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SECTION 20

Dehydration
Natural gas and associated condensate are often produced Dehydration is the process used to remove water from natu-
from the reservoir saturated (in equilibrium) with water. In ral gas and natural gas liquids (NGLs), and is required to:
addition, the gas and condensate often contain CO2 and H2S
which might require removal. This is frequently accomplished prevent formation of hydrates and condensation of free
with aqueous solutions such as amines, potassium carbonate, water in processing and transportation facilities,
etc. which saturate the gas or condensate with water. Liquid meet a water content specification, and
hydrocarbons may also contain water downstream of product
treaters or upon removal from underground storage. prevent corrosion

FIG. 20-1
Nomenclature

A = area, m 2
Qv = vaporization of water heat duty, kJ/m3
B = constant in Equation 20-14 Qw = desorption of water heat duty, kJ
C = constant in Equation 20-14 Ss = amount molecular sieve reqd in saturation zone, kg
Cp = heat capacity, kJ/(kg K) t = thickness of the vessel wall, mm
Cg = gravity correction factor for water content T = temperature, C
Cs = salinity correction factor for water content Trg = regeneration temperature, C
Css = saturation correction factor for sieve v = vapor velocity, m/s
CT = temperature correction factor V = superficial vapor velocity, m/h

D = diameter, m w = water rate, kg/h
d = depression of the water dewpoint or the gas hy- W = water content of gas, mg/Sm3
drate freezing point, C Wbbl = water content of gas, m3/Mm3
EOS = Equation of State Wr = water removed per cycle, kg

Fs = sizing parameter for packed towers,  kg/(m s) x = mole fraction in the liquid phase
G = mass velocity, kg/(m h)
2
X = mass fraction in the liquid phase
H = enthalpy, kJ/kg y = mole fraction in the gas phase
H = latent heat of vaporization, kJ/kg z = compressibility factor
Kvs = vapor/solid equilibrium K-value = specific gravity
L = length of packed bed, m = viscosity, mPa s
Lg = glycol flow rate, m3/h = density, kg/m3
LMTZ = length of packed bed mass transfer zone, m
Subscripts
Ls = length of packed bed saturation zone, m
m
= mass flow rate, kg/h i = inlet
MTZ = mass transfer zone o = outlet
M = molecular mass l = liquid
MI = molecular mass of inhibitor v = vapor
N = number of theoretical stages t = total
P = pressure, kPa (abs) CO2 = carbon dioxide
P = pressure drop, kPa H2S = hydrogen sulfide
q = actual gas flow rate, m3/h HC = hydrocarbon
Q = heat duty, kW s = solid phase
Qc = reflux condensing heat duty, kJ/m3 L = lean inhibitor
Qhl = regeneration heat loss duty, kJ R = rich inhibitor
Qr = total regeneration heat duty, kJ/m3 I = inhibitor
Qs = sensible heat, kJ/m3 H2O = water
Qsi = duty required to heat mole sieve to regeneration H = hydrate
temperature, kJ rg = regeneration
Qst = duty required to heat vessel and piping to regen- f = feed
eration temperature, kJ p = permeate
Qtr = total regeneration heat duty, kJ i = any component in a mixture

20-1
Techniques for dehydrating natural gas, associated gas con- ATER CONTENT OF
W
densate and NGLs include:
GASES AND LIQUIDS
Absorption using liquid desiccants,
Water Solubility in Liquid Hydrocarbons
Adsorption using solid desiccants,
Fig. 20-2 shows the solubilities of water in sweet liquid hy-
Dehydration with CaCl2, drocarbons. It is based on experimental data developed in GPA
Dehydration by refrigeration and inhibition, RR-169.1 In sour hydrocarbon liquids, water solubility can be
substantially higher.
Dehydration by membrane permeation,
GPA RR-622 provides water solubility data for selected
Dehydration by gas stripping, and hydrocarbons in both sweet and sour systems. Equations-
of-State (EOS) may be used to estimate water solubilities in
Dehydration by distillation. hydrocarbon systems. GPA RR-423 provides a comparison of
experimental versus calculated values using a modified Soave-
Redlich-Kwong (SRK) EOS. Results from EOS methods should

FIG. 20-2
Solubility of Water in Liquid Hydrocarbons

20-2
be used with caution and verified with experimental data when carbons, generalized pressure-temperature correlations are
possible. suitable for many applications. Fig. 20-45 is an example of one
such correlation which has been widely used for many years in
Fig. 20-3 gives hydrocarbon solubilities in water, which in the design of sweet natural gas dehydrators. It is based on the
general are considerably less than water in hydrocarbons. This work of McKetta and Wehe6 and Olds, et.al.7 The gas gravity
figure is based on experimental data developed in GPA RR-169.1 correlation should never be used to account for the presence of
Some experimental data is available in GPA RR-62. Yaws, et. H2S and CO2 and may not always be adequate for certain hy-
al.4 provide a general correlation which may be used to estimate drocarbon effects, especially for the prediction of water content
the solubility of over 200 hydrocarbons in water. at pressures above 10 000 kPa (abs). The hydrate formation
line is approximate and should not be used to predict hydrate
Water Content of Natural Gases formation conditions.
The saturated water content of a gas depends on pressure,
The following example is used to illustrate the use of Fig.
temperature, and composition. The effect of composition in-
20-4.
creases with pressure and is particularly important if the gas
contains CO2 and/or H2S. For lean, sweet natural gases con- Example 20-1 Determine the saturated water content for a
taining over 70% methane and small amounts of heavy hydro- sweet lean hydrocarbon gas at 66C and 6900 kPa (abs).

FIG. 20-3
Solubility of Hydrocarbons in Water

20-3
FIG. 20-4
Water Content of Hydrocarbon Gas

20-4
From Fig. 20-4, Water Content of High CO2/H2S Gases
W = 3520 mg/Sm 3
Acid gas components, carbon dioxide (CO2) and hydrogen
sulfide (H2S), increase the solubility of water in natural gas due
For a 26 molecular mass gas,
to the attraction of water for these molecules. The equilibrium
Cg = 0.98 (Fig. 20-4) water content of an acid gas mixture varies significantly with
pressure, temperature and mixture composition. Liquid CO2
W = (0.98)(3520) = 3450 mg/Sm 3
and H2S hold more water than gaseous CO2 and H2S, but the
For a gas in equilibrium with a 3% brine, opposite is true for hydrocarbons as shown by Kobayashi and
Katz.8 This effect is seen in the several example systems shown
Cs = 0.93 (Fig. 20-4) in Figs. 20-5 through 20-8.
W = (0.93)(3520) = 3270 mg/Sm 3

FIG. 20-5
Saturated Water Content of CO2

100000
CO2
Pure CO2, 18.3C
Pure CO2, 25C
Pure CO2, 31.1C
Pure CO2, 50C
Pure CO2, 73.8C
mg water / Sm 3 wet gas

10000 Methane
73.8 C
50 C
31.1 C
25 C

1000
50 C

18.3 C
31.1 C

18.3 C
100
1000 10000 100000
Pressure, kPa (abs)

FIG. 20-6
Saturated Water Content of H2S

1000000

171 C
mg water / Sm3 wet gas

100000
138 C

104 C

71C

10000

38 C

1000
1000 10000 100000
Pressure, kPa (abs)

20-5
Fig. 20-59,10,11 shows the water content in pure CO2 (solid changes significantly with a small change in pressure resulting
curves) at various temperatures and pressures. The water con- in a large change in water content. This effect is seen at 31C
tent of a light natural gas from Fig. 20-4 is shown for compara- and 50C. Similar behavior is seen in Fig. 20-612 for H2S. Al-
tive purposes using dashed lines. At low pressure, the water though 104.4C is above the critical temperature for pure H2S,
content of CO2 decreases with increasing pressure as expected the temperature is subcritical for the mixture of H2S and water
from ideal solubility. At higher pressures the water content in as shown by Carroll and Mather.13 In both Fig. 20-5 and 20-6,
CO2 increases with increasing pressure due to the increased the curves were generated with the Yarrison Model (RR-200),11
density of CO2 and the attraction of water for CO2. The verti- but modified as needed (particularly in the liquid state) to im-
cal dashed lines in Fig. 20-5 at 18.3C and 25C represent the prove agreement with experimental data.
change in water content due to the phase change from vapor
to liquid. The critical temperature for CO2 is 31C. Near the Fig. 20-79,14,15 shows the saturated water contents of select-
critical temperature and critical pressure, the density of CO2 ed mixtures of CH4, CO2 and H2S versus pressure at 37.8C and

FIG. 20-7
Experimental Saturated Water Content of Mixtures at 37.8C and 93.3C

100000
5.5% CH4 + 0.3% C3 + 25% CO2 + 69.2%H2S

5.4% CH4 + 0.3% C3 + 49.5% CO2 + 44.8%H2S


93.3 C

100% CO2
mg water / S m3 wet gas

10000 9% CH4 + 10% CO2 + 81%H2S


30%CO2+26.3%H2S+C1
37.8 C
100% CH4
100% CO2

30% CH4 + 60% CO2 + 10%H2S


1000
90% CH4 + 10% CO2

100% CH4

100
1000 10000 100000
Pressure, kPa (abs)

FIG. 20-8
Saturated Water Content of CO2-Rich Mixtures at 93.3C

30000

25000
mg water / Sm3 wet gas

20000

15000 Pure CO2

70% CO2 + 30% CH4


10000

10% CO2 + 90% CH4


5000
Pure CH4
0
0 5000 10000 15000 20000 25000 30000 35000 40000 45000
Pressures, kPa (abs)

20-6
93.3C. Fig. 20-86,9,16 shows the water content of pure CH4, CO2, 2.Corrections for H2S and CO2 should be applied when the
and mixtures of CH4 and CO2 at 93.3C. Several significant ob- gas mixture contains more than 5% H2S and/or CO2 at
servations can be made from these figures and other available pressures above 4800 kPa (abs). These corrections be-
data. Water content is not strongly affected by a low concentra- come increasingly significant at higher concentrations
tion of carbon dioxide in methane, but a low concentration of and higher pressures.
methane in CO2 can strongly affect the water content. Similar
behavior is expected with H2S. 3.The addition of small amounts of CH4 or N2 to CO2 or
H2S can dramatically reduce the saturated water content
1.Saturated water content of pure CO2 and H2S and mix- compared to the pure acid gas.
tures containing high concentrations of acid gases can
be significantly higher than that of sweet natural gas, Acid gas water content is a very complex subject. The data
particularly at pressures above about 4800 kPa (abs) at and methods presented here should not be used for final de-
ambient temperatures. sign. Figs. 20-5, 20-6, 20-7 and 20-8 are all based on experi-
mental data with some model predictions. A cursory study of

