
1, 11
Wax
molecules are initially dissolved in a chaotic molecular state in
the fluid. At some thermodynamic state the fluid becomes
saturated with wax molecules, which then begin to precipitate.
This thermodynamic state is called the onset of wax
crystallization or solidification. It is analogous to the usual
dew point or condensation phenomenon, except that in wax
precipitation a solid is precipitating from a liquid, whereas in
condensation a liquid is precipitating from a vapor. In wax
precipitation, resin and asphaltene micelles behave like heavy
molecules. When their kinetic energy is sufficiently reduced
due to cooling, they precipitate out of solution but they are not
destroyed. If kinetic energy in the form of heat is supplied to
the system, these micelles will desegregate and go back into
stable suspension and Brownian motion.

Big savings can be obtained from the accurate advance
prediction of the onset of wax crystallization. Knowledge of
the magnitude of wax deposition can also lead to reduction of
insulation requirements for production and transportation
systems. Furthermore, wax problems can be dealt with in an
early stage of a project, so that sufficient thermal insulation is
planned for, instead of expensive chemical injection and loss
of system capacity.
12
Improved heat transfer efficiency can
result in reduced process heat loads. Capacity reduction in
heat exchangers due to blockage or vibration problems due to
high velocity or flashing can be overcome. The size of export
pumps and flowlines can be reduced from an accurate
knowledge of the effect of wax formation on crude viscosity.
The minimum pigging frequency can be determined if the
amount of wax deposition can be estimated. Also, problems
related to start-up and shutdown can be solved cost-
effectively.

Laboratory Wax Measurement Techniques
A description of the Cloud Point and Wax Deposition
Measurement techniques covered in this paper are discussed
next.

Cloud Point. Three Cloud Point Measurement techniques are
presented and compared in this paper.

ASTM-D2500
13
is being used as the standard against which
the other two techniques are compared to. The ASTM-D2500
technique is shown in Figure 1.



Figure 1: ASTM-D2500 Cloud Point Test Apparatus

The sample is cooled at a specified rate and examined
periodically. The temperature at which a cloud is first
observed at the bottom of the test jar is recorded as the cloud
point. The ASTM-D2500 test method covers only petroleum
products which are transparent in 40 mm layers of thickness,
and with a cloud point below 49 C. Hence, all ASTM-D2500
cloud points presented in this study are of petroleum products
or solvents fortified with paraffin wax.

The Dynamic Filtration Cloud Point System
14
(DFCP) is
shown in Figure 2.

Figure 2: Dynamic Filtration Cloud Point Test Apparatus

The dynamic or filtration technique takes advantage of the
following three phenomena to determine the cloud point:
All asphaltene micelles remain in stable suspension
before the onset of wax crystallization.
All paraffin-wax molecules remain in molecular state
before the onset of wax crystallization.
BPR
Temperature Control Modules
DPI
Oil
Gas
Liquid
Flash Module
Flow Control
Module
Pressure
Control
Module
0.1 u Filter
BPR
Temperature Control Modules
DPI
Oil
Gas
Liquid
Flash Module
Flow Control
Module
Pressure
Control
Module
0.1 u Filter
SPE 80267 Cloud Point and Wax Deposition Measurement Techniques 3
After the onset of wax crystallization the first 0.1-
micron or larger wax crystals are formed.
The hydrocarbon mixture to be tested for onset is at some
pressure and temperature above wax onset conditions (say
reservoir conditions) in a piston transfer cylinder. The entire
system is maintained at the desired testing temperature and
pressure. Flow is pumped (usually at around 0.2 to 0.5 cc/min)
through the 0.1-micron filter and the BPR. The BPR maintains
the required operating pressure of the flowing fluid. The water
bath is programmed to decrease the testing temperature at
some predetermined rate, say 0.2 F/min. The computer
monitors the differential pressure (P) across the filter, the
pressure at the BPR, the temperature of the oil, and other
operating parameters. The P across the filter vs. the oil
temperature is plotted as shown in Figure 3.

Dynamic or Filtration Wax Onset
Live Oil at 3000 psig
0.0000
0.2000
0.4000
0.6000
0.8000
1.0000
30.0 50.0 70.0 90.0 110.0
Temperature, F
P
r
e
s
s
u
r
e

D
r
o
p
,

p
s
i
Hagen-Poiseuille Fit Data Curve Fit Experiment
Wax Onset at 64 F


Figure 3: DFCP Example Live Oil Cloud Point Test

The temperature at which the P across the filter begins to rise
signals the onset of wax crystallization, which is 64 F. The
actual data analysis and interpretation is actually somewhat
more involved and is explained next.

