Equilibrium Water Content of High Pressure Acid Gases: a Mathematical Model

Paper By: W. D. Monnery*, Xergy Processing Inc. W. Y. Svrcek, University of Calgary I. A. Alami, Saudi Aramco

November 2006

2 * Author to whom correspondence should be addressed (wmonnery@shaw.ca)

ABSTRACT A new simple, theoretically-based model that predicts equilibrium water content of pure acid gas components and acid gas mixtures has been developed for a temperature range of 32 to 212 F (0 to 100 C) and a pressure range of 14.7 to 2,000 psia (101 to 14,000 kPa). This new model provides a quantitative estimate of changes in equilibrium water content of acid gas mixtures due to a change in system pressure, temperature, or composition. When compared to available experimental data, the new model has an absolute average error (AAE) of 14%. At pressures above 2,500 psia and where no experimental data exist, the new model compares very well to the industry-accepted software, including AQUAlibrium and VMGSim with an AAE of less than 8%. INTRODUCTION The most popular sulphur recovery method utilizes the modified Claus process in which a combustion furnace followed by a series of catalytic reactors are used to produce elemental sulphur from H2S. Since a Claus plant does not recover 100% of the sulphur, the tail gas is incinerated emitting SO2 and CO2 to the atmosphere. Due to high capital and operating costs as well as low demand and oversupply of elemental sulphur, acid gas re-injection into deep geological formations emerged as a viable option. In addition to providing a cost-effective alternative to sulphur recovery, the deep injection of acid gas reduces emissions of noxious substances into the atmosphere and alleviates the public concern resulting from sour gas production and flaring. To effectively design an injection scheme, water content, phase behavior and physical properties of the acid gas mixture over the range of operating temperatures and pressures are required. Although phase behavior and physical properties are relatively well predicted with existing equations of state, water content is not (Clark, 1999). Our objective is to develop a theoretically based mathematical model that can be applied easily to predict the water content of acid gas mixtures at temperatures and pressures required by operating companies. AVAILABLE MODELS The problem of determining the water vapor content of sour natural gas is essentially that of calculating the composition of a mixture at certain temperature and pressure conditions. The methods available for calculating the water content of natural gas fall into three categories: (1) partial pressure approach (ideal model); (2) empirical plots and correlations; and (3) equation of state (Alami et. al., 2005). The first two approaches are limited either by the temperature and/or pressure of applicability or the H2S/CO2 concentration. Requiring the use of a computer, models based on equations of state perform better when interaction parameters used in the sophisticated mixing rules

4 are based on experimental data. AQUAlibriumTM and VMGSim, as examples of this approach, have rigorous thermodynamic models specifically designed to calculate phase equilibria between vapor, aqueous liquid and non-aqueous liquid phases for systems containing light hydrocarbons, H2S, CO2 and water. The model parameters are extracted from experimental data by regression. This type of software is widely used in the gas processing industry. These approaches are reviewed briefly in the following sections. 1. Partial Pressure Approach (Ideal Model) If the mixture were to act such that the vapor phase behaves as an ideal gas and the liquid phase behaves as an ideal solution, then the Raoults law and Daltons law can be used to describe the phase equilibria (Campbell, 1994):
Pi = Pi vap * xi

(1)

and
Pi = P * y i

(2)

Equating Raoults law and Daltons law for water w and rearranging:
yw =
vap Pw * xw P

(3)

Since water in almost immiscible in the hydrocarbon liquid phase, x w , is usually assumed to be equal to unity. Thus, the water mole fraction in the gas, y w , can be calculated as:
yw =
vap Pw P

(4)

Ideal gas behavior is a limiting case and seldom do real gas/gas mixtures approach this condition except at low pressure and high temperature. Equation (4) is recommended for system pressures up to about 60 psia (400 kPa) (Campbell, 1994). 2. Empirical Plots and Correlations i. McKetta and Wehe Correlation for Sweet Gases Empirical plots are still widely used for engineering calculations. For a lean sweet natural gas, the chart developed by McKetta and Wehe (McKetta and Wehe, 1958) may be used. The McKetta-Wehe chart includes correction factors for formation water salinity and gas gravity. The water content shown on such charts is the maximum that the gas can hold at the pressure and temperature shown. It is fully saturated; the relative humidity is 100% or, stated in another way, the temperature is the water dew point temperature of the gas at the pressure and concentration shown. To facilitate the use of