FIG. 20-9
Correlation for Estimating the Water Content of Acid Gas Mixtures

20-7
these figures reveals the complexities involved. Estimation of Fig. 20-10 shows experimental water content data for vari-
water content requires a careful study of the existing literature, ous mixtures compared to the method in Fig. 20-9.
availability of experimental data, and knowledge of the system
phase behavior. Example 20-2 Determine the saturated water content of gas
containing 79% CH4, 12% CO2 & 9% H2S @ 49C & 10 000 kPa
Water content estimates for the condition/mixture of inter- (abs).
est can be achieved through interpolation or extrapolation of
data, simple correlations, or using equations of state. Interpo- First, the acid gas composition must be converted to an
lation or extrapolation requires due caution and careful treat- equivalent H2S using Equation 20-1.
ment with understanding of the physical properties and phase yH2S (equiv) = (yCO2)(0.7) + (yH2S)
behavior of the acid gas mixture. Additional experimental data
is the best way to verify predicted values. Even the most sophis- yH2S (equiv) = (0.7)(12) + 9 = 17.4%
ticated EOS techniques must be tuned to experimental data to Enter the left side of Fig. 20-9 at 49C and move horizon-
accurately estimate water content. tally to the %H2S equivalent line (17.4%). Proceed vertically to
An exhaustive list of references containing experimental the 10 000 kPa (abs) pressure line and move left to the Water
water content data for natural gas mixtures has been compiled Content Ratio scale. The water content ratio is 1.15.
in reference 17. Multiply this times the sweet gas water content at 49C and
Numerous correlations have been proposed to estimate wa- 10 000 kPa (abs) from Fig. 20-4 (1265 kg/Sm3).
ter content in acid gas mixtures (Robinson, et al.,18 Maddox,  ater content of acid gas-natural gas mixture
W
et al.,19 Carroll and Mather,13 Carroll,20 Wichert and Wichert,5 = (1.15)(1265) = 1455 kg/Sm3
Yarrison, et al.11 Several of these involve equations of state or
hybrid approaches involving an equation of state for the gas and Water Content in the Hydrate Region
activity coefficient model for the liquid water phase. Other ap-
proaches provide graphs to enable quick approximate results. Fig. 20-4 is based on the assumption that the condensed
water phase is a liquid. However, at temperatures below the
The method of Wichert and Wichert uses Fig. 20-9 to esti- hydrate temperature of the gas, the condensed phase will be a
mate water content of acid gas mixtures relative to water con- solid (hydrate). The water content of a gas in equilibrium with
tent in sweet gas. The method is applicable to mixtures con- a hydrate will be lower than equilibrium with a metastable liq-
taining both CO2 and H2S. With gases containing CO2, the CO2 uid. This is acknowledged in the Warning in Fig. 20-4.
concentration is multiplied by 0.70 to obtain an equivalent
H2S concentration as shown in Equation 20-1. Hydrate formation is a time dependent process. The rate at
which hydrate crystals form depends upon several factors in-
yH2S (equiv) = (yCO2)(0.7) + (yH2S) Eq 20-1 cluding gas composition, presence of crystal nucleation sites in
The method is limited to an H2S equivalent of 50 mol% and the liquid phase, degree of agitation, etc. During this transient
applicable for temperatures from 10 to 177C and pressures hydrate formation period the liquid water present is termed
from 1400 to 69 000 kPa (abs). In comparison with 70 data metastable liquid. Metastable water is liquid water which, at
points covering natural gas mixtures with up to 50% equivalent equilibrium, will exist as a hydrate.
H2S concentrations from 38 to 107C and 1400 to 41 000 kPa GPA RR-45,21 50,22 and 8023 present experimental data
(abs), the error for the this method was randomly distributed showing equilibrium water contents of gases above hydrates.
with an average absolute error of 10% and a maximum of 37%. Data from GPA RR-50 is presented in Fig. 20-11. For compara-

FIG. 20-10
Comparison of Experimental vs. Calculated Water Contents for Acid Gases

Water Content mg/Sm3 wet gas


Mixture T, C P, kPa Wichert & Yarrison, et al.,
Experiment
Wichert (RR-200)
11% CO2/89% C1 37.8 13 789 652 690 666
11% CO2/89% C1 71.1 6 895 4 591 4 575 4 575
20% CO2/80% C1 37.8 13 789 652 738 716
20% CO2/80% C1 71.1 6 895 4 526 4 655 4 687
20% CO2/80% C1 71.1 13 789 2 761 3 114 3 082
8% H2S/92% C1 54.4 10 342 1 782 1 701 1 701
27.5% H2S/72.5% C1 71.1 9 597 3 965 4 173 4 173
17% H2S/83% C1 71.1 6 964 4 687 4 703 4 783
C1/CO2/H2S 37.8 7 584 1 300 1 380 1 252
30%/60%/10%
C1/CO2/H2S 37.8 13 100 7 095 NA 10 144
9%/10%/81%
5.31% C1/94.69% CO2 25.0 10 342 1 753 NA 1 413
5.31% C1/94.69% CO2 50.0 13 789 2 643 NA 3 210

20-8
tive purposes, the metastable water content of a sweet gas from in gas and/or NGL systems can plug pipelines, equipment, and
Fig. 20-4 is also shown. Water content of gases in the hydrate instruments, restricting or interrupting flow.
region is a strong function of composition. Fig. 20-11 should not
be extrapolated to other compositions. There are three recognized crystalline structures for such
hydrates. In both, water molecules build the lattice and hydro-
When designing dehydration systems (particularly TEG carbons, nitrogen, CO2 and H2S occupy the cavities. Smaller
systems) to meet extremely low water dewpoint specifications, molecules (CH4, C2H6, CO2, H2S) stabilize a body-centered cubic
it is necessary to determine the water content of the gas in equi- called Structure I. Larger molecules (C3H8, i-C4H10, n-C4H10)
librium with a hydrate. If a metastable correlation is used, one form a diamond-lattice called Structure II.
will overestimate the saturated water content of the gas at the
dewpoint specification. This, in turn, may result in a dehydra- Normal paraffin molecules larger than n-C4H10 do not form
tion design which is unable to meet the required water removal. Structure I and II hydrates as they are too large to stabilize
Where experimental data is unavailable, utilization of a sound the lattice. However, some isoparaffins and cycloalkanes larger
thermodynamic-based correlation can provide an estimate of than pentane are known to form Structure H hydrates.13
water content in equilibrium with hydrates. Gas composition determines structure type. Mixed gases
will typically form Structure II. Limiting hydrate numbers (ra-
Water Content Measurement tio of water molecules to molecules of included gaseous compo-
Specifications for water content measurement are given in nent) are calculated using the size of the gas molecules and the
GPA Publication 2140.These include the Valve Freeze Method, size of the cavities in H2O lattice.
the Bureau of Mines Dew Point Tester, and the Cobalt Bromide From a practical viewpoint, the structure type does not af-
Method. Cobalt bromide color change occurs at about 2530 fect the appearance, properties, or problems caused by the hy-
mg/kg. drate. It does, however, have a significant effect on the pressure
There are several commercial instruments available for and temperature at which hydrates form. Structure II hydrates
monitoring water content based on other principles. Measuring are more stable than Structure I. This is why gases contain-
water contents of less than 20 ppmw or making dewpoint deter- ing C3H8 and i-C4H10 will form hydrates at higher temperatures
minations at less than 40C can be very difficult. than similar gas mixtures which do not contain these compo-
nents. The effect of C3H8 and i-C4H10 on hydrate formation
conditions can be seen in Fig. 20-13. At 6900 kPa (abs), a 0.6
HYDRATES IN NATURAL GAS SYSTEMS relative density gas (composition is shown in Fig. 20-16) has a
hydrate formation temperature which is 7C higher than pure
A hydrate is a physical combination of water and other small methane.
molecules to produce a solid which has an ice-like appearance
but possesses a different structure than ice. Their formation The presence of H2S in natural gas mixtures results in
a substantially warmer hydrate formation temperature at a

FIG. 20-11
Water Content of 5.31% C3 /94.69% C1 Gas in Equilibrium with Hydrate

20-9
FIG. 20-12 FIG. 20-14
Conditions for Hydrate Formation for Light Gases Permissible Expansion of a 0.6-Gravity Natural
Gas Without Hydrate Formation

See Caution on Fig. 20-13

FIG. 20-13
FIG. 20-15
Pressure-Temperature Curves for
Predicting Hydrate Formation Permissible Expansion of a 0.7-Gravity Natural
Gas Without Hydrate Formation

13 15

See Caution on Fig. 20-13

20-10
given pressure. CO2, in general, has a much smaller impact and FIG. 20-16
often reduces the hydrate formation temperature at fixed pres- Gas Compositions Used for Fig. 20-13 through 20-15
sure for a hydrocarbon gas mixture.
The conditions which affect hydrate formation are: Mole Fraction

Primary Considerations C1 0.9267 0.8605 0.7350


C2 0.0529 0.0606 0.1340
Gas or liquid must be at or below its water dew point or
saturation condition (NOTE: liquid water does not have C3 0.0138 0.0339 0.0690
to be present for hydrates to form) iC4 0.0018 0.0084 0.0080
Temperature nC4 0.0034 0.0136 0.0240
Pressure nC5 0.0014 0.0230 0.0300

Composition Rel. Den. 0.603 0.692 0.796

Secondary Considerations Example 20-4 The gas in Example 20-3 is to be expanded


from 10 000 kPa (abs) to 3450 kPa (abs). What is the minimum
Mixing
initial temperature that will permit the expansion without hy-
Kinetics drate formation?
Physical site for crystal formation and agglomeration The 10 000 kPa (abs) initial pressure line and the 3450 kPa
such as a pipe elbow, orifice, thermowell, or line scale (abs) final pressure line intersect just below the 45C curve on
Fig. 20-15. Approximately 44C is the minimum initial tem-
Salinity perature.
In general, hydrate formation will occur as pressure increas- Example 20-5 How far may a 0.6 relative density gas at 14000
es and/or temperature decreases to the formation condition. kPa (abs) and 40C be expanded without hydrate formation?
rediction of Sweet Natural
P On Fig. 20-14 find the intersection of 14 000 initial pressure
Gas Hydrate Conditions line with the 40C initial temperature curve. Read on the x-axis
the permissible final pressure of 7600 kPa (abs).
Fig. 20-12, based on experimental data, presents the hydrate
pressure-temperature equilibrium curves for pure methane, eth- Example 20-6 How far may a 0.6 relative density gas at
ane, propane, and for a nominal 70% ethane 30% propane mix. 14 000 kPa (abs) and 60C be expanded without hydrate for-
mation?
Fig. 20-13 through 20-15, based on gas gravity, may be used
for first approximations of hydrate formation conditions and for On Fig. 20-14, the 60C initial temperature curve does not
estimating permissible expansion of sweet natural gases with- intersect the 14 000 kPa (abs) initial pressure line. Therefore,
out the formation of hydrates. the gas may be expanded to atmospheric pressure without hy-
drate formation.
The conditions at which hydrates can form are strongly af-
fected by gas composition. Compositions used for the construc- Conditions predicted by Fig. 20-13 through 20-15 may be
tion of Fig. 20-13 through Fig. 20-15 are given in Fig. 20-16. The significantly in error for compositions other than those used
gases are saturated with water. to derive the charts. For more accurate determination of hy-
drate formation conditions, the following procedures should be
Example 20-3 Find the pressure at which hydrate forms for followed. In addition, Fig. 20-14 and 20-15 do not account for
a gas with the following composition. T = 10C. liquid water and liquid hydrocarbons present or formed during
the expansion. These can have a significant effect on the outlet
Mole Mole kg/kg-mol temperature from the pressure reduction device.
Component Fraction Mass of Mixture
C1 0.784 16.043 12.58 ydrate Prediction Based on
H
C2 0.060 30.070 1.80
C3 0.036 44.097 1.59
Compositionfor Sweet Gases
iC4 0.005 58.124 0.29 Several correlations have proven useful for predicting hy-
nC4 0.019 58.124 1.10 drate formation of sweet gases and gases containing minimal
N2 0.094 28.013 2.63 amounts of CO2 and/or H2S. The most reliable ones require a
CO2 0.002 44.010 0.09 gas analysis. The Katz method25,26 utilizes vapor solid equilib-
Total 1.000 20.08 rium constants defined by the Equation 20-2.