The Hagen-Poiseuille equation describes incompressible fluid
flow for Newtonian fluids under laminar flow conditions.


2
4
10 * 68 . 6
d
L
P
u

= 1

Where:
P = pressure drop, psi
u = viscocity, centipoise
L = length of tubing, feet
= Q/A = fluid mean velocity, feet/second
d = internal tubing diameter
L, , d remain constant during the experiment. u, however,
varies with temperature. Beal's correlation
15
for estimating
viscosities of hydrocarbon liquids is:




|
.
|

\
|
+

|
|
.
|

\
|
+
|
|
.
|

\
|
+ =
API
Anti
T API
33 . 8
43 . 0 log
53 . 4
7
200
360 10 * 8 . 1
32 . 0 u 2

A modified functional form of Beal's correlation is used here
to represent the variation of viscosity with temperature and
pressure.


c
b
P
T
a
|
|
.
|

\
|
+
=
200
360
u 3

Where:
T = temperature, F
P = pressure, psig
a, b, c = constants

Combining equations 1 and 3 one gets:


c
b
P
T
a P
|
|
.
|

\
|
+
=
200
360
4

Equation 4 is used to fit the P vs Temperature data at the
pressure P of the experiment in the Newtonian range, i.e., at
temperatures above the onset of wax crystallization. The
remaining data, i.e., the data at temperatures below the onset
of wax crystallization, are fitted to a suitable equation that
makes the best fit to the data. The onset of wax crystallization
is the temperature at which the two curves intersect each other.
Figure 3 demonstrates the application of above procedure,
which yields the onset temperature at 64 F.

Figure 4: NIR Cloud Point Test Apparatus

The Near-Infra-Red (NIR) Light Attenuation
14
apparatus is
shown in Figure 4. The NIR wax onset method is based on the
observation that there is a sharp increase in light absorption or
attenuation in the near-infrared region at the onset of wax
crystallization. The mechanism of wax crystallization and why
NIR light spectra provide the information necessary for
determining the onset of wax crystallization has not been
completely understood yet. However, considerable knowledge
Oil
Pressure Control Module
Fiber Optics Cables
Spectrophotometer
Computer
Piston
Mixing Ring
Temperature Control Module
Mixing Ring
Sample Charge
4 K. J. Leontaritis AND J. D. Leontaritis SPE 80267
has been already accumulated regarding the relationship of
NIR and wax phenomena that is described next.

From spectroscopic theory and experiments, we know that the
absorption of light by a component in solution follows Beer's
Law:
13


I() = I
o
() exp(-E() l m) 5

Where:
= wavelength of light
I
o
() = intensity of light entering sample
I() = intensity of light leaving sample
E() = molar absorptivity at wavelength , liter/
(mole-cm)
l = light path length through sample, cm
m = molarity of absorbing species, moles/liter

The absorbance, A(), at wavelength , is given by the
following relation:

( )
( )
( )
|
|
.
|

\
|
=

I
I
A
o
10
log 6

Combining Equations 5 and 6, one gets the linear relationship:

A() = 0.4343 E() l m 7

Transmittance, T(), of NIR light through a sample of
waxy/asphaltenic oil has also been used to detect the onset of
wax crystallization. There is a sharp decrease in the
transmittance of NIR light through a sample of
waxy/asphaltenic oil (rather than increase as in the case of
absorbance) at the onset of wax crystallization. The
transmittance at wavelength is defined as follows:

T() = I()/Io() = exp(-E() l m) 8

Hence, combining equations 6 and 8 one gets:

( )
( )
|
|
.
|

\
|
=

T
A
1
log
10
9

Equation 9 shows that the absorbance and transmittance are
logarithmically related. This is illustrated numerically in the
following examples:
Absorbance = 0 Transmittance = 100 %
Absorbance = 1 Transmittance = 10 %
Absorbance = 2 Transmittance = 1 %

A typical absorption/attenuation plot when cooling a special
wax-Hexane mixture, at atmospheric pressure, is shown in
Figure 5. In this case, the cloud point is indicated at 59 F.

