Art Montemayor [Type text] Feb 22, 2014

Water Content of CO2 in Equilibrium with Liquid Water and/or Hydrates

Summary
Experimentally measured water content in CO2-rich fuid in the gaseous or liquid state in
equilibrium with liquid water or hydrate is presented for pressures ranging from 100 to
2000 psia !0"#$ to 1%"&$ '(a) and temperatures from -1$ to && degrees * !-2+"%% to 2,"0
degrees C)" -he water content of the CO2-rich phase along the three-phase equilibria i"e"
liquid water.liquid CO2.gas to the three-phase critical endpoint is also reported" -he
experimental results from this study on the water content in the CO2-rich phases ha/e
been combined with earlier research results of the CO2.water binary system in the
hydrate-free region from && to 200 degrees * !2,"0 to $%"%% degrees C) and pressures to
%000 psia !20"#$ '(a) to produce a comprehensi/e pressures to %000 psia !20"#$ '(a)
to produce a comprehensi/e plot" -he high degree of complexity in the phase beha/ior of
a CO2.water binary system which exhibits se/eral pairs of equilibrium phases for the
conditions is shown" -o ma0e the data more intelligible than they are in their raw form
the data are presented in terms of the pressure enhancement of the water content
presented in terms of the pressure enhancement of the water content along isotherms"
*inally the acti/ity coe1cients of water in the CO2-rich phases are summari2ed"
Introduction
3nformation on the equilibrium water content of CO2-rich fuids is necessary o/er a broad
range of pressures and temperatures to complete speci4cations for the processing and
transportation of the fuid associated with CO2 EO5 pro6ects"
*ig" 1 presents the pressure.temperature pro6ection for CO2. water binary system along its
uni/ariant three phase loci and in two-phase regions ob/iously showing the extent and
/ariety of phase equilibria most rele/ant to EO5 technologists" 7s *ig" 1 phase equilibria
most rele/ant to EO5 technologists" 7s *ig" 1 shows the phase behaior of the
CO2/water system is much more complicated oer the natural !as/water system
because of the occurrence of multiple condensed phases " e#!#$ the e%istence of
two liquid phases$ one composed of liquid water and another of liquid CO2 and a
gaseous CO2 phase at high temperatures and one composed of solid hydrate.liquid CO2
and solid hydrate.gas CO2 at low temperatures" Consequently establishin! the water"
content speci&cations was di'cult and challen!in!"
-he water content of CO2 was 4rst measured by 8iebe and 9addy who fowed expanded
CO2-rich samples through a train of absorbents and determined the weight gained by the
train" 3n this study a special experimental apparatus used by 9alloway et al" and a water
analysis scheme de/ised by :loch and ;ifand were used to measure the water content in
the CO2-rich phases" -he data reported by 8iebe and 9addy ha/e recently been
supplemented in the fuid CO2.water region by <oba/ashi et al" and by 9illespie and
8ilson" Calculation methods for the prediction of hydrate formation conditions ha/e been
de/eloped by /an der 8aals and (latteeuw =aito et al" and many others" >ewan?s
correlation yields a good estimate of the water content from the phase density and other
thermodynamic parameters in the fuid CO2.water region" Equations of state @EO=?sA such
as those formulated by (eng and 5obinson and =oa/e are frequently usedB howe/er we
used a/ailable tabulations of thermodynamic properties of CO2 pro/ided by 7ngus et al" to
reduce the errors resulting from the use of an EO="
E%perimental (pparatus and )rocedure
-he experimental apparatus initially used by 9alloway et al" to measure hydrate numbers
has been modi4ed by =loan et al" <obayashi et al" and =ong and <obayashi to measure
the water content of gases in equilibrium with hydrate" 7 line diagram of the apparatus is
shown in *ig 2"
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Art Montemayor [Type text] Feb 22, 2014
Equilibrium in the fuid CO2.water system was established by rotating the cylindrical
autocla/e containing carefully selected and aligned ball bearings" -he equilibration
process in the fuid CO2.hydrate region is considerably more complicated than that of the
fuid CO2.water region" 3t was necessary 4rst to establish gas.hydrate equilibrium by
con/erting all the metastable water into hydrate crystals by an extended rotation of the
autocla/e" 7 tandem pump @shown in *ig" 2A was used to circulate the fuid phase
throughout the system and to store CO2-rich fuid of the same composition but not at the
same temperature as the equilibrium fuid phase in the cell" 7 second hand pump was
used to charge or to charge or to add pure CO2 to the cell" -he elimination of metastable
liquid water was con4rmed by many successi/e analyses of samples @up to %0A ta0en from
the equilibrium gas phase" -he sampling and analyses are di1cult to perform because of
the low water concentration the long sample line and the tedious modi4ed
chromatographic analytic technique de/eloped by :loch and ;ifand"
-he determination of water content in the CO2-rich phase in the liquid CO2.hydrate region
was underta0en after all the studies of the gas CO2.hydrate region were completed" -o re-
establish equilibrium in the liquid CO2.hydrate region pure CO2 was slowly added to the
autocla/e to the desired pressure" Owing to the greater water-carrying capacity of liquid
CO2 than gaseous CO2 at the same temperature a small amount of the hydrate phase
decomposes in the re-equilibration process at a new pressure"
:ecause the density diCerence between CO2 in the hydrate phase and CO2 in the liquid
phase was estimated to be small @*ig" phase and CO2 in the liquid phase was estimated to
be small @*ig" %A it is necessary to stir the contents of the autocla/e gently" 3n this study
all the water-content measurements were made at states where the density of CO2 in
hydrate was greater than the density of fuid CO2" Dowe/er it could be greater than at
high pressures as shown in *ig" %"
-he subsequent experimental condition was always chosen in the direction of increasing
water concentrations in the CO2-rich phase because the elimination of metastable water
from the system containing dense CO2 was almost impossible"
E%perimental *esults
Experimentally measured water contents in the CO2-rich phases are presented in -able 1
and the phases in equilibrium are identi4ed" 3n general a series of phase equilibrium data
was ta0en along isobars @lines of constant pressureA although a few experimental points
were obtained along the three-phase D2O@lA.CO2@lA.CO2@gA locus" Experimental data from this
and earlier studies are plotted along isobars in *ig" E and plotted isothermally in *ig" ,"
=(E*E
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