Mole mass (Mgas) of gas mixture = 20.08 y


Kvs = x Eq 20-2
s
Mgas 20.08
= = = 0.693
Mair 28.964 WARNING: Not good for pure components only mixtures.

From Fig. 20-13 at 10C The applicable K-value correlations for the hydrate forming
molecules (methane, ethane, propane, isobutane,27 normal bu-
P = 2200 kPa (abs) for 0.7 relative density gas tane,28 carbon dioxide, and hydrogen sulfide) are shown in Fig.
20-17 to 20-23. Normal butane cannot form a hydrate by itself
but can contribute to hydrate formation in a mixture.

20-11
FIG. 20-17
Vapor-Solid Equilibrium Constants for Methane

FIG. 20-18
Vapor-Solid Equilibrium Constants for Ethane

20-12
FIG. 20-19
Vapor-Solid Equilibrium Constants for Propane

20-13
FIG. 20-20 FIG. 20-22
Vapor-Solid Equilibrium Constants for Iso-Butane Vapor-Solid Equilibrium Constants for Carbon Dioxide

FIG. 20-23
Vapor-Solid Equilibrium Constants for Hydrogen Sulfide

FIG. 20-21
Vapor-Solid Equilibrium Constants for N-Butane

20-14
For calculation purposes, all molecules too large to form hy- 2. Assume some temperature and predict the hydrate for-
drates have a K-value of infinity. These include all normal par- mation pressure for this gas using the solid-vapor K-
affin hydrocarbon molecules larger than normal butane. Nitro- data. Plot the results on Fig. 20-24. Sample calculations
gen is assumed to be a non-hydrate former and is also assigned for 1380 and 2070 kPa (abs) are provided below. This cal-
a K-value of infinity. culation has been repeated for 2760, 3450, 5520 and 6890
kPa (abs) to develop Fig. 20-24.
The Kvs values are used in a dewpoint equation to deter-
mine the hydrate temperature or pressure. The calculation is 1380 kPa (abs) 2070 kPa (abs)
iterative and convergence is achieved when the following objec- T = 4C y Kvs y/Kvs Kvs y/Kvs
tive function (Equation 20-3) is satisfied.
C1 0.9267 2.25 0.4119 1.75 0.5295
i=n C2 0.0529 0.50 0.1058 0.205 0.2580
(yi/Kvs) = 1.0 Eq 20-3 C3 0.0138 0.055 0.2509 0.030 0.4600
i=1
iC4 0.0018 0.0225 0.0800 0.0105 0.1714
nC4 0.0034
Prudence should be exercised when some higher molecular C5 0.0014
weight isoparaffins and certain cycloalkanes are present since Total 1.0000 0.8486 1.4189
they can form structure H hydrates.
y/Kvs = 1.0 @ 1570 kPa (abs)
Example 20-7 Calculate the pressure for hydrate formation
at 10C for a gas with the following composition.
3. The intersection of the lines in Fig. 20-24 will be the point
at which hydrates start to form. In this example, the re-
Component Mole 2070 kPa (abs) 2760 kPa (abs) sult is 3450 kPa (abs) and 11C.
Fraction
in Gas Kvs y/Kvs Kvs y/Kvs FIG. 20-24

Methane 0.784 2.04 0.384 1.75 0.448 Solution Sketch for Example 20-8
Ethane 0.060 0.79 0.076 0.50 0.120
Propane 0.036 0.113 0.319 0.072 0.500
Isobutane 0.005 0.046 0.109 0.027 0.185
n-Butane 0.019 0.21 0.090 0.21 0.090
Nitrogen 0.094 * 0.000 * 0.000
Carbon dioxide 0.002 3.0 0.001 1.9 0.001
Total 1.000 0.979 1.344

*Infinity

Interpolating linearly, y/Kvs = 1.0 at 2100 kPa (abs)

The experimentally observed hydrate-formation pressure at


10C was 2240 kPa (abs).
Example 20-8 The gas with the composition below is at
24100 kPa (abs) and 66C. What will be the hydrate conditions
when this gas is expanded?
Component Mole Fraction
C1 0.9267
C2 0.0529
C3 0.0138
iC4 0.0018
nC4 0.0034
nC5 0.0014

Total 1.0000
Note: Fig. 20-14 would predict permissable expansion only to a
Solution Steps: pressure around 4800 kPa (abs).
1. Make several adiabatic flash calculations at different The Katz correlation is not recommended above 7000
pressures and plot on a pressure versus temperature 10000 kPa (abs), depending on composition. Prediction of hy-
graph. (See Fig. 20-24) drate formation conditions at higher pressures requires the use
Initial Initial Final Final
of other methods. Sloan, et.al.29 present an alternate set of Kvs
Pressure Temperature Pressure Temperature
values which, in general, are valid to 30 000 kPa (abs). McLeod
kPa (abs) C kPa (abs) C
& Campbell30 present experimental hydrate data for natural
gas mixtures up to 70 000 kPa (abs) as well as a correlation for
24 100 66 2070 3 estimating high pressure hydrate formation conditions. Blanc
24 100 66 2760 7 & Tournier-Lasserve31 provide experimental hydrate data to
24 100 66 3450 11 100 000 kPa (abs) and compare prediction correlations with ex-
24 100 66 4140 14 perimental data.
24 100 66 4830 18

20-15
Hydrate Predictions for High Example 20-9 Estimate the hydrate formation temperature
CO2/H2S Content Gases at 4200 kPa (abs) of a gas with the following analysis using Fig.
20-25.
The Katz method of predicting hydrate formation tempera- Component mol %
ture gives reasonable results for sweet normal paraffin hydro-
carbon gases. The Katz method should not be used for gases N2 0.30
containing significant quantities of CO2 and/or H2S despite the CO2 6.66
fact that Kvs values are available for these components. Hydrate H2S 4.18
formation conditions for high CO2/H2S gases can vary signifi- C1 84.27
cantly from those composed only of hydrocarbons. The addition C2 3.15
of H2S to a sweet natural gas mixture will generally increase C3 0.67
the hydrate formation temperature at a fixed pressure.32 iC4 0.20
nC4 0.19
A method by Baille & Wichert for predicting the tempera- C5+ 0.40
ture of high H2S content gases is shown in Fig. 20-25.33 This is
based on the principle of adjusting the propane hydrate condi- M = 19.75 = 0.682
tions to account for the presence of H2S as illustrated in Ex-
ample 20-9.

FIG. 20-25
Hydrate Chart for Gases Containing H2S

20-16
Solution Steps: ture of a sweet natural gas. In this example, at 6900 kPa (abs),
the addition of H2S (10 mol%) to a sweet gas mixture increases
1. Enter left side of Fig. 20-25 at 4200 kPa (abs) and proceed the hydrate temperature by 8 C. On the other hand, CO2 has a
to the H2S concentration line (4.18 mol%) minor effect on the hydrate formation temperature and slightly
2. Proceed vertically to the relative density of the gas ( = decreases the hydrate temperature for both the sweet and
0.682) sour gases in this case.

3. Follow the diagonal guide line to the temperature at the EOS-based computer programs are probably the most con-
bottom of the graph (T = 17.5 C) sistent method of predicting hydrate formation temperatures
today. Accuracy when compared to experimental data is usually
4. Apply the C3 correction using the insert at the upper left. 1 C. This is generally adequate for design.
Enter the left hand side at the H2S concentration and
proceed to the C3 concentration line (0.67%). Proceed
down vertically to the system pressure and read the cor- Hydrate Inhibition
rection on the left hand scale (1.5 C) The formation of hydrates can be prevented by:
Note: The C3 temperature correction is negative when on the 1. Maintaining the system temperature above the hydrate
left hand side of the graph and positive on the right hand side. formation temperature by the use of a heater and/or in-
TH = 17.5 1.5 = 16 C sulation

Fig. 20-25 was developed based on calculated hydrate con 2. Dehydrating the hydrocarbon fluid (gas and/or liquid) to
ditions using the Peng-Robinson EOS. It has proven quite ac- eliminate the condensation of liquid or solid water
curate when compared to the limited amount of experimental 3. Injection of a chemical inhibitor to prevent or mitigate
data available. It should only be extrapolated beyond the ex- hydrate formation
perimental data base with caution.
In some cases, heating or dehydration may not be practical
Fig. 20-2634 presents experimental hydrate formation data or economically feasible.
for three mixtures of methane, propane and hydrogen sulfide.
Results of selected hydrate prediction methods are also shown. In these cases, chemical inhibition can be an effective meth-
od of preventing hydrate formation. Chemical inhibition utilizes
The addition of CO2 to pure methane will slightly increase injection of thermodynamic inhibitors (sometimes called equi-
the hydrate temperature at a fixed pressure.35 However, the ad- librium inhibitors) or low dosage hydrate inhibitors (LDHIs).
dition of CO2 to a typical sweet natural gas mixture will often Thermodynamic inhibitors are the traditional inhibitors (i.e.,
lower the hydrate formation temperature at a fixed pressure. one of the glycols or methanol), which lower the temperature of
Fig. 20-27 is provided to portray these compositional effects. hydrate formation. LDHIs are either kinetic hydrate inhibitors
The hydrate curves for four gas compositions are shown. These (KHIs) or antiagglomerants (AAs). They do not lower the tem-
were generated using a commercial hydrate program employ- perature of hydrate formation, but do diminish its effect. KHIs
ing the Peng-Robinson EOS. The four gas compositions are: lower the rate of hydrate formation, which inhibits its develop-
Sweet Gas (0.6 rel. den. gas from Fig. 20-16) ment for a defined duration. AAs allow the formation of hydrate
Sweet Gas containing 10% CO2 crystals but restrict them to sub-millimeter size.
Sour Gas containing 10% H2S Thermodynamic inhibitors Inhibition utilizes injec-
Sour Gas containing 10% CO2 and 10% H2S tion of one of the glycols or methanol into a process stream
Note that H2S significantly increases the hydrate tempera- where it can combine with the condensed aqueous phase to low-
er the hydrate formation temperature at a given pressure. Both

FIG. 20-26
Experimental vs. Predicted Hydrate Conditions for Gases Containing C1, C3, and H2S

Composition, mol % Experimental Data17 Predicted Temperature, C

Temperature, Pressure, Equation


C1 C3 H2S C kPa (abs)
Fig. 20-13
20-3
Fig. 20-25

88.654 7.172 4.174 0.649 4.6 706 NA 2.6 5.4


88.654 7.172 4.174 0.649 11 1419 5.0 8.4 11.3
88.654 7.172 4.174 0.649 14.2 2024 7.2 11.2 14.1
88.654 7.172 4.174 0.649 18 3367 11.7 14.9 18.4
81.009 7.016 11.975 0.696 10.4 817 1.1 5.1 10.8
81.009 7.016 11.975 0.696 19.5 2813 11.7 14.9 21.5
60.888 7.402 31.71 0.823 13.1 686 2.8 7.1 13.2
60.888 7.402 31.71 0.823 19.1 1445 8.3 15.3 20.3
60.888 7.402 31.71 0.823 24.3 2558 12.8 19.7 24.8
60.888 7.402 31.71 0.823 27.8 4275 16.7 24.1 28.7

20-17
glycol and methanol can be recovered with the aqueous phase, The inhibitor and condensed water mixture is separated
regenerated and reinjected. For continuous injection in services from the gas stream along with a separate liquid hydrocarbon
down to 40C, one of the glycols usually offers an economic ad- stream. At this point, the water dew point of the gas stream is
vantage versus methanol recovered by distillation. At cryogenic essentially equal to or slightly lower than the separation tem-
conditions (below 40C) methanol usually is preferred because perature. Glycol-water solutions and liquid hydrocarbons can
glycols viscosity makes effective separation difficult. emulsify when agitated or when expanded from a high pressure
to a lower pressure, e.g., JT expansion valve. Careful separator
Ethylene glycol (EG), diethylene glycol (DEG), and trieth- design normally allows nearly complete recovery of the diluted
ylene glycol (TEG) have been used for hydrate inhibition. The glycol for regeneration and reinjection.
most popular has been ethylene glycol because of its lower cost,
lower viscosity, and lower solubility in liquid hydrocarbons. The regenerator in a glycol injection system should be op-
erated to produce a regenerated glycol solution that will have
Physical properties of methanol and methanol-water mix- a freezing point below the minimum temperature encountered
tures are given in Fig. 20-28 through Fig. 20-31. Physical prop- in the system. This is typically 7580 wt%. Fig. 20-52 shows
erties of the most common glycols and glycol-water mixtures the freezing point of various concentrations of glycol water so-
are given in Fig. 20-32 through Fig. 20-49. Tabular information lutions.
for the pure glycols and methanol is provided in Fig. 20-50.
The minimum inhibitor concentration in the free water
Equilibrium inhibitors are used in both pipeline/flowline ap- phase may be approximated by Hammerschmidts equation.36
plications as well as in low temperature gas processing facili-
ties. To be effective, the inhibitor must be present at the very KH XI
point where the wet gas is cooled to its hydrate temperature.

d =
MI (1 XI) Eq 20-4
Fig. 20-51 shows a flow diagram for a typical EG injection
system in a refrigeration plant. In these facilities, the glycol dMI
inhibitor is sprayed into the gas upstream of the exchanger. XI =
KH + dMI Eq 20-5
The exchanger type can be shell and tube, plate or printed cir-
cuit. As water condenses, the inhibitor is present to mix with
the water and prevent hydrates. Injection must be in a manner Where KH for ethylene glycol and methanol = 1297.
to allow good distribution in the gas flow path. It is common Earlier editions of the Engineering Data Book suggested a
practice to inject 2 to 3 times the glycol rate calculated from the range of KH values (12972222) for glycols. Higher values of
correlations that follow. KH result in lower concentrations of rich (diluted) glycol (XI in
The viscosity of ethylene glycol and its aqueous solutions Equation 20-5) which, in turn, suggests a lower inhibitor injec-
increases significantly as temperature decreases. This effect tion rate. Experimental data suggests KH = 1297 is the correct
must be considered in the design and rating of exchangers in constant as illustrated in Fig. 20-53. In some field operations,
low temperature gas processing facilities.

FIG. 20-27
Hydrate Formation Conditions for Sweet Gas Showing Effects of CO2 and H2S

20-18
FIG. 20-28 FIG. 20-30
Density of Aqueous Methanol Solutions Heat of Vaporization of Methanol
at Various Temperatures Versus Temperature

FIG. 20-29 FIG. 20-31


Vapor Pressure of Aqueous Methanol Solutions Freezing Points of Aqueous
at Various Temperatures Methanol Solutions

20-19
Figures 20-32 through 20-43 are reproduced from Gas Conditioning Fact Book, 1962, and Figures 20-44 through 20-49
are reproduced from the Dow monoethylene, diethylene, and triethylene glycol guides, 2003, with permission from
The Dow Chemical Company and subject to all warranty disclaimers therein.

FIG. 20-32 FIG. 20-34


Densities of Aqueous Ethylene Glycol Solutions Densities of Aqueous Triethylene Glycol Solutions

FIG. 20-33 FIG. 20-35


Densities of Aqueous Diethylene Glycol Solutions Viscosities of Aqueous Ethylene Glycol Solutions

20-20
FIG. 20-36 FIG. 20-38
Viscosities of Aqueous Diethylene Glycol Solutions Heat Capacities of Aqueous Ethylene Glycol Solutions

FIG. 20-37 FIG. 20-39


Viscosities of Aqueous Triethylene Glycol Solutions Heat Capacities of Aqueous Diethylene Glycol Solutions

20-21
FIG. 20-40 FIG. 20-42
Heat Capacities of Aqueous Triethylene Glycol Solutions Thermal Conductivity of Diethylene GlycolWater Mixtures

FIG. 20-43
FIG. 20-41
Thermal Conductivity of Triethylene
Thermal Conductivity of Ethylene GlycolWater Mixtures GlycolWater Mixtures

20-22
FIG. 20-44 FIG. 20-46
Vapor Pressures of Ethylene Glycol Vapor Pressures of Aqueous Triethylene Glycol
at Various Temperatures Solutions at Various Temperatures

FIG. 20-45 FIG. 20-47


Vapor Pressures of Aqueous Diethylene Glycol Dew Points of Aqueous Ethylene Glycol Solutions
Solutions at Various Temperatures at Various Contact Temperatures

20-23
FIG. 20-48 FIG. 20-49
Dew Points of Aqueous Diethylene Glycol Solutions Dew Points of Aqueous Triethylene Glycol Solutions
at Various Contact Temperatures at Various Contact Temperatures

FIG. 20-50
Physical Properties of Selected Glycols and Methanol

Diethylene Triethylene Tetraethylene


Ethylene Glycol Methanol
Glycol Glycol Glycol
Formula C2H6O2 C4H10O3 C6H14O4 C6H18O5 CH3OH
Molecular Mass 62.1 106.1 150.2 194.2 32.04
Boiling Point* at 760 mm Hg, F 387.1 472.6 545.9 597.2 148.1
Boiling Point* at 760 mm Hg, C 197.3 244.8 285.5 314 64.5
Vapor Pressure at 77F (25C) mm Hg 0.12 <0.01 <0.01 <0.01 120
Density
(g/cc) at 77F (25C) 1.110 1.113 1.119 1.120 0.790
(g/cc) at 140F (60C) 1.085 1.088 1.092 1.092
kg/m3 at 77F (25C) 1110 1113 1119 1120 790
Freezing Point, C 13 8 7 5.5 97.8
Pour Point, C 54 58 41
Viscosity in centipoise
at 77F (25C) 16.5 28.2 37.3 44.6 0.52
at 140F (60C) 4.68 6.99 8.77 10.2
Surface Tension at 47 44 45 45 22.5
77F (25C), dynes/cm
Refractive Index at 77F (25C) 1.430 1.446 1.454 1.457 0.328

Specific Heat at 77F (25C) kJ/(kgK) 2.43 2.30 2.22 2.18 2.52
Flash Point, C (PMCC) 116 124 177 204 12
Fire Point, C (C.O.C.) 118 143 166 191
Note: These properties are laboratory results on pure compounds or typical of the products, but should not be confused with, or regarded as,
specifications.
* Glycols decompose at temperatures below their atmospheric boiling point. Approximate decomposition temperatures are:
Ethylene Glycol 165C Diethylene Glycol 164C Triethylene Glycol 207C Tetraethylene Glycol 238C

20-24
FIG. 20-51
Example Glycol Injection System

FIG. 20-52
Freezing Points of Aqueous Glycol Solutions
however, hydrate formation has been prevented with glycol
concentrations corresponding with KH values as high as 2222.
This is because hydrate suppression with glycols depends on
the systems physical and flow characteristics as well as gas and
glycol properties. In addition, published experimental hydrate
data is at the hydrate dissociation point not the point of hydrate
formation. The dissociation temperature can be several degrees
higher than the formation temperature depending on the sys-
tem dynamics. It is recommended that a system be designed
using a KH of 1297. Once the system is operating it may be pos-
sible to operate at lower injection rates.
Equation 20-4 and Equation 20-5 should not be used beyond
20 wt% for methanol and 50 wt% for the glycols. For methanol
concentrations up to about 50 wt%, the Nielsen-Bucklin equa-
tion37 provides better accuracy:
d = 72.0 ln (xH2O) Eq 20-6
Note that xH2O in Equation 20-5 is a mole fraction, not a mass
fraction. Fig. 20-54 shows the mol% vs. wt% relationship for
both methanol and EG. Equations 20-7 and 20-8 may also be
used.

Wt% I
MI
mol% = (100)
wt% I + (100 wt% I)

M I
Eq 20-7
18

20-25
(mol% I) (M I) 4 to 19C, and methanol concentration in the aqueous phase
wt% = (100) wt% of about 3 to 73 mole percent. Data from similar temperatures
[(mol% I) (M I) + 18 (100 mol% I)]
(within 1C) from various sources were combined and repre-
Eq 20-8 sented in Fig. 20-55 as a single average temperature. There is
substantial scatter in the data sources, and the trends shown
Where: M
 of methanol = 32 in the figure should be treated as approximate. The term on the
M of EG = 62 y-axis is a K-value (vapor-liquid equilibrium constant) with the
Fig. 20-54, Equations 20-7 and 20-8 are useful when using units [(kg/106Sm3)/mol% MeOH in the aqueous phase]. The use
Equation 20-6, Figs. 20-53, 20-55 and 20-56. of Fig. 20-55 is demonstrated in Example 20-10.