NIR Cloud Point Test of
Special Wax-Hexane Mixture
0
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
40 45 50 55 60 65 70 75 80 85 90
Temperature, F
A
b
s
o
r
b
a
n
c
e

U
n
i
t
s
Onset at 59 F


Figure 5: NIR Cloud Point Test Example

In Figure 5, as the fluid is cooled down, the trend of the data
curves upwards thus indicating that the absorbing/attenuating
molecules are undergoing a change that permits less of the
light to travel through the oil sample. It is not clear how much
of the light is absorbed or scattered. However, it is known that
during wax crystallization larger and new wax crystals are
formed. Hence, there is a strong possibility that light scattering
(by striking the newly formed crystals) does take place as the
wax crystallization process progresses and more and larger
particles are formed. The point at which the "absorbance-
scattering" begins to rise rather exponentially is called the
onset of wax crystallization. Based on the fact that new and
larger crystal particles are formed, light scattering is a more
pronounced physical phenomenon than light absorbance
during crystallization. Hence, the actual NIR curve, in addition
to yielding the onset, it also provides dynamic wax
crystal/particle size information. This information is useful to
models that simulate particle size distribution during wax
crystallization. Because of its simplicity, higher precision, and
wide applicability to all kinds of fluids and thermodynamic
conditions, the NIR light attenuation wax onset technique is
preferred over the other methods.

Wax Deposition. Two wax deposition measurement
techniques are discussed and compared in this paper. A
dynamic technique, that is with the oil flowing and simulating
the real system, and a static technique where the oil is static
thus maing the technique more qualitative than quantitative.

The Dynamic Wax Deposition Apparatus
14
is an adaptation
of the dynamic filtration wax onset apparatus. A schematic is
shown here in Figure 6.


SPE 80267 Cloud Point and Wax Deposition Measurement Techniques 5

Figure 6: Dynamic Wax Deposition Apparatus

Wax deposition is dependent on the thermal and mechanical
history of the oil. This is because the wax crystals once they
form need substantial heating and mixing above the cloud
point temperature to be dissolved. Wax deposition is different
when the oil is heated without dissolving all the wax crystals
than when the oil is heated in a way that dissolves all wax
crystals.

Dynamic Wax Deposition Test
50
51
52
53
54
55
40 50 60 70 80 90 100 110 120 130
Temperature, F
P
r
e
s
s
u
r
e
,

p
s
i
g
Wax Onset

Figure 7: Dynamic Wax Deposition Example

An example wax deposition test-run is shown in Figure 7.
Eventhough this apparatus does not have filter, the cloud point
is still evident at about 84 F. The primary wax deposition
data, however, are obtained in this case at about 52 F. At that
temperature, cooling is stopped and flow continues. The build-
up of P is noted in say psi/hr or day. This is related to the
wax deposition rate in the experimental system. It is
emphasized that the dynamic wax deposition system is a flow-
through system. It is not a flow-loop. Flow loops do not
simulate as closely as flow-through systems field wax
deposition conditions. The closed loop is a batch system;
hence, the nature of depositing wax changes continuously with
time. That is not the case in either real operating systems or in
flow-through lab set-ups.
Once the wax deposition psi/day rate data is obtained, it
may to be converted to an inch/day wax deposition rate for the
lab set-up by assuming that wax deposition is occurring evenly
in the entire lab pipe length. It is known that in reality this is
not the case. The wax deposit profile in the pipe is not flat.
However, this rate gives an approximate idea of what to
expect in the field. One can relate this wax deposition rate to
other similar rates from oils with known field wax deposition
behavior. Also, wax deposition simulators may use it as a
tuning target. An example data conversion is shown in Figure
8.

Figure 8: Dynamic Wax Deposition Example

The Static Wax Deposition Apparatus
14
is shown in Figure 9.
This is an adaptation of the conventional cold plate (or cold
finger) semi-quantitative wax deposition measurement
technique.



Figure 9: Static Wax Deposition Apparatus

The Static Wax Deposition Test or Cold Plate Test (CPT)
determines the amount of waxes that deposit on a metal plate
(i.e., cold plate), whose weight is known, dipped inside an oil
sample that is maintained at some temperature above its cloud
point. Cold fluid, usually but not always at 40 F, circulates
inside the cold plate. Inside the occlusions of the depositing
wax crystal structure resides a substantial amount (usually
more than 80 Vol.%) of liquid stock tank oil.