5 these charts, Behr (Behr, 1983) and later Kazim (Kazim, 1996) proposed alternative analytical expressions that fitted the natural gas dew point versus the water content. The use of the mentioned charts and correlations, however, will result in serious errors if used for acid or sour natural gases since both H 2S and CO2 can contain more water at saturation conditions than methane or sweet natural gas mixtures. Corrections for H2S and CO2 should be applied when the gas mixture contains more than 5% H 2S and/or CO2 at pressures above 700 psia (4800 kPa) (Gas Processors Association, 1998). ii. Maddox Correlation for Sweet and Sour Gases To correct for significant acid gas (H2S and CO2) content, Maddox (Maddox, 1974) proposed the following correlation to calculate a weighted average water content, W:
W = y HC * W HC + y CO2 * WCO2 + y H 2 S * W H 2 S

(5)

Maddox assumed that nitrogen holds about 6 to 9% less water than methane and therefore can be included as a hydrocarbon, thus providing a small safety factor. This correlation provides adequate predictions at low pressures but tends to underpredict water content at high pressures. iii. Robinson et al. Correlation for Sour Gases The Robinson et. al. (Robinson et al., 1978) correlation for sour gases was developed based on a modification by Soave of the Redlich and Kwong (SRK) equation of state (Robinson, 1976). They generated a series of charts at pressures of 300, 1,000, 2,000, 3,000, 6,000 and 10,000 psia for temperatures from 50F to 350F. Robinson et. al considered all hydrocarbon components to be essentially CH4 and they assumed that CO2 carries only about 75% as much water as H 2S over the entire pressure/temperature range. Therefore to use these charts, one uses the following relation to calculate the effective H2S dry gas composition:
equiv y H 2 S = y H 2 S + 0.75 * y CO2

(6)

The charts are applicable for H2S equivalent composition up to 40 mole % and the water content on these charts is reported in bbl/MMscf which can be converted as follows: lbm/MMscf = 350 * (bbl/MMscf) lbm/MMscf: pound mass per million standard cubic feet bbl/MMscf: barrels per million standard cubic feet This method is cumbersome to use due to the multiple interpolations involved and cannot be used for pure acid gas mixtures, i.e., no hydrocarbons in the mixture. (7)

6 iv. Wichert and Wichert Method for Sour Gases Wichert and Wichert (Wichert and Wichert, 2003) proposed a relatively simple acid gas correction based on the equivalent H2S content given by the following equation (similar to that of Robinson et al. but assumes that the CO 2 carries only 70% as much water as H2S at the same conditions):
equiv y H 2 S = y H 2 S + 0.70 * y CO2

(8)

They presented a single chart where one could obtain a correction factor, Fcorr at a given temperature, pressure and equivalent H2S composition. The water content of the sour gas is then calculated by the following equation:
W = Fcorr * W HC

(9)

This method is applicable for temperatures from 50F to 350F and pressures from 100 psia to 10,000 psia. It is limited, however, to sour gas mixtures with an H2S equivalent concentration of 50% and cannot be used for acid gas mixtures (H2S and CO2). 3. Equation of State (EOS) Models: i. Robinson et al. Approach The Robinson et al. approach, mentioned earlier, originated from the concept of partial fugacity of component i in a mixture:
f i L = f iV

(10)

The equilibrium constant Ki, expressed in terms of the fugacity coefficient for a component in a mixture, is:

Ki =

yi i L = xi i V

(11)

This predictive model was developed using the Soave modification of the Redlich-Kwong, (SRK), equation of state (Robinson, 1976). Sophisticated mixing rules were employed in which the interaction parameters were adjusted using the published data for binary mixtures of CH4-, H2S-, and CO2-H2O. Because of the limited amount of experimental data, this method tends to underpredict the water content of acid gas mixtures at high pressures. The method is not really suitable for manual calculations and requires programming into a computer. Finally, it should be limited to sour gas mixtures with up to 40 mole % equivalent H2S.

