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Water Equi l i bri um i n the Dehydrati on of Natural
Gas Wi th Tri ethyl ene Gl ycol
A. ROSMAN
ABSTRACT
To develop reliable design data foT glycol
contractors, gas-liquid equilibna in the system water-
methane- trietbylene glycol (TEG) tuere investigated
experimentally.
Eqrii[ibrium va[ues vury little at the
TEG concentrations used in modern
design, but increase significantly with
uwter concentration in the contacting
with increasing equilibrium ternperoture.
very Aigh
corrtactor
increasing
TEG, and
\Jarious methods of data correlation are described
and compared with experimental data, The
correlation provides the means /or extending the
rrstilts o/ this investigation to other pressures and
tcmp~raturcs.
INTRODUCTION
Water removal is a fundamental operation in
natural gas processing. Hydrate formation, corrosion,
and the formation of liquid water that might separate
in the transmission lines are some of the problems
caused by an excess of water in the gas. Of the
methods available for gas dehydration, water
absorption is by far the most generally used.
Glycols, especially triethylene glycol (TEG), are
the preferred absorbents.
A survey of the literature on the water dew
point of natural gas over glycol solutions reveals
significant disagreements. A sampling of published
dewpoint data for gas in equilibrium \vith TEG
(Fig. 7) illustrates the prevailing confusion. Scant,
but still contradictory, information was published
for glyco] concentrations in excess of 99.8 weight
percent. Data in that range are needed in designing
modern glycol contractors where the water dewpoint
temperature must be reduced by more than 100 F.
The main reason for discrepancies in experimental
results is the difficulty of measuring accurately
very small amounts of water in gas. Water is easily
adsorbed on the surfar. s of experimental apparatus.
Normally acceptable data scatter looms large in
relation to the low water concentrations that must
Paper SPE 4040 WJS presented at SPE-AIME 47th Annual
Fall Meeting, held in San Antonio, Tex., Oct. 8-11, IQ72. ~
Copyright 1973 American In. titute of Mining, Meta Ilurg~cal,
and Petroleum Engineers, Inc.
preferences given Kt end Of PaP~r.
This paper will be printed in ?ransactions volume 2S5, which
will cover 1073.
oCTOBER. 1973
CHEVRON OIL FIELD RESEARCH CO.
LA HABRA, CALIF.
be measured. Attempts ro establish water dew
points on the basis of plant performance have been
more successful]. However, accuracy is limited by
the difficulty in establishing the relative
contribution of various factors that interrelate in
plant operation.
Faced with these doubts, contactor designers
have chosen to provide for lEG circulation rates
that are overly high so as to insure more than
adequate water removal. Such a practice is
undesirable, however, where space and power are
at a premium, as on offshore production platforms.
Thus, the range of this investigation was governed
by the need to extend equilibrium information to the
contact temperatures
and TEG concentrations
necessary to optimize glycol contractors on offshore
production platforms.
New procedures were developed for sampling and
analyzing very small concentrations of water in gas
and in TEG. To avoid experimental difficulties
encountered by previous authors, equilibrium was
reached and samples were takml under dynamic
conditions.
Experimental equilibrium results were smoothed
and correlated by several methods. Thermodynamic
equations were used to check on the internal
consistency of data and to calculate equilibrium
constants at conditions outside the range of the
investigation itself. The White expression, l fitted
to the COFRC experimental data, adequately
describes the results within the range of
temperatures and concentrations studied.
DEFINITIONS AND METHODS
At water dewpoint temperature, the water
contained in a natural gas reaches saturation. Part
of that water will condense if the gas is brought
to a lower temperature or to a higher pressure.
Thus, the dewpoint temperature describes the
water content of the gas.
When dewpoint gas contacts TEG, the water
content of the gas decreases. The lower water
content corresponds to saturation water at a lower
temperature; that is, the dew point will be lower.
The initial dewpcint temperature is the contacting
temperature. The temperature corresponding to the
lowered water content is the equilibrium dewpoint
temperature, and the difference between the two
temperatures is the dewpoint depression.
297
The above definitions apply to a system at any
pressure. The effect of pressure on the dewpoint
data was not studied, since most authors agree that
data obtained at atmospheric pressure are valid
for the design of glycol contractors operating at
higher pressures. For instance, Scauzi110,2 who
made a study of the TEG-water-gas equilibrium data
up to 1961, found that dewpoint values for any one
contact temperature agree within 1F throughout
pressures ranging from 14.7 to 2,500 psia.
Assuming that
equilibrium dew points are
independent of pressure, data obtained at
atmospheric pressure can be used to forecast the
dewpoint depression attainable in a glycol contactor
operating at a higher pressure. Although the amount
of water in gas will be lower at the higher pressure,
the equilibrium dew point will still be the same if
the saturation temperature and the TEG concentration
remain the same.
Any serious attempt to optimize contactor design
must make use of gas-liquid equilibrium ratios,
Ku, as defined by Eq. 1:
Y
Kw=#oo..osoos..(l)
w
Although the equilibrium investigated is for a
two-phase, three-component system, the study was
limited to the distribution of one component, water,
between two mutual Iy noninteracting phases. This
is justified by the very low TEG vapor pressure in
the temperature range considered here and by the
negligible methane solubi]ity at atmospheric
pressure. Water concentrations were determined
experimentally in the gas and liquid phases.