Laboratory Wax Results
Cloud point and wax deposition data from several oils are
presented next.
BPR
Temperature Control Modules
PI
Oil
Gas
Liquid
Flash Module
Use coil in vertical position
to study deposition in conduits
with vertical orientation.
Flow
Control Module
Pressure
Control Module
BPR
Temperature Control Modules
PI
Oil
Gas
Liquid
Flash Module
Use coil in vertical position
to study deposition in conduits
with vertical orientation.
Flow
Control Module
Pressure
Control Module
Directly Measured Data Wax Build-up
u

1.7 0.04805 4.833 1.856E-07 0.5 0.0010593 84.16374 4.278119 46.70897789 0.05559
15 0.04805 4.833 1.856E-07 0.5 0.0010593 84.16374 0.484854 46.70897789 0.49048
15 0.04418 4.833 1.856E-07 0.5 0.0010593 99.554383 0.527325 60.09016621 0.68627 21.68713239
Lab Data Interpretations

Lab Pipe Area, ft
2
= 0.0608
Oil Density, lb/ft
3
= 52.2787
Wax Density, g/cc= 0.8500
Wax Volume, ft
3
/day= 0.0000
Wax Volume, cc/day= 0.2663
Wax Mass, g/day= 0.2264
Wax Dep Rate, g/day/ft
2
= 3.7254
Wax Dep Rate, ft
3
/day/ft
2
= 0.0002
Field System Data Average Field Shear Rate
Per Day Per Day Per Day Per Month Total Deposit Vol %Liq = 0.35
Length, ft. = 150004.8 Wax Vol Wax Dia Wax Vol Wax Vol Per Month
OD, inch ID, inch Surf Area, ft
2
/ft ft
3
/ft Inch Bbls/ft Bbls/ft Barrels Wax Q, ft
3
/hr v, ft/hr Shear, sec
-1
8.625 6.893 1.803668333 0.00027913 6.889284846 4.971E-05 0.0014914 223.7152323 1980 62403 241.4158798
Wax Dep Rate Linearly Extrapolated Wax Deposit Thickness Field Reynold's
inch/day Deposit Inch Deposit Inch Deposit Inch Critical Deposit Thickness 51571.02789
0.003715154 90-day Rate 180-day Rate 360-day Rate (20%of ID)/2
0.33436387 0.668727748 1.3374555 0.6893
6 K. J. Leontaritis AND J. D. Leontaritis SPE 80267

Cloud Point. The repeatability, reproducibility, and accuracy
of the Dynamic Filtration Cloud Point Test data for the wax-
Hexane mixture of Figure 5, are now checked against the
ASTM-D2500 standard method. It is noted that ASTM-D2500
has a repeatability and reproducibility of about 5 F. Table-1
shows the repeatability of the DFCP method and its accuracy
as it compares to the ASTM-D2500 method.


Table 1: Dynamic Filtration Cloud Point Method

An example run, Run 1 in Table-1, is shown in Figure 10.

Special Wax-Hexane Mixture Cloud Point
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
40.0 60.0 80.0 100.0
DeltaP, psi
T
e
m
p
e
r
a
t
u
r
e
,

F
ASTM D-2500
Cloud Point = 62 F5
Cloud Point @61 F


Figure 10: Wax-Hexane Mixture DFCP Run 1

Figure 1 shows the NIR Cloud Point run for the same sample
shown in the above Figure 10. It is evident that either method
detects the wax crystals immediately after they form. The
repeatability, reproducibility, and accuracy of the NIR and
DFCP methods for the wax-Hexane mixture of Figures 5 and
10 are now checked against the ASTM-D2500 standard
method. Table-2 shows the repeatability of the NIR and DFCP
methods and their accuracy as they compare to that of the
ASTM-D2500 method.








Table 2: Near-Infra-Red and DFCP Comparison

Because of its simplicity, higher precision, and wide
applicability to all kinds of fluids and thermodynamic
conditions, the NIR light attenuation technique is
recommended and adapted in this paper. In the following six
figures NIR cloud point versus composition data are presented
for 10 black oils and 7 gas condensates from around the world.

Cloud Point Relation to Oil C50+
0
20
40
60
80
100
120
140
160
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F


Figure 11: Oil Cloud Point and C50+ Correlation

Cloud Point Relation to Oil Normal Paraffins
0
20
40
60
80
100
120
140
160
0 1 2 3 4 5 6
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F
nc30-nc49 % C50+ %


Figure 12: Oil Cloud Point and nC30+ Correlation

Test Run Start Temp., F Cloud Point, F
Run 1 93 61
Run 2 96 62
Run3 97 61
Repeatability and Accuracy = 0.5 F
Dynamic Filtration Cloud Point Method
Special Wax-Hexane Mixture
ASTM-D2500 Cloud Point is 62 F
Test Run NIR CP, F DFCP CP, F
Run 1 59 61
Run 2 60 62
Run3 60 61
Repeatability = 0.5 F 0.5 F
Accuracy = 1 F 0.5 F
DFCP and NIR Cloud Point Methods
Special Wax-Hexane Mixture
ASTM-D2500 Cloud Point is 62 F
SPE 80267 Cloud Point and Wax Deposition Measurement Techniques 7
Cloud Point Relation to Oil Composition
0
20
40
60
80
100
120
140
160
0 5 10 15 20 25
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F
Wax % AR % ARW % nc30-nc49 % C50+ %
AR = Asphaltenes + Resins
ARW = Asphaltenes + Resins + Waxes


Figure 13: Oil Cloud Point-Composition Correlation

Cloud Point Relation to Gas C50+
0
20
40
60
80
100
120
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F


Figure 14: Gas Cloud Point and C50+ Correlation

Cloud Point Relation to Gas Normal
Paraffins
0
20
40
60
80
100
120
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F
nc30-nc49 % C50+ %


Figure 15: Gas Cloud Point and nC30+ Correlation

Cloud Point Relation to Gas Composition
0
20
40
60
80
100
120
0 0.5 1 1.5 2 2.5 3 3.5
Weight. %
C
l
o
u
d

P
o
i
n
t
,

F
Wax % AR % ARW % nc30-nc49 % C50+ %
AR = Asphaltenes + Resins
ARW = Asphaltenes + Resins + Waxes


Figure 16: Gas Cloud Point-Composition Correlation

Although the data in Figures 11 to 16 indicate some
correlation of the oil and gas condensate cloud point with the
composition data, especially but not only with the C50+
paraffins, this correlation is not due to fundamental or
mechanistic reasons. This will become apparent later in the
section Special Case: Oils Containing Natural Wax Crystal
Modifiers, where it will be shown that the cloud point is not
at all influenced by the oil SARA (Saturate-Aromatic-Resin-
Asphaltene) and HTGC (High Temperature Gas
Chromatography) compositions.

Wax Deposition. Wax deposition data are presented next for
the dynamic wax deposition and static wax deposition
apparatuses. First, some of the raw data obtained for the
dynamic wax deposition example shown in Figure 8 is shown
below in Table-3.


Table 3: Dynamic Wax Deposition Data for Example of Figure 8

It is evident from the data that wax deposition in the lab
apparatus starts high and after a while it begins to decline as
waxes deposit and the shear rate increases. The average initial
wax deposition rate is about 21.6 psi/day for data points
collected every 5 minutes in Table 3. The raw data for the
DP, psi Rate, psi/min Rate, psi/hr Rate, psi/day Avg Rate
0.475 0.0021 0.129 3.086 psi/day
0.505 0.0046 0.277 6.646 21.641
0.525 0.0067 0.400 9.600
0.550 0.0095 0.573 13.745
0.575 0.0130 0.780 18.720
0.570 0.0139 0.833 20.000
0.575 0.0163 0.975 23.400
0.560 0.0164 0.986 23.657
0.550 0.0175 1.050 25.200
0.530 0.0170 1.020 24.480
0.525 0.0200 1.200 28.800
0.515 0.0233 1.400 33.600
0.475 0.0150 0.900 21.600
0.465 0.0200 1.200 28.800
Raw Wax Deposition Data for Example in Figure 8
8 K. J. Leontaritis AND J. D. Leontaritis SPE 80267
static wax deposition example shown in Figure 9 are shown
below in Table 4.

Table 4: Static Wax Deposition Data for Example of Figure 9

In Table 4, 6 cases of the same oil were run with different
chemicals to determine the effect of 5 chemicals on wax
deposition. However, one could have placed six different oils
in the cells and compared the wax deposition from them.
Although such data would appear to have only qualitative
usefulness, if the true field wax deposition rate of one or two
of the oils is known, the wax deposition rate of the other oils
could be estimated by extrapolation or interpolation
(preferred).