7 ii. Sharma and Campbell Approach Sharma and Campbell (Sharma and Campbell, 1969) developed a predictive method based on the McLeod corresponding states approach (McLeod and Campbell, 1969). The following steps summarize this method: 1. Calculate the Eykman Molecular Refraction (EMR) critical pressure, critical temperature and Z factor of the mixture using the McLeod corresponding states approach (Sharma, 1969). Obtain K from a chart or calculate using the following equation:

2.

( f vap / Pwvap ) vap 0.0049 K = ( Pwvap / P ) * w * ( P / Pw ) ( f w / P)

(12)

3. From a generalized fugacity chart, determine the value of f / P and hence f for the gas mixture on a water-free basis 4. Determine the gas-water content from the following equation:
yw = K * ( f w / f ) Z

(13)

This model was originally intended for water content prediction of sour gases with less than 20 mole percent of any component except methane for a nominal temperature range of 100F to 160F and a pressure range of 200 psia to 2,000 psia (Sharma, 1969). The model, however, underpredicts the water content of acid gas mixtures with low hydrocarbon content, with errors, as high as 84%, especially at high pressures (Alami, 2004). iii. Awad et al. Approach Awad (Awad et al., 2002) proposed a new theoretically-based mathematical model that estimates the water content of a saturated natural gas, both sweet and sour, up to 10,000 psia and 460F:
vap vap y w = ( w / w ) * ( Pw / P ) * PC

(14)

The model uses the Soave-Redlich-Kwong equation of state to calculate the fugacity coefficient of water in a natural gas mixture. It includes interaction parameters for water with hydrocarbons and water with CO2 and H2S. The calculation procedure, however, is tedious and must be computer-based. This model, like Sharma-Campbell model, also suffered at high pressures and high acid gas contents, resulting in errors in excess of 85% (Alami, 2004).

8 iv. AQUAlibriumTM AQUAlibriumTM is a rigorous thermodynamic model specifically designed to calculate phase equilibria between vapor, aqueous liquid and non-aqueous liquid phases for systems containing light hydrocarbons, H2S, CO2 and water (Carroll, 2004). AQUAlibriumTM uses a Henrys law approach for the aqueous phases and the PengRobinson Equation of State (PR EOS) for the non-aqueous phases (Clark, 1999). The model parameters are extracted from experimental data by regression. v. VMGSimTM VMGSimTM is a process simulator with over 5,500 components, designed to rigorously simulate chemical processes (Satyro, 2006). Although it has many property packages, for the prediction of water content of acid gases, it uses a rigorous thermodynamic model in its flash calculations based on a specially modified Peng-Robinson Equation of State (PR EOS) to describe both the vapor and liquid phases. The modified PR EOS has had the mixing rule interaction parameters regressed to a wide array of experimental hydrocarbonwater solubility data. NEW MODEL Sharma-Campbell and Awad et. al. models represented the best candidates for our objective of a simple but theoretically-based model since they were both based on the equilibrium requirement of equal fugacities. The Sharma-Campbell model was not used, due to the complexity involved in calculating the true critical properties, based on the EMR approach for gaseous mixture for the calculation of the compressibility factor and the fugacity coefficient. To accomplish our goal of a simple mathematical model, with a theoretical basis, it was decided to modify the Awad et al. model using a function of the following form (see equation 14):

y w = M * (Awad Model)
where M is an empirical constant.

(15)

M was fitted and generalized using the available experimental data for pure H2S and CO2 from Selleck et al. (Selleck and et al., 1952) and Weibe and Gaddy (Wiebe and Gaddy, 1941) and from Clark (Clark, 1999) for acid gas mixtures. The modified model was developed first for pure acid gas components, H2S and CO2. As can be seen from equations 12 and 14, fitting equations for the water vapor pressure and water fugacity at vapor pressure and system pressure were needed for both our approaches. Generalized equations for vapor fugacity and water molar volume were also required (Alami et. al., 2005) (Alami, 2004).