Because the approach to equilibrium in the
recirculating system is essentially asymptotic, gas
equilibration was approached from two directions at
every selected temperature to make sure that
equilibrium had been reached. This was achieved
(1) by using overly dry gas so that water would
shift from the liquid TEG to the gas and (2) by
contacting the TEG with gas containing excess
moisture, thereby reversing the driving force.
For the first approach, the gas was previously
dried at a lower temperature with glycol of about
the same concentration as that used for the point
studied. To reach equilibrium from the opposite
direction, we used gas from a higher contacting
temperature, Experimental results from the two
approaches were usually closer than the expected
analytical variation at the corresponding concen-
tration level. Where a larger discrepancy was
observed, the steps for a point were repeated.
This equilibration method is amenable to
conducting experimental determinations at several
temperatures using essentially the same TEG-water
solution and the same gas.
experimental sequence for any
would involve determinations
temperatures:
Schematically, the
TEG concentration
at the following
40 +600+800+ 1005+1200+1400+(1500)
400<.600,-800,- 1000.- 1200.1400 4-J
The 150F temperature gives an intermediate
(and usually incomplete) equilibration that shifts
enough moisture into the gas to insure the desired
approachto the 140 equilibrium point.
A knowledge of the amount of water contained
in the gas at saturation is fundamental for the
interpretation of water. in-gas experimental data.
VoIes percent of water were converted to pounds
per MMscf according the equivalence
I mol percent water = 474.71 lb water/\fMscf.
The latter units are used in the industry for dewpoint
measurements. After a survey of the literature on
moisture content of natural gases had been
conducted, dewpoint values were taken from the
charts published by the Institute of Gas
Technology. 3 Points below the minimum chart
temperature were extrapolated from published IGT
relationships.
Research grade T17G and distilled water were
used to prepare the various mixtures used in the
liqui 1 phase. .Methane was used as tht. gas phase.
Although a natural gas would be likely to contain
very slightly less water than would pure methane,
the difference does not appear significant. For
instance, Sharma 4114reports that ethane in amounts
up to 20 percent did not appreciably affect the
equilibrium water content of methane.
ANALYTICAL METHODS AND
EXPERIMENTAL APPARATUS
As shown schematically on Fig. 1, the equilibrium
measurement apparatus was built around three
interrelating systems.
1. r/ JF rwrlarl?rrg syslrm, where equilibrium
between water in gas and in TEG is reached at
constant temperature and atmospheric pressure;
2. The sampling system, whic!r makes it possible
to sample the gas and liquid streams without
disturbing the equilibrium;
3. Tbe ana)y[icnl system, basically a chromato-
graphy with recording and integrating facilities.
THE CONTACTING SYSTEM
This system consisted of a glass TEG-gas
contactor where the methane was bubbled through a
gravimetrically prepared solution of TEG and
water, a gas chamber, and circulating apparatus.
The desired equilibrium temperature was kept
constant in the contactor within f.0,05 F. Other
parts of the system were maintained at a higher
temperature to make sure that no condensation
occurred elsewhere. Gas, circulated by means of a
diaphragm pump, went through the sampling syringe,
was brought to equilibrium temperature as it passed
through a coil in the constant temperature bath,
bubbled through the TEG, and returned to the gas
container. Stratification in the container was
avoided by means of a small but powerful fan that
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
mixed the incoming gas with the bulk.
THE SAMPLING SYSTEM
The sampling system consisted of two subsystems,
one for liquid and one for gas.
To sample the TEG prior to water analysis, the
contactor was pressurized with equilibrium gas,
which forced the liquid through an enclosed rubber
tube mounted over the injecting system. To reach
the sample, the syringe needle went through an
outer septum, and once the liquid was sampled the
needle was pushed further through the injection
port septum. Thus, the sample was injected without
allowing the TEG to come in contact with the
humidity in the air.
To sample the equilibrium gas, a large sample
(up to 55 cc) was passed from the equilibrated
syringe into a freezing coil, where the water in gas
accumulated as ice. As too large an amount of
methane would have flooded the chromatographic
column, the volume of the gas sample was measured
by mercury displacement in a twin burette that
could be read to fO.01 cc. The water was then
released from its frozen state by heating and
routed to the gas chromatography. The resulting
peak was measured against an absolute water
response standard.
THE ANALYTICAL SYSTEM
The analytical system consisted of a chromato-
graphy with thermal conductivity detector, a
multirange recorder, andan Instron electromechanical
integrator. The recorder permitted the development
of large peaks by switching from the standard I-rev
range to a range of 0.1 mv. Both the liquid and the
gas samples were separated in columns packed
with Porapak Q.
PRECISION OF THE EXPERIMENTAL DATA
A common difficulty of previous work in this area
is the inability to reproduce analytical data
reliably. Consequently, investigators must adopt
self-imposed constraints as precision criteria for
experimental repeatability. Examples of the
precision achieved are presented in Table 1.
Experiments where repeatability was exceptionally
good were not considered for inclusion in the table.
