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Vapor Phase
As discussed in the May 2011 Tip Of The Month (TOTM), for hydrate inhibition, the most commonly used
equilibrium inhibitors used in the upstream and midstream sectors of the oil and gas business are: monoethylene or
diethylene glycol (MEG or DEG) and methanol. In general, glycols are more commonly used in systems requiring
continuous inhibition. The glycol is typically recovered, regenerated and recirculated. Methanol is more commonly
used in systems that do not require continuous inhibition, i.e. systems only requiring inhibition during cold weather or
upset conditions. Methanol is not commonly recovered and reused because of the difficulty of separation of the
methanol from water. There are obviously exceptions to this. For example, methanol is used as a continuous inhibitor
in a few offshore installations and in a handful of gas processing facilities. Another significant disadvantage of
methanol relative to glycol is the high methanol losses to both the liquid hydrocarbon and vapor phase.
In the May TOTM, we reviewed experimental VLE data for methanol-hydrocarbon systems. We also revisited Figure
6.20 of reference [1] for methanol loss to the vapor phase using the experimental vapor liquid equilibrium data
reported in the Gas Processors Association Research Report 117 (GPA RR 117) [2].
In this Tip of the Month, we will investigate further the methanol loss to the vapor phase and present a simple
correlation to estimate methanol K-values. The K-value is defined as the mole fraction of methanol in vapor
phase/mole fraction of methanol in aqueous liquid phase. Since the effect of gas composition is small, the K-values
will be expressed only in terms of pressure and temperature. The estimated K-value can be used to calculate the rate
of methanol loss to the vapor phase. The objective of this TOTM is to develop a simple and generalized model for
estimation of methanol losses in terms of K-values and present a generalized chart which is less dependent on the
weight percent of methanol in the liquid aqueous phase. A step-by-step calculation procedure using K-values will be
presented as well.
At specified pressure (P) and temperature (T), read methanol K-Value from Figure 2.
2.
Convert weight % of methanol (wt%) in aqueous phase to mole fraction (x) by:
(1A)
3.
Calculate methanol mole fraction in the gas phase (y) by y = (K)(x) (1B)
4.
(1C)
SI: (MeOH kg/106 Sm3) = [(y kmole MeOH)/(Total kmole of gas)](32 kg/kmole MeOH) (kmole of gas/23.64 Sm3) (106)
= 1 353 638 y 1 353 640 y (1D)
A worked example is shown in Appendix A.
(2)
where:
Tci critical temperature, R or K
Pci critical pressure, psi, kPa or bar
i acentric factor
P system pressure, psia, kPa or bar
T system temperature, R or K
This correlation is applicable to low and moderate pressure, up to 500 Psia (3.5 MPa), and the K-values are assumed
to be independent of composition.
We propose to use a similar equation in the form of equation 3 to estimate methanol K-value at specified pressure
and temperature.
(3)
In the above equation, P*, T* and * are the normalized pressure, temperature, and acentric factor; respectively. The
same data that were used to generate Figure 2 were also used regress the above equation parameters using a nonlinear program and the following expressions were developed.
P* = P/35 with P in Psia (4)
T* = T/615 with T in R (5)
* = 2.95-(0.02607)P*+(8.9282810-5)(P*)2-0.851257/ T* (6)
We will refer to the above model as the K-Value Express. Spreadsheet estimation of methanol vapor losses can be
developed by using equation 3 to determine methanol K values, and then applying the calculation method as
discussed for the application of Figure 2.
Overall, 156 data points covering temperature range of -10 to 100 F, and pressure range of 100 to 5000 psia for 25
weight % methanol solution were used. The overall Average Absolute Percent Error (AAPE) for the K-Values was
3.6% with a Maximum Absolute Percent Error (MAPE) for K was 19.7%. The MAPE occurred at -10 F and 2000 psia
where ProMax K was 0.001 and K-Value Express K was 0.0008.
Figure 3 presents the comparison between the methanol K-Values calculated by ProMax (solid lines in Figure 3) and
those estimated by K-Value Express (identified by dashed line in Figure 3).
Results and Discussion:
The K-Value Express model with the parameters shown in Equations 4 to 6 were used without any further fitting to
predict K-values over 15 and 50 weight % methanol for wide ranges of pressures and temperature. For the case of 15
weight % methanol with 149 data points, the AAPE for K was 5.2% with a MAPE of 14.7%. For the case 50 weight %
methanol with 155 data points, the AAPE for K was 3.6% with a MAPE for K was 22.1%.
The maximum average absolute % error occurred at -10 F and 2000 psia where ProMax K was 0.00098
and K-Value Express K was 0.00077 for the case of 50 weight % methanol.
Figure 4 presents the K-Value Express K-Values vs ProMax K-Values for more than 500 data points over 15, 25, and
50 weight % methanol solution. This figure indicates relatively good agreement between the two methods.
Figure 5 is a revised and extended version of Figure 6.20 in reference [1]. Notice y-axis and x-axis variables are
switched. In this way the dependent variable is on the y-axis and independent variable is on x-axis.
Conclusion:
ProMax was used to reproduce Figure 6.20 in reference 1 and presented here in this work as Figure 5. This figure
covers wider ranges of pressure, temperature, and methanol weight percent (up to 70 weight %). However, we
suggest using Figure 2 as a better chart since it is less sensitive to methanol weight % in aqueous phase. In addition,
we developed a simple and generalized K-Value Express model that can be used to estimate methanol K-values for
wide ranges of pressure, temperature, and methanol weight %. As shown in Figures 3 and 4, the proposed model is
in good agreement with the results obtained from ProMax. The sample calculations in Appendix indicate good
agreement between the methanol losses to vapor phase obtained from Figures 2, 3, 5, and the K-Values
Express model.
Figure 3 (FPS). Comparison of predicted methanol K-Values by ProMax and the proposed Express K-Value model.
Figure 3 (SI). Comparison of predicted methanol K-Values by ProMax and the proposed Express K-Value model.
Figure 5. Variation of methanol loss to vapor phase with pressure and temperature for methanol concentration of 25
weight % in the aqueous phase
Figure 5 (SI). Variation of methanol loss to vapor phase with pressure and temperature for methanol concentration of
25 weight % in the aqueous phase
To learn more about similar cases and how to minimize operational problems, we suggest attending the John M.
Campbell courses; G4 (Gas Conditioning and Processing) and G5 (Gas Conditioning and Processing-Special).
John M. Campbell Consulting (JMCC) offers consulting expertise on this subject and many others. For more
information about the services JMCC provides, visit our website at www.jmcampbellconsulting.com, or email your
consulting needs to consulting@jmcampbell.com.
By Dr. Mahmood Moshfeghian
Reference:
1.
Campbell, J. M. Gas conditioning and processing, Volume 1: Fundamentals, John M. Campbell and
Company, Norman, Oklahoma, USA, 2001.
2.
Ng, H. J., Chen, C. J., and D. B. Robinson, D.B.; RR-117, The Solubility of Methanol or Glycol in Water
Hydrocarbon Systems, Gas Processors Association (Mar. 1988).
3.
Peng, D. Y., and Robinson, D. B., Ind. Eng. Chem. Fundam., Vol. 15, p. 59, 1976.
4.
ProMax 3.1, Bryan Research and Engineering, Inc, Bryan, Texas, 2010.
5.
Wilson, G., A modified Redlich-Kwong equation of state applicable to general physical data calculations,
Paper No15C, 65th AIChE National meeting, May, (1968).
Using Eq 3: