Proceedings of the 7th International Conference on Gas Hydrates (ICGH 2011),

Edinburgh, Scotland, United Kingdom, July 17-21, 2011.

A SIMPLE CORRELATION FOR CALCULATING THE HYDRATE

SUPPRESION TEMPERATURE BASED ON WATER ACTIVITY

Saied Mazloum, Antonin Chapoy, Jinhai Yang and Bahman Tohidi

Centre for Gas Hydrate Research, Institute of Petroleum Engineering
Heriot-Watt University
Edinburgh, EH14 4AS
UNITED KINGDOM

ABSTRACT
Currently, the most common method for preventing hydrates in the oil and gas industry is the
injection of thermodynamic inhibitors (e.g., methanol and ethylene glycol). The total inhibitor
requirement can be calculated based on the amount required for treating the aqueous phase, plus
the amount of inhibitor lost to the hydrocarbon phase(s). Although a safety margin is usually
considered in this calculation, hydrates may still form in case of unexpected events. It is not
uncommon to use a large safety margin to reduce the risk of hydrate blockage. Excessive use of
an inhibitor has environmental and economical consequences and can result in significant
increase in capital and operational expenditures, in particular at high water-cut conditions.
While the effectiveness of thermodynamic inhibitors have been well proven and modelling of
hydrate thermodynamic properties in the presence of these inhibitors have reached a good degree
of reliability, only few researchers have addressed inhibitor optimisation and monitoring. This
paper presents a simple method for monitoring and optimising thermodynamic hydrate inhibitors
dosage in various production systems. The method is based on predicting the hydrate suppression
temperature from the measured water activity values of the downstream aqueous phase. Water
activity of the aqueous phase is measured using a simple commercial water activity meter.
Initially, a correlation was developed relating water activity values to the hydrate suppression
temperature using our in-house thermodynamic model. Next a large dataset was generated by
measuring water activities of a wide variety of aqueous solutions containing various salts and/or
organic inhibitors over a wide range of concentrations. The reliability of the above correlation
was examined by comparing its predictions with the actual measured water activity data. Finally,
the hydrate stability zones predicted by this approach were compared with independent
experimental data. The results are in good agreement, demonstrating the reliability of this
method.

Keywords: gas hydrates, kinetic inhibitors, thermodynamic inhibitor, water activity, phase
boundary, correlation

NOMENCLATURE INTRODUCTION
aw water activity Formation of hydrate is a problem to the oil and
C pressure effect constant gas industry because it can eventually block
P pressure [bar] pipelines and stop production and also leads to
T hydrate equilibrium temperature [oC] safety hazards to production/transportation
T0 hydrate equilibrium temperature of distilled systems and substantial financial losses.
water [oC] Furthermore, restarting the facility, especially in
T hydrate suppression temperature [oC] offshore environments, can be a long and costly
process since the remediation and dissociation of
hydrate plugs is difficult to achieve.
Conventional hydrate flow assurance methods
focus on preventing hydrate formation either by
modifying one of the elements required for hydrate
formation (i.e., dehydration of natural gas or
lowering the operating pressure) or by injecting
thermodynamic hydrate inhibitors which shift
hydrate phase boundary away from the operating
conditions. Thermal insulation and active heating
methods are also used to increase the pipeline
temperature outside the hydrate risk zone.
However, thermal methods are inherently very
expensive and are economical only for short
distances. New flow assurance methods are
moving towards delaying hydrate formation and/or
preventing their agglomeration by means of Low
Dosage Hydrate Inhibitors (LDHIs) which are
divided into Kinetic Hydrate Inhibitors (KHIs) and
Anti-Agglomerants (AAs) respectively, the detail
can be found in open literature [1], [2], [3].
The most common flow assurance method used in
the oil and gas industry is injection of
thermodynamic hydrate inhibitors, i.e. methanol
(MeOH) and mono ethylene glycol (MEG) at
wellhead. Successful inhibition with methanol or
glycol typically requires inhibitor concentrations
from 15 to 50 mass% (or even higher) in the
aqueous phase. Methods for calculating the
required inhibitor dosage are based on determining
the hydrate phase boundary for the fluid under
consideration either experimentally or using
thermodynamic models. The appropriate injection
rate for each inhibitor to treat the free water phase
depends on how far the phase boundary needs to
be shifted for a specific system at a given pressure.
The required inhibitor dosage (injection rate) to
prevent hydrate formation is the amount of
inhibitor required to treat the free water, plus the
amount of inhibitor lost to the vapour phase and
the hydrocarbon liquid phase. Although a safety
margin is usually considered in this calculation,
hydrates still form, which can be due to the
problems with injection pumps, a sudden increase
in the water-cut, a change in fluid flow rate,
emergency shut-downs, problems associated with
start-ups, lack of information on the composition
of produced water, changes in the system
temperature and pressure, etc. To overcome these
problems, in most cases too much inhibitor is used
because if hydrate forms due to insufficient
inhibitor dosage, the problems caused by the
formation of hydrates will have much greater
economical consequences. Excessive use of an
inhibitor has environmental and economical
consequences and can result in significant increase
in capital and operational expenditure, in particular
at high water-cut conditions. While the
effectiveness of thermodynamic inhibitors have
been well proven and hydrate thermodynamic
properties in the presence of these inhibitors have
reached a good degree of reliability, only a limited
effort has been devoted for optimizing and
monitoring the concentration of inhibitors in
pipelines [10, 11].
This paper presents a simple method for
monitoring and optimising thermodynamic hydrate
inhibitors dosage in the system. The method is
based on predicting the hydrate suppression
temperature of fluid from measured water activity
value of the downstream aqueous phase. Water
activity of the aqueous phase at constant
temperature depends on the concentration of
thermodynamic inhibitors and salt present in the
system, therefore monitoring of this parameter can
provide an indication of how far the system is
from hydrate phase boundary. These inhibitors and
salts are able to bind to water molecules through
intermolecular bonds, thus preventing bound water
molecules from forming hydrogen bonds with
each other and with the remaining free water.
More specifically, these compounds reduce the
free-water concentration, which is considered as
water activity in the system. Water activity of the
aqueous phase in this work is measured using a
simple commercial device, which is much easier
than measuring hydrate dissociation point and can
significantly reduce the time and cost of the
experiments. A general correlation has been
developed to relate the measured water activities
values to the hydrate suppression temperate by
generating pseudo-experimental data using a well-
proven thermodynamic model [5] [4]. To examine
the reliability of the model in predicting water
activity, experimental water activity data were
measured using LabMaster-aw water activity
meter. The water activity meter measures water
activity from change of humidity of the air around
the sample using a resistive electrolytic humidity
sensor. A large database of different salt and
alcohols (methanol and MEG) solutions over a
wide range of concentrations has been created to
develop the correlation.
THERMODYNAMIC MODELLING
A general phase equilibrium model based on the
uniformity of component fugacities in all phases is 50
used to predict the water activity and the hydrate
suppression temperature of aqueous solutions of 40