Good precision is more significant for the analysis
of low concentration components, since any
deviation apparent there will have more relative
impor~ than if applied to the abundant component.
Different sample sizes could reproduce relative
concentrations well. However, efforts were made to
maintain constant sample volume. As the volume
of the liquid sample was only 2 microliters,
maintaining constant sample size was difficult. In
the example on Table 1, assuming that the counts
per microliter are constant throughout the series of
runs, a maximum deviation of
3.3 percent
corresponds to an absolute sample-size variation
of 0.000066 cc. In many runs, the count variation
was less than 3.3 percent.
Because Kw is the ratio of two concentrations,
analytical accurac, and precision cannot exceed
the worst of the two analyses involved. The gas
~ __, ~____
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II ~ CONSTANT TEMP BATH
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WITH TEG-GAS CONTACTOR
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CIRCULATING
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SPACE
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1;
Ill
SEBLED SYRINGE
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SEPTUM SYSTEM
20CC 1
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SYRINGE
1, I I PORAPAK O
!? % !!F d
COLUMNS
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FREEZING
1 I SAMPLE LOOP
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GAS
BURETTE
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IL_
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CHROMATOGRAPHY
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SAMPLI NGSYSTEM
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CONTACTI NG SYSTEM
FIG. 1 SCHEMATIC OF TEG-WATER-GAS EQUILIBRIUM MEASUREMENT APPARAT\JS,
OCTOBER, 1973
analyses at-e likely to show the larger variations
because of the small amount of water present.
Thus the most severe analytical limitations on the
study of equilibria exist at high TEG concentrations
and low temperatures, where water concentrations
are in the ppm range.
Experimental Run 65, listed in Table 1, illustrates
some of the least favorable conditions encountered
in our work, That run studied water distribution
between gas and 99.95 weight percent TEG at
60 F. Water in the gas phase was analyzed four
times, The results averaged 0.0034 mol percent
with a standard deviation of 0.00029. Water in the
liquid phase was analyzed three times. Results
(not shown in Table 1) averaged 0.4314 mol percent,
with a standard deviation of 0.01087. The range of
water equilibrium constant values spreads from a
minimum Kw of 0.007032 to a maximum K w of
0.008775. Average K is 0.00790420.000872,
How much of an achievement is a variation of
311 percent in the calculated K-value? While not
directly comparable, many studies were made on
the precision of hydrocarbon analysis by
chromatography. One study S shows that relative
variation between consecutive runs performed by
the same operator on the chromatography, increases
for any one component with its decreasing
concentration in the sample. Accordingly, the
relative deviation expected at a true concentration
of 0.003 percent is f35 to 70 percent. This work
reports water concentrations of 0.003 mol percent
(30 ppm) with a deviation of t8.5 percent.
Analytical accuracy is harder to demonstrate
since an analysis might be repeatable but wrong.
When data were suspect, a decision was made on
the basis of consistency checks. A study was
conducted to establish possible sources of
experimental error, and where consistency checks
were inconclusive the experiments were pursued
further.
EXPERIMENTAL RESULTS
EQUILIBRIUM DEWPOINT DEPRESS1ON
Water equilibrium dew points were established
for TEG concentrations ranging from a nominal 94
to 99.95 weight percent and equilibrium temperatures
of 40, 600, 80, 100, 120 and 140 F. Fig, 2 shows
the relationship between dewpoint depression and
TEG concentration at 80 F equilibrium temperature.
-. ...
TABLE 1 - PRECISION OF THE EXPERl!d ENTAL DATA
Percent
Fxneriment Stondfird Standard -. .-. . .
Number Type of Dots RUI-I 1 Run 2 Run 3 Run 4 Average - - Deviation Deviation Observations
.
Mol %H. O in aas 0.0030 0.0034 0.0035 0.0037 0.0034 0.00029
.-
Mol % CH4 in gas
Wt %H20 in liquid
Wt %TEG in liquid
Sample size, ml gos
Water counts, gas
TEG counts, liquid
Water counts, liquid
Mo] % HaO In gas
Mol % CH4 in gas
Wt %H20 in liquid
Wt %TEGin liquid
Sample size, ml 90s
Water counts, gas
TEG counts, liquid
water counts, liquid
Mol % HZO in gas
Mol % CH4 in gas
Wt % H20 in liquid
Wt % TEG in liquid
Sample size, ml gas
Water counts, gas
TEG counts, liquid
Water counts, liquid
Mol % H20 in gas
Mol % CH4 in gos
Wt % H20 in Iiqujd
Wt % TEG in liquid
Sample size, ml gas
Water counts, gas
TEG counts, liquid
Water counts, liquid
99.9970
0.0.533
99.9A67
18.7
43.4
185,681,
212.0
0.0145
99,985S
0.0633
99.9367
19.32
249,
194,853.
264.1
0,0902
99.9098
fl.0712
99.9288
18.
1,477.
190,621.
291.
0.3083
99,6917
5.5S66
94.4434
3.54
99Q
160,33%
17,383.
99,9966
0.0519
99.9481
54.38
143.4
192,043.
213,5
0.0140
99.9860
0.0601
99.9399
19.32
239,5
189,118,
243.7
0,0822
99.9178
0.0790
99.9210
17.86
1,329.