9 Pure Components Since analysis of the correction, to match the Awad et al. model to actual acid gas experimental data, looked like a cumulative probability curve, the following equation with the constraint shown was used. .
2 P C 4 * ln 1 ( ) C 3 2 M =C1 +C 2 * ex ( 1 p C4
2

(17)

where: P = pressure in psia, Condition: P C 3 + C 4 * ln(1

2 ) 2

If the above condition is true, equation (32) will be evaluated and value of "M" retained. If the condition is not satisfied, "M" = C1, the transition of "M" from the value of C1 to the one calculated by equation (17) occurs at or near the pressure corresponding to the change in water content of the gas due to phase changes. Therefore, parameters C1, C2, C3 and C4 had to be fitted such that they can capture this transition at different temperatures and resulted in two sets of equations for these parameters. For H2S, the equations were as follows:
C1H 2 S = 0.8501 C 2 H 2 S = exp( 3.91 0.0148 * T ) C 3 H 2 S = ( 4.066 + 2.155 * T ) 2

C 4 H 2 S = exp( 5.66 836 .96 / T 2 )

(18) (19) (20) (21)

For CO2, the equations were:

C1CO 2 = 0.8501 C 2 CO 2 = exp( 2.255 0.0125 * T ) C 3CO 2 = ( 218 .48 +17 .13 * T ) 51 .76 * LnT C 4 CO 2 = exp( 8.701 ) T

(22) (23) (24) (25)

Figures 1 and 2 show that the developed equations provide good predictions for the individual pure components, H2S and CO2, with maximum absolute average error (AAE) of less than 12% for both components.

10
H2S-100F

0.05000 0.04500 0.04000 yw, mol fraction 0.03500 0.03000 0.02500 0.02000 0.01500 0.01000 0.00500 0.00000 0 500 1000 1500 2000 2500 3000

3500

Pressure, psia Experimental New Model Orig. Model

Figure 1 Water Content of H2S vs. Pressure at 100 F

CO2-100F

0.00700 0.00600 Water Content, mol. frac. 0.00500 0.00400 0.00300 0.00200 0.00100 0.00000 0 500 1000 1500 2000 2500 3000

3500

Pressure, psia Experimental New Model Orig. Model

Figure 2 Water Content of CO2 vs. Pressure at 100 F

11 In Figure 1, the reader might notice that after about 1,000 psia, water content of H2S tends to slightly decrease with increasing pressure resulting in a deviation of about 22%. This is not physically correct at this point as experiments showed that once in the liquid or dense phase, water content of H2S slightly increases with increasing pressure (Carroll, 2002). This non-physical behavior can be attributed to the fact that the chosen function of M with its parameters does not increase enough to compensate for the decrease in water content as determined from the original model. After an extensive search in the fitting equations database, it is the opinion of the authors that the above relationships were the best describing functions for the behavior of pure H2S and CO2 and any mixture of them. The errors resulting from this trend are still very well within the experimental uncertainties.

12

Acid Gas Mixtures The next step in the development process was to combine these two sets of equations so that the model was applicable to acid gas mixtures. To maintain the simplicity of the model, the new mixing rule is only a function of composition. Using the available water content data for acid gas mixtures, the parameters, C1, C2, C3, and C4 within the multiplier M were mixed and generalized as follows:
C1mix = 0.8501 C 2 mix = (0.8252 + 0.174 * x H 2 S ) * x H 2 S * C 2 H 2 S + (0.986 0.0118 * xCO 2 ) * xCO 2 * C 2 CO 2

(28)

(29)

C 3 mix = (1.260 0.262 * x H 2 S ) * x H 2 S * C 3 H 2 S + (1.757 0.773 * xCO 2 ) * xCO 2 * C 3CO 2 C 4 mix = (1.656 0.668 * x H 2 S ) * x H 2 S * C 4 H 2 S + ( 2.276 1.294 * xCO 2 ) * xCO 2 * C 4 CO 2

(30) (31)

For pure components H2S or CO2, these mixture parameters will reduce to pure component Cis as one mole fraction goes to zero. Results and Model Comparisons For over 159 experimental water content data, Table 1 shows how the new model results compare to the original model and AQUAlibriumTM and VMGSimTM. Detailed model comparisons, along with comparison plots, are presented in Alami (Alami, 2004). The original model refers to the base model used in this study without the multiplier M. Figures 3 through 8 present some examples of visual comparisons of the model predictions and experimental data.