Maddox et al.38 presents a method of estimating the required Methanol losses to the hydrocarbon liquid phase are more dif-
inhibitor concentration for both methanol and EG. The method ficult to predict. Solubility is a strong function of both the water
is iterative but converges easily after a few iterations. phase and hydrocarbon phase compositions. Fig. 20-5642 pres-
ents experimental data43,44,45,46,47,48 ,49 showing solubility of meth-
Fig. 20-53 provides a comparison of various inhibitor cor- anol in a various hydrocarbon liquids paraffin and mixtures
relations with experimental data.39,40,41 Experimental data at of paraffins and toluene. The y-axis is a distribution coefficient,
very high inhibitor concentrations is limited. mol fr. of methanol in the aqueous phase divided by the mol fr.
Once the required inhibitor concentration has been calcu- of methanol in the hydrocarbon phase. Lower values for the dis-
lated, the mass of lean inhibitor solution required in the water tribution coefficient indicate higher hydrocarbon solubility. The
phase may be calculated from Equation 20-8. use of a distribution coefficient to estimate methanol losses to
the hydrocarbon liquid phase is shown in Example 20-10.
XR mH2O
mI = Solubility of EG in the liquid hydrocarbon phase is typically
XL XR Eq 20-9 minimal.36 A solubility of 0.036 kg/m3 of NGL is often used for
design purposes. However, entrainment and other physical
The amount of inhibitor to be injected not only must be suf- losses may result in total losses significantly higher than this.
ficient to prevent freezing of the inhibitor water phase, but also
must be sufficient to provide for the equilibrium vapor phase Example 20-10 2.83 (106) Sm3/day of natural gas leaves an
content of the inhibitor and the solubility of the inhibitor in offshore platform at 38C and 8300 kPa (abs). The gas comes
any liquid hydrocarbon. For methanol, the vapor pressure is onshore at 4C and 6200 kPa (abs). The hydrate temperature of
sufficiently high that a significant quantity of inhibitor will the gas is 18C. Associated condensate production is 56 m3/106
be lost to the vapor phase. Methanol vaporization losses may Sm3. The condensate has a density of 780 kg/m3 a M of 140 and
be estimated from Fig. 20-55.42 The data in Fig. 20-55 is de- is substantially paraffinic. Calculate the amount of methanol
rived from a variety of sources,43,44,45,46,47,48 at pressures ranging and 80 wt% EG inhibitor required to prevent hydrate formation
from about 200034 000 kPa (abs), temperatures from about in the pipeline.

FIG. 20-53
Hydrate Suppression vs. Inhibitor Concentration in Mol%

140
Hammerschmidt
KH = 2222
120
Hammerschmidt
KH = 1297

100
Nielsen & Bucklin

80
d, C

85 wt% MeOH RR-106

60
73.7 wt% MeOH RR-106

65 wt% MeOH RR-106


40
25 wt% ME G R -R92
50 wt% MeOH RR-106

20
50 wt% MEG RR-92 50 wt% MeOH RR-92

25 wt% MeOH RR-92


0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90%

Inhibitor concentration, mol%

20-26
Solution Steps: d = 14 C, M = 32

Methanol Solving for XI,


1. Calculate the amount of water condensed per day from From Equation 20-5, XI = 0.255,
Fig. 20-4, Win = 850 kg/106 Sm3
Wout = 150 From Equation 20-6, mol fr. = 0.175 (use this value in
kg/10 Sm
6 3
subsequent calculations)
W = 700 kg/10 Sm3
6

Water condensed = (700)(2.83) = 1980 kg/d From Fig. 20-54, Mass % = 27.5

2. 
Calculate required methanol inhibitor concentration 3. Calculate mass rate of inhibitor in water phase from
from Equation 20-5 and 20-6 Equation 20-9 (assume 100% methanol is injected)
XR mH2O (0.275)(1980)
mI = = = 750 kg/d
FIG. 20-54 XL XR (1 0.275)
Mass % vs. Mol% for Methanol and EG Solutions 4. Estimate vaporization losses from Fig. 20-55.
@ 4 C and 6200 kPa (ga), losses = (30 kg/106 Sm3)/
100%
mol% MeOH in water phase
daily losses = (30)(2.83)(17.5) = 1490 kg/d
90%
5. E
 stimate losses to hydrocarbon liquid phase from Fig.
80%
20-56.
70% @ 4 C and paraffinic fluid, Dist. Ratio = 110
mol % MeOH in hyd. liquid = 17.5/110 = 0.16 mol%
60%
Mass %

1 m3 of condensate has a mass of 780 kg


50%
= (780/140) =5.6 kmol/m3 of condensate
40%
= (5.6)(0.0016) =0.009 kmol MeOH
30%
= (32)(0.009) = 0.29 kg/m3
20%
Methanol
Total MeOH losses to the hydrocarbon liquid phase
10% EG = (0.29)(2.83)(56) = 46 kg MeOH/d

0% Total methanol injection rate = 750 + 1490 + 46


0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% = 2286 kg/d
mol %

FIG. 20-55
Ratio of Methanol Vapor Concentration to Methanol Liquid Concentration

200

15.3 oC
)

19.4 oC
Mole percent methanol in aqueous liquid
kg methanol per million Std m3

100
10.4 oC

0.5 oC

19.4 C

15.3 C 5.0 oC
10.4 C
( Methanol in Vapor Phase

5.0 C

0.5 C
-4.3 o C
-4.3 C

Distributionof methanol between aqueous


and vapor phase, from various sources
including VLE and LLE data.
10
10 100 400
Pressure, bar

20-27
Methanol left in the gas phase can be recovered by conden- During regeneration, contaminants in the water phase
sation with the remaining water in a downstream chilling pro- (such as dissolved solids) leave with the water, not the
cess. Likewise, the methanol in the condensate phase can be methanol
recovered by downstream water washing.
Can be transported in the vapor phase (significant meth-
80 wt% EG anol vaporization at injection point) which is useful for
removing hydrates that have formed downstream of the
1. Calculate required inhibitor concentration from Equa- injection point in the system
tion 20-5
d = 14C, M = 62, KH = 1297 Methanol Disadvantages

Solving for XI, XI = 0.40 Higher inhibitor losses to the hydrocarbon vapor and liq-
uid phases
2. Calculate mass rate of inhibitor solution in water phase
from Equation 20-9 More difficult to recover methanol from the aqueous
phase
(0.40)(1980)
mI = More toxic than EG
(0.80 0.40)
More flammable than EG (lower flash point)
= 1980 kg/d
Methanol losses to the hydrocarbon vapor and liquid phases
Vaporization and liquid hydrocarbon losses are negligible. has become a more significant issue due to increasingly strin-
gent contaminant specifications for condensate, NGLs and
Hydrate inhibition with methanol or EG is widely used in natural gas.
pipelines as well as in gas processing plants. The choice of in-
hibitor is influenced by several factors. A few of these are listed EG Advantages
below:
Very low solubility losses to the hydrocarbon phases and
Methanol Advantages generally not regarded as a contaminant
Generally less expensive than EG Much easier to recover from the water phase (regenera-
tion)
Requires lower concentrations in the aqueous phase
Less toxic and less flammable than methanol
Can inhibit to very low temperatures
Can also provide corrosion inhibition for top of the line
Has a lower viscosity than EG corrosion in pipelines

FIG. 20-56
Liquid-Liquid Methanol Distribution Ratios

1000
)Mole fraction MeOH in Aqueous Phase
Mole fraction MeOH in Organic Phase

100

No Toluene

28-33mol% Toluene
(

10 50-70 mol% Toluene


Distribution Ratio

70-80 mol% Toluene

Distribution of methanol between aqueous


and hydrocarbon phases, data from various
sources. Hydrocarbon phases includes various
alkane and cycloalkane compounds. Data
shows the variation of distribution with
changes in the amount of toluene in the
hydrocarbon phase.
1
-50 -30 -10 10 30 50
Temperature (oC)

20-28
EG Disadvantages Increased production rates, where inhibitor injection ca-
pacity or flowline capacity is limited.
Higher concentrations required in the aqueous phase
Lower toxicity of KHIs.
Higher viscosity makes physical separation from hydro-
carbon liquid phase more difficult Kinetic Hydrate Inhibitors KHIs were designed to in-
hibit hydrate formation in flowlines, pipelines, and downhole
Is transported in the liquid phase so generally not very equipment operating within hydrate forming conditions such
effective in removing hydrates that have formed down- as subsea and cold weather environments. Their unique chemi-
stream of the injection point in the system cal structure significantly reduces the rate of nucleation and
During regeneration, contaminants in the water phase hydrate growth during conditions thermodynamically favorable
(such as dissolved solids) accumulate in the EG phase for hydrate formation, without altering the thermodynamic hy-
requiring special regeneration designs, typically vacuum drate formation conditions (i.e., temperature and pressure).
systems This mechanism differs from methanol or glycol, which depress
the thermodynamic hydrate formation temperature so that a
As a general rule, EG is usually the first choice when con- flowline operates outside hydrate forming conditions.
tinuous inhibition is required. Methanol is typically used when
inhibition is only occasionally required, such as during periods Some applications benefit from combining KHIs and metha-
of cold weather or during start-ups and shut-downs. nol or glycol. The mixed inhibition package reduces the hydrate
equilibrium temperature relative to uninhibited fluids, but
Inhibition with Electrolytes does not reduce it below the operating temperature. Because
there is some methanol or glycol, the lower hydrate equilibrium
Hydrates are also inhibited by dissolved salts in the water temperature results in a lower subcooling or driving force for
phase. GPA RR-15650 presents experimental hydrate formation hydrates than in a KHI only inhibition scheme. KHI is effective
data for water solutions with various concentrations of NaCl, at the reduced subcooling in preventing the formation of hy-
KCl and CaCl2. drates in the flowing system. This is useful where the operating
Electrolytes also provide hydrate inhibition in the presence temperature is too low for KHI to function by itself and where
of equilibrium inhibitors such as methanol and EG. Fig. 20-57 methanol only strategies are not desirable, e.g., for reasons of
shows the inhibition performance of four solutions of methanol limited storage volume or injection rates.
and NaCl. KHIs Compared to Methanol or Glycols KHIs inhibit
hydrate formation at a concentration range of 0.11.0 weight
Low Dosage Hydrate Inhibitors (LDHIs) percent polymer in the free water phase. For relative compari-
LDHIs can provide significant benefits compared to thermo- son, methanol or glycol typically may be required at concentra-
dynamic inhibitors including: tions ranging 20 to 50 weight percent respectively in the water
phase. At the maximum recommended KHI dosage, the current
Significantly lower inhibitor concentrations and there- inhibition capabilities are up to 16C of subcooling in gas sys-
fore dosage rates. Concentrations range from 0.1 to 1.0 tems without acid gas components and less than 11C in sour
weight percent polymer in the free water phase, whereas gas or oil systems. New KHIs continue to expand the region of
alcohols can be as high as 50%. effectiveness. Subcooling is the difference between the equilib-
Lower inhibitor loss caused by evaporation, particularly rium hydrate temperature and the system temperature. The
compared to methanol. LDHIs typically have a vapor degree of subcooling that can be achieved with KHIs is time
pressure so low that no detectable amount of the LDHI
is lost to the gas phase except via water droplet entrain-
ment. Likewise, LDHIs have low solubility in liquid hy- FIG. 20-57
drocarbons. Most LDHIs partition less than 10% to the Hydrate Inhibition with Methanol and NaCI
liquid HC phase. Most of the loss to the liquid HC phase
is from water droplet entrainment or emulsification.
Reduced capital expenses through decreased chemical
11000
Pure Water
storage and injection rate requirements; and usually 10000
no need for regeneration because the chemicals are not
20% NaCl
9000
currently recovered. However, in cases where the pipe- 20% MeOH

line water is injected into a water disposal well system, 8000


5% MeOH-15% NaCl
Pressure, kPa

Kinetic hydrate inhibitors (KHIs) in the aqueous phase 7000


may come out of solution if the reservoir temperature
15% MeOH-5% NaCl
6000
is above the KHI solution Cloud Point temperature (or
Lower Critical Solution Temperature). If the KHI does 5000
come out of solution, it may cause a large decrease in the 4000
water injectivity due to plugging rock pores. In these cas-
es, KHIs may have to be removed from the water before
3000

injection into the water disposal well system. 2000

These are especially appropriate for offshore where 1000


weight and space are critical to costs. 0
0 4 8 12 16 20
Reduced operating expenses in many cases through de-
Temperature, C
creased chemical consumption and delivery frequency.

