Sour Gas Hydrate Formation Phase Behavior | Campbell Tip of the Month 05/08/2019, 3+04 PM

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Sour Gas Hydrate Formation Phase Behavior

A phase envelope with hydrate and water dew point curves is an excellent tool to find what phase water is in
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at operating conditions, during start-up, during shut-down and during upsets. In the November 2007 Tip of
the Month (TOTM), we discussed the phase behavior of water-sour natural gas mixtures. In this tip, we will
4 extend our study on the sour natural gas hydrate formation phase behavior. Specifically, we will study the Search for:
Like impact of H2S and CO2 on the formation of hydrate in natural gas.
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The hydrate formation temperature of a gas depends on the system pressure and composition. There are
several methods of calculating the hydrate formation conditions of natural gases. At equilibrium, the
chemical potential of water in the hydrate phase is equal to that in each of the other coexisting phases. English TOTM Home
Parrish and Prausnitz [1] developed a thermodynamic model to describe this phenomenon, and later, the model was
improved by Holder et al. [2]. These methods are suitable for calculations using a computer with equations of state. The Spanish TOTM Home
details of hand calculation methods can be found in Chapter 6 of Volume 1 [3] of “Gas Conditioning and Processing” and
Chapter 20 of GPSA DATA BOOK [4]. In this work we will use the Soave-Redlich-Kwong (SRK EoS) [5] in ProMax [6]
software. Archives

June 2019
The compositions of the gas mixture studied in this study are shown in Table 1.
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Table 1. Water-saturated compositions of gas mixtures studied
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Figure 1 presents the calculated hydrate formation curve (solid curve) and the dew point portion of the phase envelope of August 2017
a sweet natural gas (solid curve with the square). Figure 1 also presents the dew point and hydrate formation curves for
the same gas mixture containing 10 and 20 mole % CO2. Figure 1 indicates that as the CO2 mole % increases from 0 to July 2017
20 mole %, the hydrate formation curves shift slightly to the left, depressing the hydrate formation temperature. Note that
the points to the left and above the hydrate curves represent the hydrate formation region. From an operational point of June 2017
view, this region should be avoided/prevented. This figure also indicates, as CO2 mole % increases, the cricondenbar May 2017
decreases and the phase envelope shrinks.
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Sour Gas Hydrate Formation Phase Behavior | Campbell Tip of the Month 05/08/2019, 3+04 PM

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Figure 1. The impact of CO2 on the hydrocarbon dew point and hydrate formation curve. July 2014
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Similarly, Figure 2 presents the calculated hydrate formation curve (solid curve) and the dew point portion of phase
May 2014
envelope for the same sweet natural gas (solid curve with the square). Figure 2 also presents the dew point and hydrate April 2014
formation curves for the same gas mixture containing 10 and 20 mole % H2S. Figure 2 indicates that as the H2S mole %
increases from 0 to 20 mole %, the hydrate formation curves shift considerably to the right, promoting the hydrate March 2014
formation temperature. This is opposite to the effect of CO2 and it is more pronounced. From an operational point of view,
February 2014
this is undesirable because H2S expands the hydrate formation region to the right. Note that the points to the right and
below of the hydrate curve represent the hydrate-free region. Figure 2 also indicates, as H2S mole % increases, the January 2014
cricondenbar decreases and the phase envelope shrinks. The shrinkage of the phase envelope is less than that of CO2.
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Figure 2. The impact of H2S on the hydrocarbon dew point and hydrate formation curve. May 2012
April 2012
Figure 3 presents the calculated hydrate formation curves for a sweet gas, a sour gas with 20 mole % CO2 and a sour gas
March 2012
with 20 mole % H2S. This figure clearly indicates that the impact of H2S is much bigger than the CO2 impact; CO2 February 2012
depresses (shifts to the left) the hydrate formation condition slightly but H2S promotes hydrate formation considerably. As
an example, at 1000 psia (6900 kPa), CO2 reduces hydrate formation temperature for this gas by about 5.5˚F (3˚C) while,
January 2012
H2S increase hydrate formation temperature by about 20˚F (11.1˚C). December 2011
November 2011
Conclusions: October 2011
September 2011
The presence of CO2 and H2S in natural gas has an opposite impact on the hydrate formation condition. While the impact
of CO2 is small, H2S has considerable impact on the hydrate formation condition. CO2 depresses hydrate formation (acts August 2011
as hydrate inhibitor and shifts the hydrate curve to the left) while H2S shifts the hydrate curve to the right, promotes
July 2011
hydrate formation conditions, and may cause severe operational problems.
June 2011

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Sour Gas Hydrate Formation Phase Behavior | Campbell Tip of the Month 05/08/2019, 3+04 PM

To learn more about similar cases and how to minimize operational problems, we suggest attending our G40 May 2011
(Process/Facility Fundamentals), G4 (Gas Conditioning and Processing), P81 (CO2 Surface Facilities), and PF4
(Oil Production and Processing Facilities) courses. April 2011
John M. Campbell Consulting (JMCC) offers consulting expertise on this subject and many others. For more information March 2011
about the services JMCC provides, visit our website at www.jmcampbellconsulting.com, or email us at
consulting@jmcampbell.com.
February 2011
January 2011
By: Dr. Mahmood Moshfeghian
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Figure 3. The opposite impact of CO2 and H2S on the hydrate formation curve.
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Reference: March 2009
1. Campbell, J.M., “Gas conditioning and Processing, Vol 1: The Basic Principles”, 8th Edition, Edited by R.A. February 2009
Hubbard, John M. Campbell & Company, Norman, USA, 2001.
2. Parrish, W.R., and J.M. Prausnitz, “Dissociation pressures of gas hydrates formed by gas mixtures,” Ind. Eng.
January 2009
Chem. Proc. Dev. 11: 26, 1972. December 2008
3. Holder, G. D., Gorbin, G. and Papadopoulo, K.D, “Thermodynamic and molecular properties of gas hydrates from
mixtures containing methane. argon, and krypton,” Ind. Eng. Chem. Fund. 19(3): 282, 1980. November 2008
4. Gas Processors Suppliers Association; “ENGINEERING DATA BOOK” 13th Edition – FPS; Tulsa, Oklahoma, USA, October 2008
2012.
September 2008
1. G. Soave, Chem. Eng. Sci. 27, 1197-1203, 1972.
August 2008
6. ProMax 3.2, Bryan Research and Engineering, Inc, Bryan, Texas, 2012.
July 2008
June 2008
May 2008
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Posted on December 1, 2012 at 10:20 am
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October 2007
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Written by Dr. Mahmood Moshfeghian
June 2007
DR. MAHMOOD MOSHFEGHIAN is a Senior Technical Advisor and Senior Instructor. He is the author of most Tips of the May 2007
Month and develops technical software for PetroSkills. He has 40 years teaching experience in universities as well as for
oil and gas industries. Dr. Moshfeghian joined JMC in 1990 as a part time consultant and then as full time April 2007
instructor/consultant in 2005. Moshfeghian was Professor of Chemical Engineering at Shiraz University. Dr. Moshfeghian
is a senior member of AIChE and has published more than 125 technical papers on thermodynamic properties and March 2007
Process Engineering. Dr. Moshfeghian has presented invited papers in international conferences. He is a member of the
Editorial Board for the International Journal of Oil, Gas, and Coal Technology and a member of the GPSA Technical
February 2007
Committee Group F. He holds B.S. (74), M.S. (75) and and PhD (78) degrees in Chemical Engineering, all from Oklahoma January 2007
State University.
December 2006
View all posts by: Dr. Mahmood Moshfeghian
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Next Post » September 2006

7 responses to “Sour Gas Hydrate Formation Phase Behavior” August 2006
July 2006
1. Ahmed Hassan says:
December 4, 2012 at 6:10 am June 2006
thanks May 2006
2. Hassan says: April 2006
January 12, 2013 at 7:07 am March 2006
No comments , only question : why the TOTM of Jan-2013 does not issue yet? February 2006
regards January 2006
3. Karam says: December 2005
January 17, 2013 at 4:56 am
November 2005
is this kind of exercises are part of G-4 Training course? October 2005
Dr. Mahmood Moshfeghian says: September 2005
June 15, 2013 at 8:53 am
August 2005
Yes. Of course, much more.
July 2005
4. Hossein says:
March 31, 2014 at 2:25 am June 2005
Dear Prof. Moshfeghian, Complete Archives
Are there any commercial software to simulate the process of CO2 capture by hydrate technology in a process? Free Subscription
Best Regards,

5. SIGINT says: Topics

December 29, 2015 at 3:09 am

Your place is valueble for me. Thanks!… Gas Processing

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10. Ade says:
April 24, 2017 at 7:26 am WordPress.org
Dear Prof,
Please kindly help me with Hydrate formation Reservoir Composition, this is to aid my project topic on Modelling
hydrate formation using software pipesm.
Thanks.

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