13
Table 1 Models Comparison for the Total Data Set Original Model Sum of Abs. Errors: Maximum Abs. Error: Abs. Average Error (AAE): Average Error (AE): Root Mean Square (RMS): Data Points 5772 91.93 36 -19.5 46 AQUAlibriumTM 2317 80.36 15 3.77 21 159 VMGSimTM 2223 92.3 14 0.09 20 New Model 2153 46.59 14 0.22 17

14

0.02500

CO2-167F

0.02000 Water Content, mol. frac.

0.01500

0.01000

0.00500

0.00000 0 500 1000 1500 2000 2500 3000 3500 Pressure, psia

Experimental AQUAlibrium

New Model VMG

Orig. Model

Figure 3 Experimental vs. Models Water Content of CO2 at 167F

H2S-160F 0.06000

0.05000

yw, mol fraction

0.04000

0.03000

0.02000

0.01000

0.00000 0 200 400 600 800 1000 1200 1400 Pressure, psia

Experimental AQUAlibrium

New Model VMG

Orig. Model

Figure 4 Experimental vs. Models Water Content of H2S at 160F

15
20/80-86F 0.005 0.0045 Water Content (mol frac.) 0.004 0.0035 0.003 0.0025 0.002 0.0015 0.001 0.0005 0 0 200 400 600 800 1000 1200 1400 Pressure, psia

Experimental AQUAlibrium

New Model VMG

Orig. Model

Figure 5 Expt vs. Models Water Content of 20 H2S/80 CO2 Acid Gas Mixture at 86F
80/20-140F 0.03 0.025 Water Content, mol frac. 0.02 0.015 0.01 0.005 0 200

400

600

800 Pressure, psia

1000

1200

1400

Experimental AQUAlibrium

New Model VMG

Orig. Model

Figure 6 Expt vs. Models Water Content of 80 H2S/20 CO2 Acid Gas Mixture at 140F

16
50/50-86F 0.009 Water Content (mol frac.) 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0 0 200 400 600 800 1000 1200 1400 Pressure, psia

Experimental AQUAlibrium

New Model VMG

Orig. Model

Figure 7 Expt vs. Models Water Content of 50 H2S/50 CO2 Acid Gas Mixture at 86F
25/75-104F

0.01 0.009 Water Content, mol frac. 0.008 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0 200 700 1200 Pressure, psia Experimental AQUAlibrium New Model VMG Orig. Model 1700 2200

Figure 8 Expt vs. Models Water Content of 25 H2S/75 CO2 Acid Gas Mixture at 104F

17 New Model Extrapolation The next step was to test the validity of the model at high pressures where no experimental data exist. Using AQUAlibrium and VMGSim, a set of 16 water content data points were obtained for different acid gas mixtures at 100 F and pressures from 2500 to 5000 psia. Results of the new and original models water content predictions are presented in Tables 2 and 3 below. These tables clearly show that the new model extrapolates very well into high pressure regions with a maximum error of 11 18% and an average absolute error of 6 8%, compared to the rigorous models. Although this comparison is between models because no experimental data exist, it clearly shows that the new model compares very well to the industry-accepted software.

Table 2 New Model Extrapolation Test

CO2 H2S T, F P, psia Water Content, Water Content, AE (New mol frac. mol frac. Model), % (AQUAlibrium) (New Model) 0.00583 0.0061 0.00645 0.00666 0.00672 0.00702 0.00741 0.00766 0.01046 0.01078 0.01124 0.0115 0.01596 0.0162 0.01655 0.0168 0.00591 0.00597 0.00585 0.00569 0.00684 0.00696 0.00685 0.00668 0.01036 0.01045 0.01024 0.00998 0.01527 0.01488 0.01420 0.01376 Sum Errors: Max. Abs. Error: AE, % AAE, % 1.4 -2.1 -9.3 -14.5 1.8 -0.9 -7.6 -12.8 -1.0 -3.0 -8.9 -13.2 -4.3 -8.2 -14.2 -18.1 -115 18.1 -7.18 7.58 Water Content, mol frac. (Orig. Model) 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 -90.4 -90.9 -91.5 -1314 91.93 -83.68 83.68 AE (Orig. Model), % -73.6 -75.8 -78.3 -79.6 -77.1 -79.0 -81.1 -82.3 -85.3 -86.3 -87.5