20-29
dependent and flow dependent. Shorter times allow higher The KHI polymer suffers degradation effects at tempera-
subcooling values in flowing systems. Non-flowing Hold Times tures above 249C.
are often too short for pipelines to restart without intervention,
such as, temporary glycol injection or lower pressure restart un- Antiagglomerant (AA) Inhibitors Antiagglomerants
til the KHI has been re-distributed throughout the length of the were developed out of the necessity to extend the range of sub-
pipeline. It is important that the design subcooling is consistent cooling for LDHIs beyond that of KHIs, and AAs can achieve
with the expected system residence time subcooling of greater than 4C. Unlike KHIs, which delay the
formation of hydrates, AAs allow their formation at normal
KHI Screening Considerations Although KHIs are rates, but as small nonagglomerating hydrate crystals that
applicable under most producing conditions, certain conditions are dispersed into an oil or condensate preventing the forma-
must be considered when evaluating a potential application, tion and accumulation of large hydrate crystals. Thus, AAs
which include water salinity, freezing conditions, hold time are suitable only in the presence of liquid hydrocarbon or in
(i.e., period of effectiveness), water saturation, acid gas compo- nearly 100% water systems where less than 30% of the water
nent concentrations and high temperature processes. is converted to hydrates due to limited quantities of gas. The
mechanism of dispersion is emulsification with the AAs acting
KHIs are frequently antagonized by commonly used oil- as emulsification agents.
field chemicals, such as, corrosion inhibitors, drilling flu-
id components, et cetera, particularly where these other AAs Compared to Methanol or Glycols The compari-
chemicals are surface active. An extensive pre-screening sons of AAs to methanol and glycols are similar to KHIs except
program to determine the impact of KHIs on CIs, and that AAs achieve greater subcooling and may not require ther-
vice versa is required. The testing can take six months to modynamic inhibition after a shut-in/restart.
complete.
AA Screening Considerations Although AAs are appli-
At water salinity levels greater than approximately 17% cable under most producing conditions, certain conditions must
NaCl, the polymer may come out of solution, thereby re- be considered when evaluating a potential application. These
ducing KHI effectiveness. conditions include water salinity, emulsification and demulsifi-
cation (i.e., separation), pipeline hydraulics, water cuts, mate-
A solution of KHI in water does not provide protection rial compatibility, water treating, and downstream impacts.
from freezing or icing conditions, neither in the line being
treated nor in the KHI storage tank. If ambient tempera- Some AAs have a maximum or minimum salinity crite-
tures are expected to fall below freezing, the KHI storage rion. The maximum salinity criterion is normally not ex-
volume must be freeze-protected through the use of in- ceeded with produced water.
sulation on the container and piping or addition of anti-
freeze (typically ethylene glycol) to the KHI solution. Since AAs are based on dispersing (i.d., emulsifying) po-
lar hydrate crystals in a nonpolar oil or condensate phase
A solution of KHI cannot be used for melting ice or hy- (i.e., continuous phase), they may sometimes require a
drate plugs. It is recommended to have other strategies, demulsifier for oil and water separation. Further, the ad-
such as a sufficient quantity of ethylene glycol or metha- dition of a heater upstream or heat coil inside a separator
nol for remediation purposes in the event of a blockage. may be required to melt the hydrate crystals.
The KHI delivery system must be capable of providing
sufficient dosage to achieve a hold time greater than the Since AAs form crystals that are then dispersed in the
water residence time in the flowing piping. Factors to liquid hydrocarbon phase, careful consideration of the po-
consider include: tential impact on viscosity should be considered including
steady state flow, shut-in flow and restart conditions.
The design basis for treating the pipeline with
thermodynamic inhibitor or lower pressure dur- An additional consideration for AAs is that the water cuts
ing/after an unplanned shut-in. (i.e., percent water in the liquids) may have to be less
than about 50% or higher than about 80% with limited
The minimum required flow rate to entrain the gas fraction. Intermediate water cuts refer to concentra-
KHI-treated liquids to the top-of-line. Liquid tions below the inversion point (i.e.,where the continuous
slugging can mitigate lack of droplet entrainment liquid phase changes from liquid hydrocarbon to water).
in gas systems. At the intermediate water cuts, AAs may fail to produce
a flowable hydrate slurry for various reasons.
The potential for water to pool in low sections of
piping (e.g., turn-down hydraulics, flowline pro- AAs can impact the performance of some metallurgy and
file, pigging frequency, flowline interconnects elastomers, so impacts on existing hardware should be
that are not used continuously) and dead legs. reviewed.
The seasonal duration of the cold point tempera- Some oil-soluble AAs typically partition (i.e., disperse)
ture below hydrate temperature, if applicable. to the liquid hydrocarbon phase, but low residuals can
remain in the produced water, which can impact toxic-
If the gas is undersaturated with respect to water, the ity test results. Water-soluble AAs do present potential
water in the KHI solution will evaporate and leave a high toxicity issues in the produced water.
viscosity fluid. This can be addressed by using a more
dilute KHI solution, or by changing the KHI carrier fluid Residual AA concentration in the hydrocarbon liquid
to ethylene glycol. phase could possibly impact downstream processes and
should be considered in the context of overall contribu-
The KHI polymer and the solvents in the KHI product tion to a total feed-stream.
will form separate phases if the inhibited fluid is above
the lower critical solution temperature (LCST) of the Chemical compatibility of LDHIs with other production
KHI/pipeline water solution. chemicals can vary greatly; therefore, it is important to carry

20-30
out compatibility studies to investigate the effect of the LDHI refers to the difference between the actual outlet water dew
on the performance of existing chemicals. The effect of the exist- point of the gas and the water dew point in equilibrium with
ing chemicals on the LDHI performance is equally important. the incoming lean glycol.
The most frequently used production chemicals, especially in
subsea pipelines, are corrosion inhibitors, scale inhibitors and Several equilibrium correlations 52,53,54,55,56,57,58 have been de-
paraffin inhibitors. These chemicals are either formulated in veloped and published since 1950. All are limited by the ability
aqueous base solvents or hydrocarbon solvents. to measure accurately the equilibrium concentration of water
in the vapor phase above a highly concentrated TEG solution.
Hence, accurate infinite dilution activity coefficients are critical
GAS DEHYDRATION to the reliable modeling of TEG dehydration systems. Parrish,
et. al.51 and Bestani and Shing59 have reported infinite dilution
Glycol Dehydration Systems activity coefficients for the TEG-water system. There is good
In those situations where inhibition is not feasible or practi- agreement between these two sets of experimental data. The
cal, dehydration may be used. Both liquid and solid desiccants data of Bestani and Shing along with data from Herskowitz and
are employed, but economics frequently favor liquid desiccant Gottlieb were used to develop the activity coefficient correlation
dehydration when it will meet the required dehydration speci- which provided the basis for the equilibrium calculations for
fication. Fig. 20-59.

Liquid desiccant dehydration equipment is simple to oper- Equilibrium water dewpoints are relatively insensitive to
ate and maintain. It can easily be automated for unattended pressure. Fig. 20-59 is based on a contactor pressure of 6900
operation; e.g., glycol dehydration at a remote production facil- kPa (abs). Higher pressures result in slightly lower dew points
ity. Liquid desiccants can be used for sour gases, but additional and lower pressures result in slightly higher dew points. For
precautions in the design are needed due to the solubility of the the pressure range 345013 800 kPa (abs) psia, the change in
acid gases in the desiccant solution. At high acid gas content equilibrium dew points is typically less than 23C.
and higher pressures the glycols can also be soluble in the Please note that the equilibrium water dew points on the
gas. ordinate of Fig. 20-59 are based on the assumption the con-
Glycols are typically used for applications where dew point densed water phase is a metastable liquid. At low dew points
depressions of the order of 33 to 66C are required. Diethylene the condensed phase will be a hydrate. The equilibrium dew
glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol point temperature above a hydrate is higher than that above a
(TREG) are used as liquid desiccants, but TEG is the most com- metastable liquid. Therefore, in these cases Fig. 20-59 predicts
mon for natural gas dehydration. dew points which are lower than those which can actually be
achieved. The difference is a function of temperature, pressure,
Following the process flow in Fig. 20-58, the regenerated and gas composition but can be as much as 811C (see Fig.
glycol (lean glycol) is pumped to the top of the contactor (ab- 20-11). When dehydrating to very low dew points, such as those
sorber) which may contain trays or packing. The glycol absorbs required upstream of a refrigeration process, the TEG concen-
water as it flows down through the contactor countercurrent to tration should be sufficient to dry the gas to the hydrate dew
the gas flow. Water-rich glycol is removed from the bottom of point not the metastable dew point.
the contactor, passes through the reflux condenser coil at the
top of the regenerator, flashes off most of the soluble gas in the Once the lean TEG concentration has been established, the
flash tank, and flows through the rich-lean heat exchanger to TEG circulation rate and number of trays (height of packing)
the regenerator. In the regenerator, absorbed water is distilled must be determined. Most economical designs employ circula-
from the glycol at near atmospheric pressure by application of
heat. The regenerated lean glycol exits the surge drum, is part- FIG. 20-58
ly cooled in the lean-rich exchanger and is pumped through the
glycol cooler before being re-circulated to the contactor. Example Process Flow Diagram for
Glycol Dehydration Unit
Good practice dictates installing an inlet gas separator up-
stream of the contactor, even if the dehydrator is near a produc-
tion separator. The inlet gas separator will prevent carryover
of liquid water (fresh or salty), hydrocarbons, treating chemi-
cals or corrosion inhibitors into the glycol contactor. Even small
quantities of these materials can result in excessive glycol losses
due to foaming, reduced efficiency, and increased maintenance.
Integral separators at the bottom of the contactor are common
but it is important to ensure that the diameter and height of the
separator are suitable for efficient liquid removal from the gas.
Evaluation of a TEG system involves first establishing the
minimum TEG concentration required to meet the outlet gas
water dew point specification. Fig. 20-5951 shows the water dew
point of a natural gas stream in equilibrium with a TEG solu-
tion at various temperatures and TEG concentrations. Fig. 20-
59 can be used to estimate the required TEG concentration for
a particular application or the theoretical dew point depression
for a given TEG concentration and contactor temperature. Ac-
tual outlet dew points depend on the TEG circulation rate and
the number of equilibrium stages in the contactor, but typical
approaches to equilibrium are 611C. Approach to equilibrium

20-31
tion rates of about 15-30 kg lean TEG/kg H2O absorbed (1327 The graphs in these figures apply only if the feed gas is water
liters lean TEG/ kg H2O absorbed). The relationship between saturated. The curves were developed based on contactor oper-
circulation rate and number of equilibrium stages is based on ating conditions of 6900 kPa (abs) and 40C. The water removal
the absorption calculation techniques set out in Chapter 19. is not a strong function of temperature and pressure, however
This has been done for TEG systems with the results presented a higher inlet gas water content results in a larger temperature
in Figs. 20-60 through 20-6460. rise across the contactor due to the heat of absorption of the wa-
ter. This temperature rise decreases the absorption efficiency.