186,618.
316,
0.2949
99.7051
5.7813
94.2167
3,72
997.
152,487.
17,242.
99.9965 99.9963
0.0507
99,9493
54,9 36.52
150,2 108.
189,313.
205.5
0.014LI 0.0144
99.9855 99.9856
0.0588
99.9412
19.2 19.26
246. !3 245,5
189,852. (197,988. )
239.2 (212.0 )
0.0852 0.0882
99.9148 99.9118
0.1838 0.0837
999162 99.9)63
18. 18.
1,391. 1,434,
189,262. 189,003.
340. 339.
0.2825 0.2986
99.7175 99.7014
5,5119
94.4881
4.08 3.50
1,050. 951.
152,761.
16,421.
99.9966 0,072
0.0520 0.0013
99.9480 0.088
189,012. 3,192.
210.3 4,25
0.01435 0.00024
99.9856 0.072
0.0607 0.0023
99.9393 0.063
19.275 0,057
245.1 4,03
191,274. 3,114,
249. 13.3
0.0864 0.0035
99.9136 0.11
0.0794 0.0059
99.9205 0.063
17.965 0.07
1,407,8 63.2
188,876. 1,659,
321.5 23.16
0.2961 0.0107
99.7039 0.130
5,6166 0.144
94.3834 0.165
3.71 0.265
999.3 40.45
155,194. 4,456.
17,015, 519.4
65
67
70
101
8,5
0.07
2.5
0.09
(1) (2)
(1)
1.7 (4)
2.0 (4)
1.7
0.07
3.8
0.06
0.3 (2)
l,rj
1.6 (3)
5.3 (3)
4.0
0.11
7.4
0.06
0.4 (2)
4,5
0.9
7.2
3.6
0.13
2.5
0.17
7.1 (2)
4,0
2.9
3.1
(1)
(2)
(3)
(4)
300
No direc+ comparison because of different sample sizes.
Before calculation volume is corrected for barometric pressure and ombient temperature.
Figures in parentheses not used for calculation.
Sample size: 2 microliters = 0.002 cc.
SOCIETY OF PETROLEUM ENGINEERS JOURNAL
Similar plots can be drawn for other equilibrium
temperatures. Dewpoint depression, measured in
equivalent degrees F, decreases with decreasing
contacting temperature. The rate of the decrease
appears to be a function of the equilibrium
temperature. Everything else being equal, the
higher the contacting temperature (i.e., water
saturation) of a gas, the larger the amount of water
removed at equilibrium. The amount of water removed
from the gas decreases with increasing dilution of
the contacting TEG. Presumably, the TEG-water
solution ceases to be very effective as a dehydrating
agent once it reaches a certain composition. By
extrapolation on Fig. 2, that composition is found
at approximately 60 weight percent water.
The semiIogarithmic relationship between dewpoint
160
MO-
K%
120-
100-
\
%
80 -
$
60 -
\
\%
40 -
\
\
*oo~%!84q
10 50 ;
CONcEN(RA1lON 0S I+ZOIN T~G ~ %
2 DEWPOINT DEPRESS1ON VS TEG CONCEN-
TRATION, 80% EQUILIBRIUM TEMPERATURE.
110
100 -
90 -
80 -
70 -
:
# 60
g 50 -
~ 40
r
~ 30
1-
= 20
: 10 -
Ho
~ -,0 .
>
~-zo
+
s -30
-40
-5 o
-6o
-7o
WI % TEG
/
90
x?:
-80
t
-90 - ~.
60 80 100 120 I40 160
EQUILIBRIUMTEMPERATURE. t.F
FJIG. 3 WATER DEWPOINT TEMPERATURE OF
METHANE IN EQUILIBRIUM WITH TEG. LEAST-
SQUARES FIT OF EXPERIMENTAL DATA (LINEAR).
6)CTO~ER, 1973
depression and TEG concentration points up the
fact that small increments in TEG concentration
correspond to increasingly larger dewpoint
depressions and significant gains in absorber
performance.
Values interpolated from plots like Fig, 2
were used to present the experimental data as
Equilibrium Dew Point vs Equilibrium Temper-
ature on Fig. 3, and as Equilibrium Dew Point
vs Water Concentration in TEG on Fig. 4. They
also form the basis for an empirical correlation
that will be further discussed in the section on
Data Interpretation.
Experimental data on Fig. 3 confirm that the
equilibrium water dew point of a natural gas
decreases with increasing concentration of the
contacting TEG, and with decreasing contacting
temperature. The family of concentration isograms
was extended below the lowest TEG concentration
actually studied (94 weight percent). However,
data are not shown beyond the highest experimental
concentration of 99.97 weight percent.
Fig. 4 is useful as a consistency check for data
generated experimentally. The equilibrium temper-
atures are operating parameters, so Fig. 4 is
expected to show a family of isotherms where
equilibrium dew point at 100 percent water is the
equilibrium temperature itself. In effect, the
isotherms may be drawn as straight lines up to
approximately 60 percent water, after which they
curve slightly toward the expected temperature.
Water Distribution Between TEG and Methnne
Fig. 5 presents a plot of gas-liquid equilibrium
ratios, Kw, as a function of TEG concentration, for
the temperature range 40 F to 140 F and atmospheric
pressure. Logarithmic coordinates were chosen as
a matter of convenience because they compress a
wide range of data into one figure. To emphasize
the important role of even small amounts of liquid
water, the abscissa shows weight percent water in
the contacting TEG rather than the concentration
of TEG itself.
On first approximation, K-values show little
-:70., ;2 ~5 ,0 ~.
I
$0 IN 200 50Q {000 20 50 10004
W1H3MT % WATt R IN1t G
FIG. 4 WATER VAPOR DEW POINT VS WEIGHT
PERCENT WATER IN EQUILIBRIUM TEG (NON-
SMOOTHED EXPERIMENTAL DATA).
301
dependency on contacting TEG concentration,
throughout the concentration range of this study.
Horizontal isotherms, drawn through the average
value of all K-data at ~ne temperature, present a
reasonable fit. However, a statistical analysis of
the data, confirmed by thermodynamic fitting,
indicated that K increases slightly with increasing
TEG concentration.
Equilibrium values roughly doubled for every
20F increase in equilibrium temperature. Fig. 6,
which shows a plot of K vs equilibrium temperature
for a contacting 99.0 weight percent TEG is typical.
Regardless of the method used to smooth the data,
the relationship is quasilinear within the studied
range of TEG-water compositions. If the relatively
small effect of TEG concentration is ignored, one
single line applies to the temperature range 400 to
140 F. Its empirical equation offers an easy-to-use
first approximation of water equilibrium values at
atmospheric pressure:
Kw=e
0. 035129 L23. 082f 55. . (2)
For more accurate calculations, the curvature of
the plots (Fig. > and 6) cannot be ignored, however.
Comparison wltb Pub Iisbed Data
The Chevron Oil Field Research Co. (COFRC)
results reveal some general similarities in shape
with published data. However, differences in value
are significant. Closest to our observations are
data published by Union CarbideG and by Worley,7
Fig. 7 presents several typical isograms of
equilibrium dew points vs equilibrium temperatures
from the two sources mentioned above. Generally,
COFRC equilibrium dewpoint temperatures are
lower than Union Carbides for corresponding TEG
concentrations. On the other hand, both sets of data
show a very similar dependence on the contact
temperature. The similarity is particularly apparent
for TEG concentrations around 99 weight percent.
The equilibrium dew points in Ref. 7, which
?0
1, , ,
I
,
I
1
001 I
, [ , ,(#i 1 ! , , J
01 L% *O .$ 10 60 10
WATCR W+4CLNTRA110N IN TCO. !MIG.T %
FIG. 5 WATER EQUILIBRIUM CONSTANTS IN
THE TEG-GAS-WATER SYSTEM; 14.7 PSIA
EXPERIMENTAL,
were obtained from operating glycol contractors
and extrapolated to an infinite number of trays and
glycol rates, coincide very well with COFRC values
at the extremes of the concentration range. The
similarity does not hold true for intermediate
concentrations, where differences in dewpoint
temperature range up to 16 F, the COFRC data
being the more conservative.
I
1
w
.
J
01
00
x
/
COFRC ExPERIMENTAL
oAT A 990wT%ltG
$
/
e
/
/
/
+
~ , ~ 0035129 1 - 2308265
Tm OR
)0) (520) (540) (5601 (580) (600) R
40 bb 8( Icc ,X 4 F
61)un,,I+K: R). 11,p! IIAIIJR~ p v
FIG. 6 VARIATION OF WATER EQUILIBRIUM
CONSTANT WITH TEMPERATURE.
110[-
wEIGI+T %TEC
100
[
90 -
80
101- /
, . .. .. -w
/
/
/
/
/
/--71
/
/
/ -
/
/ //
/
A
/
/
/
/
/
//-
/
/
.-
.
/
:=
40 60 80 [M 120 140 160
ECIUILKIRIUM TEMPERA1uR6. t F
FIG. 7 WATER DEWPOINT TEMPERATURE OF
NATURAL GAS IN EQUILIBRIUM WITH TEG.
aoz SOCIETY OF PETROLEUM E~Cl~EE~S JouR~~L
Comparisons of COFRC equilibrium dew points
with other values in the literature, for example
those published by Dingman and LeBas,8 or Dow
Chemical Co.,g~10 are much less satisfactory.
Data published in 1961 by Scauzillo2 deserve
special mention since they are calculated on the
basis of older experimental fugacity values rather
than determined experimentally. Scauzillos data
are very similar to Worley s, which they precede by
5 years.
Few papers on the subject allow a direct
comparison with the gas-liquid equilibrium values,
K, originated in this investigation, In most
instances, K-values must be calculated indirectly,
from equilib~ium dewpoint data for natural gas or
from vapor pressure over aqueous TEG solutions.
Calculations are limited by some implied
assumptions: in the case of dewpoint data we need
to know what moisttire charts, if any, were used
by the author in translating water content of gas
into equilibrium dewpoint temperatures.
TEG-water so]utions have two partial vapor
pressure components. TEG vapor pressure is very
low at experimental temperatures. Townsends 11
estimated value, 0.01 mm Hg at 68 F, is in line.
with the Union Carbide and Dow Chemical published
data. Wise etal.~2 indicated that TEG vapor pressure
(PTEG) between 69 and 84F obeys the relationship
log PTEG = ~; f i + 7. 758 s (3)
In either case we conclude that, within our
experimental range, errors that result from neglecting
the TEG vapor pressure would not be significant.
Despite differences in value, most shapes of
K-vs-TEG concentration plots obtained from
published data are similar to those found in our
investigation. However, some isograms have more
pronounced curvatures and exhibit a minimum for
certain TEG concentrations.
In conclusion, water equilibrium constants are
virtually independent of TEG concentrations at the
high TEG concentrations required in gas dehydration
(98 to 99.5 weight percent TEG). With increasing
concentrations of water in TEG (95 percent TEG),
equilibrium constants do increase. The difference
in K-values between the conditions at the top and
at the bottom of a glycol contactor could therefore
be significant.
INTERPRETATION OF DATA
DATA SMOOTHING AND CORRELATION
Least-squares smoothing methods were applied
where data appeared to be in a linear or
sernilogarithmic relationship. In most of the data
sets the correlation coefficient was very close to
unity. The smoothed data were then correlated by
an empirical equation, based on the variation of
the equilibrium dewpoint depression with TEG
concentration, at various temperatures. Given two
variables within our range of investigation, the
third can be calculated.
WATER VAPOR DEWPOINT DEPRESSION
The variation of dewpoint depression with glycol
concentration and temperature, one example of
which is shown on Fig. 2, can be fitted to an
equation of the type
W=aebD) . . . oo( 4) 4)
where a is the intercept on the water concentration
coordinate and b is the slope of dewpoint depression
variation with weight percent water in TEG. In
physical terms , a is the weight percent of water in
an aqueous glycol solution where the glycol is too
diluted to remove water from natural gas. Both a
and b are temperature dependent and can be
correlated by semilogarithmic exponential equations.
Eq. 4 can then be rewritten in a generalized form:
w=
( o0074f1
I n T- 6. 7932
G
)
exp
[(
6)]
i n T- 6. B7! 36~D . . . . .(5)
11. 364
When TEG concentration and equilibrium temperature
are known, dewpoint depression can be calculated
from the following form of Eq. 4:
D=
in W- I n a
77- - ( 6)
where all terms are either known or can be
calculated.
Eq. 4 is not amenable to an explicit solution for
the contacting temperature, T, even if both ~~and
D are known. However, T can be easily calculated
with a computer by trial and error.
EQUILIBRIUM DEWPOINT CALCULATION
Water vapor dewpoint temperature, TD(OF) can
be calculated from the following equation:
D
=T - (D + 459. 7). . . . . . (7)
Within the range of concentrations and temperatures
investigated, the equations above permit a quick
evaluation of attainable water dew points, provided
the natural gas and TEG come close tc equilibrium.
Since the attainable dew point is assumed to be
independent of pressure, the above equations can
be applied to real systems.
Fig. 8 is a plot of the equilibrium dewpoint
temperatures calculated from Eqs. 6 and 7. TEG
concentrations were extended below experimental
range to account for the lowest iikely composition
at the bottom of a glycol contactor. The resulting
concentration isograms exhibit a slight curvature
that becomes more pronounced as the equilibrium
temperature increases.
To test the validity of the generalized dewpoint
equation, data calculated from individually smoothed
dewpoint depression plots (Fig. 2, for instance)
were plotted for comparison along the 90.0, 99.0
and 99.9 weight percent TEG lines, With one
oCTOBER, 1973
.903
exception at 40 F, the individual data points fall
within 3F of the predicted dewpoint temperature.
The fit is even better in the high-temperature,
high-concentration range where exact data are
scarce.
Another validity test is to check how well the
curves on Fig. 8 can predict values beyond the
range of this ifivestigation. An equilibrium dew
point was originated experiment~lly at 1600F and
99.906 weight percent TEG. Tht solid circle shows
the experimental results, the open circle the
predicted dewpoint temperature. The difference of
1.44 F is only 0.9 percent of the 159.1F total
dewpoint depression.
BASIC EQUILIBRIUM RELATIONSHIPS
FOR THE SYSTEM TRIETHYLENE
GLYCOL-WATER-NATURAL GAS
Several previous attempts to describe the
TEG-water-gas system by means of an equation of
state were limited by the disparity in the nature of
the components and the uncertainty of the
experimental data. The thermodynamic approach
was used by Wise et al.lzto measure equilibria in
the binary system TEG-water. Townsendl 1 and
later Scauzillo2 considered TEG-water-nattual gas
systems from a thermodynamic point of view.
Results were not too satisfactory, however.
To extend correlating applications, various
thermodynamic equations were fitted to the COFRC
experimental data. Among them, the White equationl
110
100
90
[ /
80
G
70
:
n 60
1-
g 50 -
~ G
a 40
u
~ 20 - EG
2 l o
-1
s 90.