salt and alcohol. A description of the

T / C
30

o
thermodynamic model can be found elsewhere [4].
In summary, the statistical thermodynamics model
20 50 bar
100 bar
uses the Valderrama modification of the Patel and 10 200 bar

Teja equation of state [5] and non-density- 300 bar

0
dependent [4] mixing rules for fugacity -0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0
calculations in all fluid phases. The hydrate phase water activity /ln (aw)

is modelled using the solid solution theory of van Figure 1 Hydrate suppression temperature vs
der Waals and Platteeuw [6], as developed by logarithm of the water activity
Parrish and Prausnitz [7]. The equation
recommended by Holder [8] is used to calculate
the heat capacity difference between the empty As can be seen from Figure 1, all the points
hydrate lattice and pure liquid water. The Kihara closely fit to a line suggesting a linear relation
model for spherical molecules is applied to between the hydrate suppression temperature and
calculate the potential function for compounds the Neperian logarithm of water activity of the
forming hydrate phases [9]. aqueous phase. To take into account the effect of
pressure on the correlation, an equation has also
CORRELATION DEVELOPMENT been developed as shown in Figure 2
A general correlation has been developed to relate
the measured water activities values to the hydrate P/ bar
suppression temperate by generating pseudo- 0 50 100 150 200 250 300
-70
experimental data using the above described
thermodynamic model [5]. Using pseudo- -72

experimental data instead of real experimental data -74

in developing the correlation makes it possible to -76

C(P)

generate a large database of different -78

concentrations of salt and alcohols (methanol and -80

MEG) solutions over a wide range of -82
concentrations at shorter time and lower cost. Over -84
200 aqueous solutions were used in developing the
correlation. Figure 2 Slope of constants in the correlation,
All of these aqueous systems were assumed to be C(P), vs system pressure
in contact with a typical natural gas and hydrate
suppression temperatures for these systems were
predicted at 50, 100, 200 and 300 bar to evaluate
The correlation is given by the following
the effect of pressure on the correlation. Figure 1
shows the predicted hydrate suppression
expressions:
temperatures as a function of Neperian logarithm
of water activity of the aqueous phase containing T = T-T0 = C(P) * ln(aw) Eq 1
different concentrations of salts and
thermodynamic hydrate inhibitors. C(P) = -4.784 * ln(P) 54.790 Eq 2