FIG. 20-59
Equilibrium H2O Dew Point vs. Temperature at Various TEG Concentrations

40.0

30.0
97.0 wt %
20.0
98.0 wt %
10.0 98.5wt %
99.0 wt %
0.0
99.5 wt %
Dewpoint, C

-10.0
99.7 wt %

-20.0
99.9 wt %
-30.0
99.95wt %
-40.0

-50.0
99.99 wt %

-60.0

-70.0

-80.0
10.0 20.0 30.0 40.0 50.0 60.0 70.0
Contactor Temperature, C

FIG. 20-60
Absorber Performance at Lean TEG Concentration = 98.5 wt%

1.00

0.90
N=3.0
Water Removal Fraction

N=2.5
0.80 N=2.0

0.70 N=1.5

0.60

N=1.0
0.50
0 10 20 30 40 50 60 70
Circulation Ratio, mass lean TEG sol/mass water absorbed

20-32
In general, the correlations in Figs. 20-60 through 20-64 tend For TEG contactors, the height of a transfer unit (HTU) de-
to overestimate water removal at lower feed gas pressures and pends on the mass transfer rate. Increases in HTU represent
higher feed gas temperatures and underestimate water remov- a decrease in mass transfer. HTU decreases with increasing
al at higher pressures and lower temperatures. The variation packing specific area and glycol circulation rate and increases
depends on TEG concentration and circulation ratio but is typi- with increasing gas rate and gas density. HTU is also affected
cally less than 2-3%. by the TEG properties, particularly viscosity. Increases in TEG
viscosity increase HTU. This may be a factor when operating at
Conversion from equilibrium stages to actual trays can be contactor temperatures less than 16C.
made assuming an overall tray efficiency of 25-30%. For packed
columns it is more common to use transfer units than theoreti- Fig. 20-66 can be used to estimate the HTU of structured
cal stages. Fig. 20-65 provides an approximate conversion from packing in glycol contactors as a function of packing specific
theoretical stages (N) to transfer units (NTU) as a function of area and gas density.
TEG circulation ratio.

FIG. 20-61
Absorber Performance at Lean TEG Concentration = 99.0 wt%

1.00

0.95

0.90 N=3.0
Water Removal Fraction

N=2.5
0.85
N=2.0
0.80

0.75
N=1.5
0.70

0.65

0.60
N=1.0
0.55
0 10 20 30 40 50 60 70

Circulation Ratio, mass lean TEG sol/mass water absorbed

FIG. 20-62
Absorber Performance at Lean TEG Concentration = 99.5 wt%

1.00

0.95 N=4.0
N=3.0
Water Removal Fraction

0.90
N=2.5

0.85
N=2.0

0.80

0.75
N=1.5

0.70
0 10 20 30 40 50 60 70

Circulation Ratio, mass lean TEG sol/mass water absorbed

20-33
The height of packing can be estimated from Equation 20-10. volume at the bottom of the column and, for packed columns,
the liquid distributor. Bubble cap trays have historically been
Packing Height = (NTU)(HTU) Eq. 20-10 used in glycol contactors due to the low liquid rates versus gas
It is common practice to add a minimum of two packing lay- flow, but structured packing is widely used today. Relative to
ers to the value calculated from Equation 20-10. The typical bubble cap columns, structured packing typically allows a sig-
thickness of a layer of structured packing is 200 mm. For trayed nificantly smaller contactor diameter and a slightly smaller
contactors the typical tray spacing is 610 mm. contactor height.

The total height of the contactor column will be based on Contactor diameter is set by the gas velocity. Sizing is iden-
the number of trays or packing required plus an additional 23 tical to that outlined for separators in Section 7. Recommend-
m to allow space for vapor disengagement above the top tray, ed values for K-factors and C-factors for glycol contactors are
inlet gas distribution below the bottom tray, rich glycol surge shown in Fig. 20-67.

FIG. 20-63
Absorber Performance at Lean TEG Concentration = 99.9 wt%

1.00

N=4.0
Water Removal Fraction

N=3.5
0.95
N=3.0

N=2.5
0.90

N=2.0
0.85
0 10 20 30 40 50 60 70
Circulation Ratio, mass lean TEG sol/mass water absorbed

FIG. 20-64
Absorber Performance at Lean TEG Concentration = 99.99 wt%

1.00

0.99

0.98
Water Removal Fraction

N=4.0
0.97
N=3.5
0.96

0.95
N=3.0
0.94

0.93

0.92

0.91 N=2.5

0.90
0 10 20 30 40 50 60 70

Circulation Ratio, mass lean TEG sol/mass water absorbed

20-34
Structured packing vendors frequently quote an Fs value for From Fig. 20-61 (99 wt% TEG) at a circulation ratio = 28 kg
sizing glycol contactors, where Fs is defined in Equation 20-11. TEG/kg H2O, the required theoretical stages = 2.0
Fs = v (v)0.5 Eq 20-11 This is equivalent to 8 bubble cap trays. At 610 mm tray
spacing this is 4.3 m between bottom and top tray.
Values of Fs = 3.0 to 3.7 will generally provide a good esti-
mate of contactor diameter for conventional structured packing. For packing, from Fig. 20-65 at a circulation ratio = 28 kg
For high capacity structured packing, Fs values can range from TEG/kg H2O the required NTUs = 4.1
4.3 to 4.9.
(4100)(0.65)(28.97)
Example 20-11 0.85 106 Sm3/d of a 0.65 sp gr natural gas Feed gas density =
(0.92)(8.314)(273+38)
enters a TEG contactor at 4100 kPa (abs) and 38C. The outlet
= 32 kg/m3
water content specification is 110 kg H2O/106 Sm3 and the TEG
circulation rate is 28 kg lean TEG/ kg H2O absorbed (25 liters From Fig. 20-66, HTU = 0.76 m.
lean TEG/kg H2O). Estimate the contactor diameter and num-
ber of bubble cap trays or height of structured packing required Total height of packing = (4.1)(0.76) + 0.4 = 3.5 m
to meet this requirement. Assume z = 0.92 and that the specific The 0.4 m represents two additional 200 mm packing layers
area of the packing is 250 m2/m3.
The total height is equivalent to 17-18 packing layers
Solutions Steps:
3. Estimate contactor diameter
1. Estimate required TEG concentration from Fig. 20-59
Bubble caps, 610 mm tray spacing:
H2O dew point = 4C, which from Fig. 20-4 is equivalent
to a water content of 110 mg H2O/Sm3 @ 4100 kPa (abs) From Section 7 and Fig. 20-67:

Assume a 6C approach to equilibrium so the equilibrium G = C [v (L v)]0.5


dew point is 10C @ T = 38C, lean TEG concentration = 176 [32 (1120 32)]0.5 = 32 800 kg/m2 h
98.9 wt% (use 99.0 wt%)
2. Estimate number of theoretical stages. 228 000 Sm3
= 1 kmol
m 23.64
 d
Calculate water removal efficiency
 rom Fig. 20-4 the inlet gas water content at 38C and
F
4100 kPa (abs) = 1450 kg/106 Sm3 (0.65)(28.97)kg 1 d

kmol 24 h = 28 200 kg/h
Win
Wout 1450110
= = 0.924

Win 1450
28 200
m
A = = = 0.86 m2
G 32 800

FIG. 20-65
Transfer Units (NTUs) vs. Theoretical Stages (N)

12.0

10.0

8.0
NTUs

6.0
N=4.0
N=3.5

4.0 N=3.0
N=2.5
N=2.0
2.0
N=1.5
N=1.0

0.0
0 10 20 30 40 50 60 70

Circulation Ratio, mass lean TEG sol/mass water absorbed

20-35
FIG. 20-66
Estimated HTU vs. Gas Density for Various Structured Packings

1.0

0.9
As = 250 m 2/m 3
=(76 ft 2/ft 3)
0.8
HTU, m

As = 300 m 2/m 3
0.7 =(91 ft 2/ft 3)

As = 350 m 2/m 3
0.6 =(107 ft 2/ft 3)

0.5

0.4
0 25 50 75 100 125
Gas Density, kg/m3

0.5 0.5
4A (4)(0.86) FIG. 20-67
D = = = 1.05 m
3.14 Contactor Sizing Parameters for Glycol Contactors

K factor, m/s C factor, m/h
For Structured packing:
Bubble Cap Trays

CBubble cap 0.5
D
= CStructured packing (DBubble cap) 50 cm tray spacing 0.043 154
60 cm tray spacing 0.049 176
176

0.5 75 cm tray spacing 0.052 187
= (1.05) = 0.7 m Packing
384

Structured (Standard) 0.091 to 0.122* 329439
TEG will typically absorb about 3.74.5 Sm of sweet natu- 3
Structured (High Capacity) 0.122 to 0.152* 439-549
ral gas per m3 of glycol at 6900 kPa (abs) and 38C. Gas solubil- Random
ity will be considerably higher if the gas contains significant
amounts of CO2 and H2S. 2.5 cm Pall rings 0.04 to 0.055 143198
5 cm Pall rings 0.058 to 0.079 208285
The estimated solubility of CO2 and H2S in TEG is shown in
Figs 20-68 thru 20-71.61 These were developed using the data * Depending on packing density and vendor
in GPA RR-183 and 189.62,63 Equation 20-1261 may also be used
to estimate the solubility of H2S and CO2 in TEG and EG as a
function of pressure, temperature and acid gas composition in Pi = yi P
the vapor phase. At low acid gas partial pressures [less than
yi is the mole fraction of acid gas in the vapor phase
1400 kPa (abs)], the error is small, less than 10%. Accuracy de-
creases with increasing acid gas partial pressure. xi is the mole fraction of the acid gas in the liquid phase
(0.01) Pi T is the absolute temperature, K
x =


i
1 P
xH2O is the mole fraction of water in the liquid phase
exp A + B T E CxH2O + D T
Eq 20-12 P is the absolute pressure, kPa (abs)

Pi is the partial pressure of the acid gas (component i: CO2


or H2S)

20-36
Constants for Equation 20-12 Glycol Reboiler Duty: Basis 1 m3 TEG

System A B C D E Sensible Heat:


H2S in EG/
Qs = m Cp t
4.256 1298 1.824 0.02604 0.003354
Water (1120 kg)
2.78 kJ
= kg C (200C 150C)
H2S in TEG/
3.037 1414 1.4058 0.02130 0.003354
m3
Water