0.9 0.9 0.9 0.9 0.8 0.8 0.8 0.8 0.5 0.5 0.5 0.5 0.2 0.2 0.2 0.2

0.1 0.1 0.1 0.1 0.2 0.2 0.2 0.2 0.5 0.5 0.5 0.5 0.8 0.8 0.8 0.8

100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

2500 3000 4000 5000 2500 3000 4000 5000 2500 3000 4000 5000 2500 3000 4000 5000

18 Table 3 New Model Extrapolation Test

CO2 H2S T, F P, psia Water Content, Water Content, AE (New mol frac. mol frac. Model), % (VMGSim) (New Model) 0.00547 0.00577 0.00616 0.00636 0.00626 0.00656 0.00695 0.00725 0.00951 0.00980 0.01029 0.01059 0.01400 0.01424 0.01463 0.01493 0.00591 0.00597 0.00585 0.00569 0.00684 0.00696 0.00685 0.00668 0.01036 0.01045 0.01024 0.00998 0.01527 0.01488 0.01420 0.01376 Sum Errors: Max. Abs. Error: AE, % AAE, % 8.0 3.5 -5.0 -10.5 9.3 6.1 -1.4 -7.9 8.9 6.6 -0.5 -5.8 9.1 4.5 -2.9 -7.8 14.1 10.5 0.9 6.1 Water Content, mol frac. (Orig. Model) 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 0.00136 0.00154 0.00148 0.00140 AE (Orig. Model), % -71.8 -74.4 -77.3 -78.6 -75.4 -77.4 -79.9 -81.2 -83.8 -84.9 -86.4 -87.2 -89.0 -89.6 -90.4 -1227 90.4 -81.8 81.8

0.9 0.9 0.9 0.9 0.8 0.8 0.8 0.8 0.5 0.5 0.5 0.5 0.2 0.2 0.2 0.2

0.1 0.1 0.1 0.1 0.2 0.2 0.2 0.2 0.5 0.5 0.5 0.5 0.8 0.8 0.8 0.8

100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100

2500 3000 4000 5000 2500 3000 4000 5000 2500 3000 4000 5000 2500 3000 4000 5000

Note that the non-physical behavior of the pure H2S water content at high pressures would still have an effect on acid gas mixtures at elevated pressures. Over mixtures of 10/90, 20/80, 50/50 and 80/20, an average declination error of 5.8% was noticed, which is relatively insignificant.

19

CONCLUSIONS To design a sour gas injection scheme, water content, phase behavior and physical properties of the acid gas mixture over the range of operating temperatures and pressures of interest are required. Existing correlations and models cannot be applied to pure and/or acid gas mixtures. AQUAlibriumTM and VMGSimTM, which perform rigorous thermodynamic flash calculations, are two of the best models that can be utilized for acid gas injection applications. A new, simpler and theoretically-based model that predicts equilibrium water content over a temperature range of 32F to 212F (0C to 100C) and a pressure range of 14.7 psia to 2,000 psia (101 kPa to 14,000 kPa) for pure acid gas components and acid gas mixtures that contain up to 5 mol % hydrocarbons has been developed. This new model provides a quantitative estimate of changes in the equilibrium water content of acid gas mixtures. Compared with the available experimental data set (159 points) the new model results in an absolute average error (AAE) of 14% compared to 15% for AQUAlibriumTM and 14% for VMGSimTM. For 16 water content data points for different acid gas mixtures at 100 F and pressures from 2,500 to 5,000 psia, and where no experimental data exist, the new model extrapolates very well into high pressure regions with a maximum error of 18% and an average absolute error of 8% compared to AQUAlibriumTM, and with a maximum error of 11% and an average absolute error of 6% compared to VMGSimTM. ACKNOWLEDGMENT The authors would like to thank Paul Davis from Alberta Sulphur Research Ltd. (ASRL), Edward Wichert from Sogapro Engineering Ltd. and John Carroll from Gas Liquids Engineering Ltd. for sharing their valuable input.

20 REFERENCES

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 16. 18.