Special Case: Oils Containing Natural Wax Crystal
Modifiers
It was mentioned earlier that some oils contain natural
asphaltene dispersants and wax crystal modifiers and as a
result, although these oils contain substantial amounts of
asphaltene and wax molecules, they remain stable at most
thermodynamic conditions encountered during their
production. The following two examples demonstrate this
point.

Special Case 1: The complete composition and fluid
characterization of the Oil A is shown in Table 5.



Table 5: Oil A PARA EOS Fluid Characterization

The above method of characterizing reservoir fluids, called
PARA (Paraffin-Aromatic-Resin-Asphaltene) EOS Fluid
Characterization, has been previously described.
14, 16
This oil
contains 0.15 wt% C50+ and 2.13 wt% C30-C49. However,
the oil did not precipitate any waxes in the following two tests
whose data are shown in Figures 17-18 and Table-6.
Oil A Near-Infra-Red Cloud Point Test
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
20 40 60 80 100 120 140 160
Temperature, F
N
-
I
-
R

L
i
g
h
t

A
t
t
e
n
u
a
t
i
o
n
,

A
U
No wax onset indicat ed
from 158 t o 38 F.


Figure 17: Oil A NIR Cloud Point Test



Figure 18: Oil Static Wax Deposition Test

Table 6: Static Wax Deposition Data for Example of Figure 18

Special Case 2: The complete composition and fluid
characterization of the Oil B is shown in Table 7.
Component MW Tc, K Pc, bar Omega Mole Fr. Weight Weight Fr.
N2-CO2 44.010 304.206 72.948 0.225 0.000984 0.043296 0.000481
METHANE 16.043 190.550 45.990 0.011 0.559697 8.979217 0.099731
ETHANE 30.070 305.330 48.710 0.099 0.063172 1.899592 0.021098
PROPANE 44.097 369.850 42.470 0.152 0.037729 1.663736 0.018479
I-BUTANE 58.124 408.322 36.018 0.185 0.008034 0.466957 0.005186
N-BUTANE 58.124 425.250 37.920 0.199 0.017356 1.008773 0.011204
C5-C9 102.725 540.855 27.313 0.355 0.099486 10.219652 0.113508
C10-C15 168.735 677.669 21.759 0.631 0.081986 13.833971 0.153652
C16-C29 274.966 806.437 15.705 0.890 0.049726 13.673064 0.151864
AROMATIC 425.000 867.799 12.376 1.155 0.060792 25.836635 0.286963
C30-C49 462.557 843.814 8.699 1.262 0.004145 1.917469 0.021297
C50+ 678.381 923.658 6.505 1.697 0.000204 0.138710 0.001541
RESINS 600.000 942.131 5.204 1.710 0.014418 8.651074 0.096086
ASPHALTE 750.000 960.604 5.053 1.812 0.002270 1.702571 0.018910
1.000000 90.034716 1.000000
AsphWax Reservoir Oil PARA Fluid Characterization
Date: 18-Feb-02
Fluid: AsphWax Well #1 STO
Initial Oil Temperature, F: 140.0
Chemical Treatment Temperature, F: 140.0
Hot Water Bath/Oil Temperature, F: 140.0
Cold Plate Temperature, F: 40.0
Beaker # Chemical PPM Deposit, g % Effectiveness
1 None 0 0 NA
Cold Plate Test Report
Date: 17-Aug-02
Fluid: AsphWax Well #1 STO
Initial Oil Temperature, F: 140.0
Chemical Treatment Temperature, F: 140.0
Hot Water Bath/Oil Temperature, F: 120.0
Cold Plate Temperature, F: 40.0
Beaker # Chemical PPM Deposit, g % Effectiveness
1 None 0 0.9101 NA
2 WPPD* 1000 0.7588 16.6
3 WCM* 1000 1.647 -81.0
4 WCM* 1000 1.8344 -101.6
5 MUAW

1000 0.3962 56.5

6 MAW

1000 0.4921 45.9

* Wax Crystal Modifier
Wax Dispersant
Cold Plate Test Report
SPE 80267 Cloud Point and Wax Deposition Measurement Techniques 9


Table 7: Oil B PARA EOS Fluid Characterization

The above oil contains 0.19 wt% C50+ and 2.27 wt% C30-
C49. However, the oil did not precipitate any waxes in the
following cloud point test down to 30 F shown in Figure 19.

Oil B Near-Infra-Red Cloud Point Test
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
0.20
20 40 60 80 100 120 140 160
Temperature, F
N
-
I
-
R

L
i
g
h
t

A
t
t
e
n
u
a
t
i
o
n
,

A
U
No Wax Onset indicated down to 30F


Figure 19: Oil B NIR Cloud Point Test

Conclusions
Cloud point and wax deposition data were presented for
several synthetic mixtures and crude oils. The cloud point data
have been obtained via three different techniques: Near-Infra-
Red (NIR) light attenuation, Dynamic Filtration Cloud Point
(DFCP), and ASTM-D2500. Also, two wax-deposition
techniques were presented; the dynamic and static wax
deposition techniques. The following conclusions can be
made:
For the transparent mixtures, the ASTM-D2500
method was the standard cloud point method against
which the other two techniques are compared to. The
data showed that all three techniques are consistent
with each other, although their precision is different.
Because of its simplicity, higher precision, and wide
applicability to all kinds of fluids and thermodynamic
conditions, the NIR light attenuation technique is
recommended.
Wax deposition data from two dynamic and static
techniques were presented from various crude oils
from around the world. Some of these oils contain
natural asphaltene dispersants and wax crystal
modifiers and as a result, although these oils contain
substantial amounts of asphaltene and wax
molecules, they remain stable at most thermodynamic
conditions encountered during their production.
Cloud point data were correlated with compositional
data of crude oils and gases from around the world.
The compositional data were obtained via the PARA
analysis method. This EOS Fluid Characterization
method of characterizing reservoir fluids has been
previously described.
14, 16

It is evident from the results of this study that the
behavior of heavy wax molecules from reservoir
hydrocarbons is largely dependent on compounds or
molecules that are not readily identified by
conventional analytical techniques such as Gas
Chromatography Compositional analysis.

Acknowledgements
The authors wish to thank the partners of AsphWax, Inc. for
allowing publication of the material in this paper.

References
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Component MW Tc, K Pc, bar Omega Mole Fr. Weight Weight Fr.
N2-CO2 43.428 297.733 71.514 0.218 0.003279 0.142411 0.001376
METHANE 16.043 190.550 45.990 0.011 0.477216 7.655982 0.073984
ETHANE 30.070 305.330 48.710 0.099 0.039828 1.197617 0.011573
PROPANE 44.097 369.850 42.470 0.152 0.036108 1.592242 0.015387
I-BUTANE 58.124 408.322 36.018 0.185 0.008362 0.486048 0.004697
N-BUTANE 58.124 425.250 37.920 0.199 0.018864 1.096440 0.010595
C5-C9 103.729 543.344 27.105 0.359 0.149335 15.490365 0.149691
C10-C15 167.591 675.627 21.808 0.628 0.108498 18.183200 0.175714
C16-C29 276.526 807.724 15.602 0.893 0.080481 22.254994 0.215061
AROMATIC 425.000 867.799 12.376 1.155 0.062165 26.419920 0.255309
C30-C49 463.385 843.723 8.704 1.263 0.005069 2.348852 0.022698
C50+ 679.080 923.658 6.505 1.692 0.000284 0.192570 0.001861
RESINS 600.000 942.131 5.204 1.710 0.009756 5.853640 0.056567
ASPHALTE 750.000 960.604 5.053 1.812 0.000757 0.567770 0.005487
1.000000 103.482049 1.000000
AsphWax Reservoir Oil PARA Fluid Characterization
10 K. J. Leontaritis AND J. D. Leontaritis SPE 80267
13. The American Society of Testing and Materials.: Standard Test
Method for Cloud point of Petroleum Products, ASTM
Standard Designation: D 2500-91, December 1991.
14. Fluid Characterization for Flow Assurance.: Chapter-7 of
AsphWax Professional Course Manual.
15. Standing, M., B.: "Volumetric and Phase Behavior of Oil Field
Hydrocarbon Systems," Society of Petroleum Engineers of
AIME, Dallas, Texas, 1977.
16. Leontaritis, K.J.: "PARA-Based (Paraffin-Aromatic-Resin-
Asphaltene) Reservoir Oil Characterization," SPE Paper No.
37252, SPE International Symposium on Oilfield Chemistry,
February 18-21, 1997, Houston, Texas.