Where T is the hydrate dissociation temperature in

Celsius or Kelvin, T0 is the hydrate dissociation
temperature of the same fluid in the presence of
distilled water (without salt and/or inhibitor) in
Celsius or Kelvin, aw is water activity of the
aqueous solution and C(P) is a constant function of
the system pressure, P. The developed correlation
is simple and enables fast estimation of the a) MEG
hydrate-free zone of various reservoir fluids, in the
1
presence of salts and/or organic inhibitors. The 0.9
only prerequisite to use the correlation is the 0.8

water activity /aw

hydrate dissociation temperature of the same fluid 0.7

in the presence of distilled water (T0), which can 0.6

0.5
be calculated using predictive thermodynamic 0.4
software capable of predicting hydrate phase 0.3
boundaries of various reservoir fluids. 0.2 Measured aw @25C
0.1
0
VALIDATION 0 20 40 60 80 100
A LabMaster-aw water activity meter was used to ethylene glycol /mass%
measure the water activity of aqueous solutions at
25 oC. The measuring system of the LabMaster-aw
is a resistive electrolytic humidity sensor. This b) 5 mass% NaCl + MEG
device analyses static samples at atmospheric 1.0
pressure. The aqueous phase is equilibrated within 0.9
the head space of a sealed chamber housing the 0.8

water activity /aw

sensor. The resistive-electrolytic measurement 0.7
0.6
method uses the physical principle of the 0.5
conductivity measurement in a liquid chemical 0.4

substance. This liquid is very stable and 0.3

0.2
hygroscopic. The water molecules from the 0.1
Measured aw @ 25 C
Salting-out
surrounding air penetrate in the chemical structure 0.0

and consequently the conductivity changes. Small 0 20 40 60

ethylene glycol /mass%
80 100

air humidity changes induce large conductivity

variations. Thus the instruments can precisely
detect the surrounding air humidity. These sensors
can detect relative humidity of the air-water c) NaCl + 25 mass% MEG
mixture from 3% to 100%. The temperature of the 1.0
cell could be changed from a range of 0 C to 50
C. The system allows a high measurement 0.9
water activity /aw

accuracy and repeatability. The calibration of the 0.8

device has been checked by using the standards
from the supplier. Water activity of aqueous 0.7

solutions containing methanol, ethylene glycol, 0.6 Measured aw @ 25 C

different salts (NaCl, KCl, and CaCl2), artificial NaCl salting out

produced water, real produced water and 0.5

0 5 10 15 20 25 30 35 40
combinations of above were measured with the NaCl /mass%
LabMaster-aw device. The results have been used
to validate the correlation and also to examine the
reliability of the model in predicting the water d) NaCl + 50 mass% MEG
activity.

RESULTS AND DISCUSTIONS

Aqueous solutions of MEG without and with

salt (NaCl)
Different combination of MEG and NaCl were
tested in this section. The results are presented in
Figures 3a-e. In these figures, solid lines present
the predicted water activity values.
 1.0

0.9
a) NaCl
water activity /aw

0.8
1
0.7
0.95

water activity /aw

0.6
0.9
0.5 Measured aw @ 25 C
NaCl salting out 0.85
0.4
0 5 10 15 20 25 30 35 40 0.8 this work
NaCl /mass% ASTM Values
Model Predictions
0.75
NaCl salting out

0.7

e) NaCl + 75 mass% MEG 0 5 10 15 20 25 30 35

NaCl /mass%

0.6

b) KCl
0.5
water activity /aw

1.0

0.4

water activity /aw 0.9

0.3
Measured aw @ 25 C
NaCl salting out
0.2
0.8
0 5 10 15 20 25 30 35 40
NaCl /mass% Measured aw @ 25 C
KCl salting out
0.7
0 5 10 15 20 25 30 35 40
KCl /mass%
Figure 3 Water activity of MEG aqueous
solutions in the presence of salt (NaCl). Solid lines
present the predicted water activity values.
c) CaCl2
1.0
In the system containing 25 mass% MEG, the
experimental and predicted data are very close up 0.9
water activity /aw

to 25 mass% NaCl concentration where the salting 0.8

out starts (salt crystals came out of the solution).
As it is illustrated in these figures, by increasing 0.7

the amount of MEG in the system, salting out 0.6

happens at lower concentration of NaCl, i.e. at 15 Measured aw @ 25 C

and 5 mass% NaCl in the systems with 50 and 75 0.5

0 5 10 15 20 25 30 35 40
mass% MEG, respectively. CaCl2 /mass%

Figure 4 Water activity of different salt systems.

Aqueous solution with different types and Solid lines present the predicted water activity
varying concentrations of salts values.

Different systems with various types and

concentrations of salts were tested in this section Different Produced water systems in the
and the results are presented in Figure 4. presence of MEG

To validate the correlation and examine the ability

of the device in more complex systems, different
types of produced water (from different fields)
were synthesised in the laboratory and their 1.0
activity were measured in the presence of varying 0.9

concentrations of MEG. Compositions of 0.8

water activity /aw

produced water are given in Table A.1. As can be 0.7
0.6
seen in Figures 5a-d, the measured and predicted 0.5

water activity values are very close up to salting 0.4

Measured aw @ 25 C
out points. Finally, a real produced water (named 0.3
0.2 HWHYD aw @ 25 C
Real produced water B) were tested in this section. 0.1

Figure 6 illustrates the results, which suggest that 0.0

0 20 40 60 80 100
the water activity of real produced water can also ethylene glycol /mass%
be accurately measured by LabMaster water
activity meter.
d) MEG + Produced water S
1.0

a) MEG + Produced water M 0.9

0.8

water activity /aw

0.7
0.6
1.0
0.5
0.9
0.4
0.8 Measured aw @ 25 C
0.3
water activity /aw

0.7 HWHYD aw @ 25 C
0.2
0.6
0.1
0.5
0.0
0.4 0 20 40 60 80 100
Measured aw @ 25 C
0.3 ethylene glycol /mass%
0.2 HWHYD aw @ 25 C

0.1 Figure 5. Water activity of different produced

0.0 waters in the presence of MEG. Solid lines present
0 20 40 60 80 100
ethylene glycol /mass%
the predicted water activity values.

MEG + Real produced water B

b) MEG + Produced water P
1.0
1.0
0.9 0.9
0.8
water activity /aw

0.8
water activity /aw

0.7
0.6
0.7
0.5
0.4 0.6 Measured aw @ 25 C
Measured aw @ 25 C
0.3 HWHYD aw @ 25 C
HWHYD aw @ 25 C 0.5
0.2
0.1
0.4
0.0 0 10 20 30 40 50 60 70 80
0 20 40 60 80 100
ethylene glycol /mass%
ethylene glycol /mass%
Figure 6. Water activity of the real produced
water B in the presence of MEG. The solid line
presents the predicted water activity values.
c) MEG + Produced water F

Aqueous solutions of methanol without and

with salt (NaCl)
As with the MEG solutions, different aqueous
solutions of methanol (MeOH) in the presence and
absence of salt (NaCl) were tested to investigate
the ability of the device for solutions containing
methanol. The results are presented in Figures 7a- are provided in Table A.2; two aqueous solutions
b. containing 10 and 50 mass% of MEG were used.
As can be seen in Figure 8, the correlation is in
good agreement with the model predictions and
a) MeOH the experimental data, the deviation in the hydrate
1.0
dissociation temperature is less than 1 C for
pressures up to 500 bar.
0.9
water activity /aw

0.8 500
450 10 mass% (NG1)

0.7 400 50 mass% (NG2)

Measured aw @ 25 C
350
HWHYD aw @ 25 C
300

P / bar
0.6
0 20 40 60 80 100 250
methanol /mass% 200
150
100
50
b) MeOH + NaCl 0
-20 -10 0 10 20 30
1.0 T / oC

Figure 8. Experimental and predicted (dotted

0.9
lines) and correlated (solid lines) hydrate
water activity /aw

dissociation conditions for the two natural gases

0.8
and two aqueous solutions containing different
0.7
concentrations of MEG. (Error bars: 1 oC).
Measured aw @ 25 C
HWHYD aw @ 25 C
0.6 CONCLUSIONS
0 10 20 30 40 50 60

methanol /mass%
In this work a simple and robust
Figure 7. Water activity of methanol aqueous correlation has been developed based on
solutions in presence of salt (NaCl). Solid lines pseudo experimental data generated by an
present the model prediction. in-house thermodynamic model.
This correlation could be used for systems
containing different salt and alcohol
As can be seen in Figure 7, in the very low MeOH (methanol and MEG).
concentration the measured water activities are not The model and the data have been
far away from the predictions. However, for the validated by a wide range of experimental
concentration greater than 5 mass% the data generated in this work and the results
measurements are not correct. In the systems with show a very good agreement.
salt present, large deviations are observed between
The developed correlation has been
the measurements and the predictions over the
validated by comparing the predictions
entire methanol range. Based on these results it is
with literature data and the results show a
concluded that the existing sensor of the
very good agreement between correlation
LabMaster device cannot measure the water
and experimental data.
activity of methanol aqueous solutions.
An executable program has been
developed which directly read the water
Validation of the developed correlation
activity data and calculate the hydrate
phase boundary using the correlation.
The developed correlation was validated by
This developed system could be used for
comparing the natural gas hydrate phase boundary
monitoring hydrate phase boundary.
correlated by Equations 1 and 2 with the
experimental data [12] and the model prediction
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APPENDIX