80
/%
/
/
&
g -30
-40
-60 gg~
-80 ~%
-90-
1 1
40 60 60 100 120 140 160
EWILIBRIUM TEMPERATuRE.f F
FIG. 8 WATER DEWPOINT TEMPERATURE OF
METHANE IN EQUILIBRIUM WITH TEG (EXPONENTIAL
LEAST-SQUARES FIT OF EXPERIMENTAL DATA).
sol
was chosen because of its successful application
. .
to binary systems of widely different boiling
points. 13 The equation calculates water activity
coefficients, which in turn can be defined in terms
of the equilibrium constant.
APPLICATION OF THE WHITE EXPRESSION
TO THE EXPERIMENTAL DATA
The White equation describes vapor-liquid
equilibria in terms of temperature, pressure, liquid
composition, and two independent constants. Similar
to the Van Laar equation, the expression includes
a temperature factor and possesses other correlating
advantages that will be discussed later. For a
binary system the equation takes the following form:
()
b,
1. 5
1
[ T l o9 yl l - 0*5 = ~ $
( )0
1. 5
bl be, . . . . . . . .
+
a21
q
()
1. 5
b2 2
CT l og y2] - 05 = ~ ~
( )()
1. 5
b2
+
bl . . . . . . ..(8b)
a12
q
The ratios of constants in Eq. 8a are also constants:
()
b 1, 5
~
=m= constant . . . .(9)
G
b2 n
=
= constant . ( 10)
bl
Their values can be calculated from the slope and
intercept of the linear plot:
[ T log yl]-05 VS X, 1X2
This is a significant advantage when experimental
values for the equilibrium of the second component
(TEG) are very difficult to evaluate. A numerical
solution of the expression (T log yl )-05 is likely
to be imaginary, but that fact appears to have no
effect upon the applicability of Eq. 8a, provided
that xl/x2 <2.
In this work, the White equation was used both
as a means of smoothing experimental data and as
a correlating instrument. The correlation had the
form
SOCIETY OF PET ROLEIIM ENGINEERS JO UR31AL
Xw
(T I n ~w) - o. 5
= 0000g2 XTEG
+0. 0535 ( 11)
when fitted to nonsmoothed experimental data, and
Xw
( T I n ~w) - 005
= o*0063 xTEf j
+0. 05449 ( 12)
when fitted to data smoothed by the least-squares
method.
Small differences in the constants obtained for
the two cases do not amount to a significant
difference in the calculated values.
AS xw/xTEG
<<1.0 over most of the concentration range studied,
the two equations give practically equivalent
results. We believe that Whites expression, in the
form of Eq. 12, is the best correlating instrument
for the present investigation. The various aspects
of the calculated values are considered below.
CALCULATION OF WATER EQUILIBRIUM
CONSTANT, K
The activity coefficient is related to the
equilibrium constant, K, as follows.
Yi p
P
Yi =~V=K
. (13)
i Pi
I wo
To calculate K at other pressures and
temperatures, Eqs. 12 and 13 are combined into the
following expression:
K=
r
1
( ) 1
p, ..
exp -
~+l n
.(14)
~
~nLT
where
n E 0. 0063
(
w
FE G
+ 0. 05449 ( 5)
Fig. 9 is a plot of calculated K-values for various
equilibrium temperatures as a function of water
concentration in the contacting TEG. The calculated
values exhibit the same features as the equilibrium
constants shown on Fig. 5. However, trends in the
results are easier to distinguish from experimental
scatter. The apparent independence of the equilibrium
constants from contacting TEG concentration is
confirmed by the flat equilibrium isotherms at
concentrations over 98 weight percent. However,
equilibrium constants are increasingly larger for
more dilute TEG as would be found at the bottom
of a conta ctor.
Fig. 10 shows the variation of the equilibrium
constant with equilibrium temperature. The plots
exhibit a slight curvature and are very close
together and parallel for TEG concentrations of
OCTOBER, 1973
95.0, 98.0 and 99.9 percent. The experimental
values on Fig. 6 compare reasonably well with
those calculated.
Equilibrium water-vapor dew points can be
derived from the calculated equilibrium constants.
Water concentration in :he gas phase is translated
into dewpoint temperatures by means of a suitable
natural gas moisture chart. For higher TEG
concentrations, calculated dew points are slightly
higher than the experimental data at the lower
equilibrium temperatures, but coincide well or are
slightly higher at temperatures in the range of 120
to 140 F. The 160 F experimental check of the
correlations extended vaIues shows a difference of
only 1.7 F, or 1.1 percent of the total dewpoint
depression.
r
t ,..
,.
.
v
.
.
i:l:~
. .
.
.
.
. . .
.
. d
.W
I
40,6
:
:
%
ml
,,, , I I I I
0! C6 10 5 10 50 10
WATER CONCi Ni RA7(0N IN 7[0 w1kG T %
FIG. 9 WATER EQUILIBRIUM CONSTANTS IN
THE TEG-GAS-WATER SYSTEM; 14.7 PSIA WHITE
I
1
31X*
X3
01
001
EQUATION.
W %TEG
/%
WHITEEOUATIONFITTEOTO
COFRCEXPERIMtNTALOAIA
98
999
.
40 60 80 100 1?0 140
EOWIIBRIUMIE?APERATuRE F 7
FIG, 10 VARIATION OF WATER EQUILIBRIUM
CONSTANT WITH TEMPERATURE; 14.7 PSIA.