Satyro, Marco, Virtual Materials Group Inc., Calgary, Alberta, Canada, Personal Communication, 2006 Alami, I. A., W. D. Monnery and W. Y. Svrcek. "Model predicts equilibrium water content of high-pressure acid gases." Oil and Gas Journal 103.26 (2005): 4854. Alami, I. A "Water Content of High Pressure Acid Gas: A Mathematical Model" Diss. University of Calgary, 2004. Carroll, John, Gas Liquids Engineering LTD., Calgary, Alberta, Canada, Personal Communication Personal Correspondence, 2004 Awad, M. E. et al. "New model estimates water content in saturated natural gas." Oil and Gas Journal 100.17 (2002): 50-53. Behr, W. R. "Correlation Eases Absorber-Equilibrium-Line Calculations for TEGNatural Gas Dehydration." Oil and Gas Journal 81.45 (1983): 96-98. Campbell, J. M. The Basic Principles. 7 ed. Norman, Oklahoma: Campbell Petroleum Series, 1994. Carroll, John. The Water Content of Acid Gas and Sour Gas From 100 to 220F and Pressures to 10,000 PSIA. Dallas, TX, USA: Gas Processors Association, Tulsa, OK, USA, 2002. Clark, M. A. "Experimentally Obtained Saturated Water Content, Phase Behavior and Density of Acid Gas Mixtures." Diss. University of Calgary, 1999. Gas Processors Association. Engineering Data Book. 11 ed. 2 vols. Tulsa, OK: Gas Processors Suppliers Association, 1998. Kazim, F. M. A. "Quickly calculate the water content of natural gas." Hydrocarbon Processing 75.3 (1996): 105. Kumar, Sanjay. Gas Production Engineering. 7 vols. Houston, TX: Gulf Publishing Company, 1987. Maddox, R. N. Gas and Liquid Sweetening. 2 ed. 4 vols. Norman, Oklahoma: Campbell Petroleum Series, 1974. McKetta, J. J. and A. H. Wehe. "Use This Chart for Water Content of Natural Gases." Petroleum Refiner (Hydrocarbon Processing) 37.8 (1958): 153. McLeod, W. R and J. M. Campbell. "Simple method permits prediction of naturalgas critical properties." Oil and Gas Journal 67.27 (1969): 115-17. Reid, R. C., J. M. Praunsniz, and B. E. Poling. The Properties of Gases and Liquids. 4th ed. New York: McGraw-Hill, 1986. Robinson, J. N. "Equilibrium Water Vapor Content of Sour Natural Gases at High Pressure." Diss. University of Calgary, 1976. Robinson, J. N. et al. "Charts Help Estimate H2O Content Sour Gases." Oil and Gas Journal 76.6 (1978): 76-78. Selleck, F., L. T. Carmichael, and B. H. Sage. "Phase Behavior in the Hydrogen Sulfide-Water System." Industrial & Engineering Chemistry Research 44 (1952): 2219-26.

21 19. Sharma, S. C. "Equilibrium Water Content of Gaseous Mixtures." Diss. University of Oklahoma, 1969. 20. Sharma, S. C. and J. M. Campbell. "Predict natural-gas water content with total gas usage." Oil and Gas Journal 67.31 (1969): 136-37. 21. Wichert, Gordon C. and Edward Wichert. "New charts provide accurate estimations for water content of sour natural gas." Oil and Gas Journal 101.41 (2003): 64-66. 22. Wiebe, R. and V. L. Gaddy. "Vapor Phase Composition of Carbon Dioxide-Water Mixtures at Various Temperatures and Pressures to 700 Atmospheres." J Am.Chem.Soc. 63 (1941): 475-77.

22 Nomenclature
Pi = partial pressure of component i

Pi vap = vapor pressure of component i

xi = liquid mole fraction of component i
P =system

pressure

y i =mole fraction of component i in the vapor phase W HC = water content of the hydrocarbon portion of the gas from McKetta-Wehe chart

WCO 2 = effective water content of CO2

W H 2 S =effective water content of H2S

y HC , y CO 2 , y H 2 S = mole fractions of hydrocarbon, CO2 and H2S respectively.

W =water content of the sour gas
Fcorr =correction factor
vap Pw = vapor pressure of water at the system temperature vap f w = fugacity of water at its vapor pressure and system temperature

f W = fugacity of water at the system pressure and temperature y w = mole fraction of the water in the gas

Z = compressibility factor of mixture

f =fugacity

of the total gas mixture at the system pressure and temperature

w =fugacity coefficient of water vapor in natural gas mixture, psia

Vw =water liquid molar volume, ft3/lbmol

R = gas constant, 10.732 (psia*ft3)/(R*lbmol)

vap vap w = fugacity coefficient of water at its vapor pressure, Pw , and system temperature T

PC = Poynting Correction

vap = EXP (Vw / RT ) * ( P Pw )