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CORRELATIONS
Estimating the Hydrate Safety Margin in the Presence of Salt and/or Organic
Inhibitor Using Freezing Point Depression Data of Aqueous Solutions
Hesam Najibi,*, Amir H. Mohammadi, and Bahman Tohidi
Faculty of Petroleum Engineering, Petroleum UniVersity of Technology (PTU), Ahwaz, Iran, and Centre for
Gas Hydrate Research, Institute of Petroleum Engineering, Heriot-Watt UniVersity,
Edinburgh EH14 4AS, Scotland, U.K.
Developing systematic methods for controlling and monitoring gas hydrate risks along the pipeline and/or
downstream conditions could provide the solution for future challenges. In this paper, the possibility of
predicting the hydrate suppression temperatures of fluids from freezing point depression data of aqueous
solutions containing different concentrations of salt and/or non-hydrate-forming organic inhibitor is investigated
by developing a general correlation. The developed correlation considers only the changes in the freezing
point of the aqueous solution, and there is no need for the analytical composition of the aqueous solution.
Since measurement of the freezing point for the aqueous phase is much easier than measuring the hydrate
dissociation point, such a relation can reduce the experimental costs. A well-proven thermodynamic model
is used for generating pseudoexperimental data of hydrate suppression and freezing point depression for 160
different aqueous solutions containing various salts and/or organic inhibitors over a wide range of concentrations
in order to develop this correlation. To examine the reliability of this model in predicting the freezing point
depression, some experimental freezing point depression data are measured and compared with literature
data and the predictions of the model. Independent data are used to examine the reliability of this method.
The predictions of this approach are in acceptable agreement with the independent experimental data,
demonstrating the reliability of this predictive method.
1. Introduction
Application of extended subsea tiebacks and transportation
of unprocessed well streams are among favorable options for
reducing field development and operational costs. These pipelines normally convey a cocktail of multiphase fluids, including
formation water and liquid and gaseous hydrocarbons, and may
therefore be prone to hydrate formation, which potentially can
block the pipeline and lead to serious operational and safety
problems. The conventional method to prevent or reduce hydrate
risks in transfer lines and process facilities is to use the socalled thermodynamic inhibitors. These are water-soluble
chemicals that reduce the water activity, hence shifting the
hydrate phase boundary to higher pressure and/or lower temperature conditions. The common industry practice is to use
methanol or glycols. However, due to uncertainties in the
inhibitor losses to other phases, changes in the system variables
(e.g., water cut, hydrocarbon rates, seasonal temperature changes)
hydrate could form.1
Downstream monitoring could significantly reduce the risks
associated with gas hydrate formation. However, systematic
ways of controlling and monitoring along the pipeline to examine the degree of inhibition are very limited. Hydrate monitoring
systems can be produced based on simple techniques such as
freezing point depression measurement of aqueous phase.
* To whom correspondence should be addressed. E-mail:
najibi@put.ac.ir or najibih@yahoo.com.
PTU.
Heriot-Watt University.
T )
1,297W
M(100 - W)
(1)
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wt %
EG ( 0.1
wt %
methanol ( 0.1
freezing
point ( 0.2, K
1.0
3.0
5.0
7.0
10.0
0.0
0.0
0.0
0.0
0.0
3.2
4.2
7.0
8.2
7.1
6.3
10.2
12.8
12.4
0.0
0.0
0.0
0.0
0.0
10.0
20.0
30.0
40.0
50.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2.8
4.2
6.4
7.8
11.5
12.9
10.1
10.8
12.9
272.7
271.4
270.0
268.5
266.4
269.6
264.8
258.3
249.2
236.2
269.0
267.1
263.0
260.4
258.0
257.5
255.9
252.1
250.1
Ind. Eng. Chem. Res., Vol. 45, No. 12, 2006 4443
2-23
2-13
2-32
2-32
2-40
2-30
2-30
0
0
0
0
0
3.2-12.5
3-9.7
12
7
16
16
20
15
15
18
8
4
7
8
9
5
T ) T0 - 0.6825TF
(2)
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