30s
CONCLUSIONS
Water-vapor dewpoint temperatures can be lowered
to a greater extent than predicted by most published
glycol equilibrium data.
Experimental dew points are dependent 0~
equilibrium TEG concentration and temperature and
can be described by means of a thermodynamic
relationship. Close first approximations may be
obtained from an exponential least-squares
correlation that allows calculation of either dew
point, TEG concentration, or equilibrium temperature
if the two other quantities are known.
Water equilibrium constants are virtually
independent of TEG concentration in the high
con centration range required for advanced gas
dehydration. If TEG contains more than a nominal
3 weight percent water, equilibrium constants
increase significantly with increasing concentrations
of water. The difference in TEG concentrations
between the top and the bottom of a glycol contactor
could therefore be significant.
The dependence of the equilibrium constant on
contact temperature is exponential. The equilibrium
water content of the natural gas roughly doubles for
every 20 F increase in temperature. The relationship
provides a useful first approximation for all TEG
concentrations studied.
The effect of contacting pressure on water vapor
dewpoint temperature and water distribution constant
was not investigated. A consensus of published data
indicates that equilibrium dewpoint depression is
independent of pressure and that the water
equilibrium constant decreases with increasing
pressure. The thermodynamic expression of White,
found valid for our data, indicates that the latter
assertion is correct.
The White correlation fitted to our smoothed
experimental data (Eq. 12) is recommended as the
preferred method for obtaining design data on
triethylene
D=
P=
PTEG =
T=
TD .
w=
a12 =
61,62 =
p. =
p; =
glycol contractors.
NOMENCLATURE
dewpoint depression = saturation temper-
ature - equilibrium dewpoint tempera-
ture, F
system pressure, psia
TEG vapor pressure, mm Hg
equilibrium temperature, R
water-vapor dewpoint temperature, F
weight percent water in equilibrium TEG
- a21 = constants
constants in White equation
partial pressure of pure water
vapor pressure of the pure component i
at system temperature
Xw =
mole fraction of water at equilibrium in
the liquid phase
yi =
yw .
y.
mole fraction of component i in vapor
phase
mole fraction of water at equilibrium in
the gas phase
activity coefficient
SUBSCRIPTS
w = water
TEG = triethylene gIycol
ACKNOWLEDGMENTS
I wish to express my thanks to Chevron Oil Field
Research Co. for permission to publish this paper
and to C. A. Johnson for his competent and
meticulous handling of the demanding experimental
program.
I.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11,
12.
13.
14.
REFERENCES
White, R, R.: Vapor-Liquid Equilibria in Non-Ideal
Solutions, Trans., AIChE (1945) Vol. 41, 539.
Scauzillo, F, R.: Equilibrium Ratios of Water in
the Water-Triethylene Glycol-Natutal Gas System,})
J, Pel. Tech. (July 1961) 697-702; Trans., AIME,
vol. 222.
Bukacek, k, F.: Equilibrium Moisture Content of
Natural Gases, IGT Research Bull. 8, Chicago
(1955); Charts of the Equilibrium Moisture Content
of Natural Gases, $J Supplement to IGT Research
Bull. 8 and ASTM Method D 1142-58, Chicago (1959),
Sharma, S. C.: Equilibrium Water Content of Gaseous
Mixturea, PhD thesis, U. of Oklahoma, Norman
(1969),
Millhone, R, S. and Fett, E. R.: Chromatographic
Analysis of Natural Gas Liquids, Ptoc,, 41st
Annual Fall Meeting of WGP and ORA, Anaheim,
Calif. (Oct. 1966) 91-109.
GIYCOIS, Bull. F-4763H, Union Carbide Corp.
(1964) Table 29, (Page 46).
Worley, M. S.: TEG Still the Least Expensive
Route, Cdn, Petroleum (June 1967) 34.
Dingman, J, C. and LeBas, C. L.: NOW New
Dew Point Data for Triethylene Glycol Solutions,
Oil and Gas ]. (Feb. 3, 1964) 7.5.
Gas Conditioning Fact Book, Dow Chemical Co.,
Midland, Mich, (1962).
GIYcoIs, Properties and Uses, Form No. 125-285-
61, Dow Chemical Co., Midland, Mich. (1961).
Townsend, F, M.:
~~Equilibrium Water Content S of
Natural Gas Dehydrated by Aqueous Diethylene and
Triethylene Glycol Solutions at Varioua Temperatures
and Press ures, PhD thesis, U. of Oklahoma, Norman
(1955).
Wise, H., Puck, T. T. and Failey, C. F,: Studies
in Vapor-Liquid Equilibria: The Binary System
Triethylene Glycol-Water, j, Pbys. Chern, (1950)
vol. 54, 734.
Ha-la, E., Pick, J., Fried, V, and Vil~m, O.: Vapour-
Liquid Equilibrium, 2nd English Ed., trans. by G.
Standart, Pergamon Press, Oxford (1967).
Sharma, S. C, and Campbell, J. M.: Water Content
of Natural Gas, paper presented at 1969 NGPA
National Convention.
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S06 SOCIETY OF PETROLEUM ENGINEERS JO CRNAL