= 156 000 kJ/m3
CO2 in EG/
6.125 1232 1.287 0.01934 0.003354
Water Vaporization of Absorbed H2O:
CO2 in TEG/
4.813 1239 1.429 0.01617 0.003354
Qv = (Hvap)(W)
Water
2260 kJ 1 kg H2 O = 90 000 kJ/m3

=
0.025 m3 TEG
Flash tank sizing should be sufficient to degas the glycol so- kg H2O
lution and skim entrained liquid hydrocarbons, if necessary. A
minimum retention time of 35 minutes is required for degas- Condenser Duty @ 25% Reflux Ratio:
sing. If liquid hydrocarbons are to be removed as well, retention
Qc = (0.25)(Qv) = 22 500 kg/m3
times of 2030 minutes may be required for adequate separa-
tion. Flash tank pressures are typically less than 520 kPa (abs). Total Duty Including 10% Heat Loss:
Regenerator sizing requires establishing the reboiler duty Qr = (156 000 + 90 000 + 25 500)(1.1)
and, when high TEG concentrations are required, providing
sufficient stripping gas. = 295 000 kJ/m3

A quick estimate of reboiler duty can be made using Equa- Total Duty Based on 0.85 Sm3/d of gas:
tion 20-3. Q = (295 000 kJ/m3)(0.025 m3/kg)
Q = (418 000) (Lg ) Eq 20-13 (0.85 106 Sm3/d/86 400)
((1450110) kg/106 Sm3) = 97 kW
Equation 20-13 is approximate and usually gives values
which are higher than the actual duty. A more rigorous deter- Regeneration of TEG at 204C and 1 atmosphere will pro-
mination of reboiler duty is shown in Example 20-12. duce about 98.6 wt% glycol. Regeneration at higher altitude
(lower regenerator pressure) will result in higher concentra-
Example 20-12 Determine reboiler duty for conditions in tions at 204C or a reduced regeneration temperature at the
the previous example. Assume the rich TEG temperature en- same concentration.
tering the regenerator is 150C and the reboiler temperature
is 200C.

FIG. 20-68
Approximate Solubility of H2S in Triethylene Glycol at 3500 kPa vs.
Temperature, H2S Content of Gas Phase, and Water Content of TEG

10.000
H2S
H2S Solubility, std. m3H2S / m3 TEG solution

H2S

H2S

1.000 H2S H2S

H2S

H2S

0.100 H2S H2S


H2S

H2S

H2S
0.010

0.001
20 30 40 50 60 70 80 90 100
Temperature,C

20-37
CONTROL OF BTEX EMISSIONS FROM Vapor-liquid equilibrium constants (K-values) for benzene,
toluene, ethylbenzene, and o-xylene (BTEX) in TEG solutions
TEG REGENERATORS are presented in GPA RR-131.64
Heavier paraffin hydrocarbons are essentially insoluble
Figs. 20-72 and 20-7365 show the estimated percentage ab-
in TEG. Aromatic hydrocarbons, however, are very soluble in
sorption of BTEX components in TEG at 2100 and 6900 kPa
TEG, and significant amounts of aromatic hydrocarbons may be
(abs) as a function of circulation ratio and contactor tempera-
absorbed in the TEG at contactor conditions. This may present
ture. The circulation ratio is m3/h of TEG solution/106 Sm3/d of
an environmental or safety hazard when they are discharged
gas. BTEX solubility increases with increasing circulation ratio
from the top of the regenerator.

FIG. 20-69
Approximate Solubility of H2S in Triethylene Glycol at 7000 kPa vs.
Temperature, H2S Content of Gas Phase, and Water Content of TEG

H2 S
H2S Solubility, std. m3H2S / m3 TEG solution

10.00
H2S

H2S

H2S
H2S

1.00 H2S

H2S

H2S H2S

0.10 H2S

H2S

H2S

0.01
20 30 40 50 60 70 80 90 100
Temperature,C

FIG. 20-70
Approximate Solubility of CO2 in Triethylene Glycol at 3500 kPa
vs. Temperature, CO2 Content of Gas Phase, and Water Content of TEG

CO2
CO2 Solubility, std m 3 CO2 / m 3 TEG solution

CO2
CO2

CO2
1.00
CO2

CO2

CO2

CO2 CO2

CO2
0.10

0.01
20 30 40 50 60 70 80 90 100
Temperature, C

20-38
and decreasing temperature. The effect of pressure on solubil- pendency is demonstrated with three sets of solubility curves
ity is more complicated. EOS correlations suggest solubility in- (25C, 35C, and 50C). In general, increased contactor temper-
creases with increasing pressure at low pressures, but decreas- ature means higher inlet gas water content and a higher TEG
es with increasing pressure at pressures above 48006900 kPa circulation rate. This is why the 50C curves are presented at
(abs). The two pressures used in Figs 20-72 & 20-73 (2100 and high circulation ratios and the 25C curves are presented at low
6900 kPa (abs)) are the two pressures at which experimental circulation ratios.
data was collected in GPA RR-131.
Example 20-13 Estimate the quantity of benzene absorbed in
The BTEX absorption Figs 20-72 and 20-73 is presented for the glycol system presented in Example 20-11. The concentra-
benzene, toluene, e-benzene and o-xylene. The temperature de- tion of benzene in the feed gas is 300 ppm (0.0003 mol fr).

FIG. 20-71
Approximate Solubility of CO2 in Triethylene Glycol at 7000 kPa
vs. Temperature, CO2 Content of Gas Phase, and Water Content of TEG

10.00
CO2 Solubility, std m 3 CO 2 / m 3 TEG solution

CO2

CO2
CO2

CO2

CO2
1.00
CO2

CO2

CO2
CO2

CO2

0.10
20 30 40 50 60 70 80 90 100
Temperature, C

FIG. 20-72
BTEX Absorption in TEG Contactors at 300 psia (2068 kPa)

Circulation Ratio, (m3/h TEG)/(106 Sm 3/d of gas)


0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8
60 60
Solid lines: 25C (77F)
Dashed lines: 35C (95F)
Dotted lines: 50C (122F)
50 50
BTEX Absorption, %

BTEX Absorption, %

40 40

30 30

20 20

10 10

0 0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

Circulation Ratio, US GPM TEG/MMSCFD of gas

20-39
FIG. 20-73
BTEX Absorption in TEG Contactors at 1000 psia (6895 kPa)

Circulation Ratio, (m3/h TEG)/(10 6 Sm 3 /d of gas)


0.0 0.4 0.8 1.2 1.6 2.0 2.4 2.8
50 50
Solid lines: 25C (77F)
Dashed lines: 35C (95F) 45
Dotted lines: 50C (122F)
40 40
BTEX Absorption, %

BTEX Absorption, %
35

30 30

25

20 20

15

10 10

0 0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35

Circulation Ratio, US GPM TEG/MMSCFD of gas

Calculate TEG circulation rate in m3/h: stream. Emission rates of BTEX pollutants increase rapidly
with condenser operating temperature and stripping gas rate
(0.025 m /kg H2O absorbed)
3
(if stripping gas is used). These factors will largely dictate the
(0.85 10 Sm /d)(1450110) kg H2O/10 Sm = 1.2 m3/h
6 3 6 3
emission control performance for a given condenser and over-
24 h/d head vent stream.
Circulation ratio = (1.2 m3/h)/(0.85 106 Sm3/d) = 1.4 Air Cooled Condensers: Air cooled condensers with ei-
ther natural or forced draft cooling are the most common
From Fig. 20-72, estimated benzene absorption at 38C options because of the relatively simple design and com-
and 2070 kPa (abs) is approx 9% petitive capital cost. However, the condensing tempera-
From Fig. 20-73, estimated benzene absorption at 38C ture will typically be 11oC higher than the ambient dry
and 6900 kPa (abs) is approx 10% bulb air temperature which limits the effectiveness of
condensation in warm climates.
At 4100 kPa (abs) and 38C use 10% absorption
Glycol Cooled Condensers: Glycol cooled condensers use
Mass flow of benzene in regenerator overhead stream. rich glycol from the contactor (prior to the glycol flash
tank) as the coolant. The condenser outlet temperature is
(850
000 Sm3/d)(0.0003)(78 kg/kmol)(10%) = 84 kg/d
typically at or above the ambient temperature.
(23.64 Sm3/kmol)
Water Quench Condensers: Water quench condensers
The feed gas to a glycol dehydration system will often contain combine a cool water stream with the regenerator over-
small quantities of BTEX and as seen in Example 20-13, signifi- head vent stream to condense the water and hydrocar-
cant amounts of these BTEX components will be absorbed by glycol bons. The quench water is cooled in a separate heat ex-
in the contactor. Almost all of the BTEX components are stripped changer using air cooling or a refrigeration system.
from the TEG solution in the regenerator and will be present in
the regenerator overhead vapor. In most countries, these compo- Combined Air CooledWater Cooled Condenser: Com-
nents are considered hazardous air pollutants and emissions of bined air cooledwater cooled condensers use an air
these components are strictly regulated. Listed below is a sum- cooled condenser to partially condense the hydrocar-
mary of the commonly used emission control options. bons and water. A water cooled condenser then cools the
stream further and condenses essentially all the water
There are three main approaches to BTEX emission control and hydrocarbons present in the regenerator overhead
from a glycol system. The first is to recover them as a salable vent stream. Cooling water is supplied to this condenser
liquid product by condensing the regenerator overhead vent from a small cooling tower using water condensed from
stream. The second is to burn BTEX components in an incin- the regenerator overhead vent stream. The cooling wa-
erator/flare or as fuel. The third method is to recycle the compo- ter temperature will approach the wet bulb temperature
nents back into the process. which in dry climates will often allow the condensing
temperature to be below the ambient air temperature.
Condensers
If stripping gas is used in the regenerator there may be a
There are a variety of condensation systems using air, wa- significant amount of non-condensable hydrocarbons in the
ter, gas, or glycol to condense the regenerator overhead vent regenerator vent. This stream will be predominately methane

20-40
FIG. 20-74
Simplified Process Flow Diagrams of Enhanced TEG Regeneration Systems

but will also contain heavier hydrocarbons, including BTEX Recycle


components. If the unit employs a direct-fired reboiler, the un-
condensed vent stream is often used as fuel gas in the reboiler. In some facilities, a near atmospheric pressure vapor
If the reboiler heat source is hot oil, steam or electric coils, this stream may exist in the process. A common example is the low
vent stream is typically routed to a flare/incinerator or is re- pressure flash gas leaving the last stage of crude oil or conden-
cycled back into the process. sate stabilization. A relatively simple method of handling the
regenerator overhead vent stream is to use a blower or low pres-
Incinerators/Flares sure compressor such as a sliding vane or liquid ring compres-
sor to boost the regenerator vapors into the flash gas steam.
Regenerator overhead vent stream combustion is difficult
The hydrocarbons and water in the regenerator vent end up in
because of the very high concentration of water in the stream
the crude oil product or the produced water disposal system.
and the possibility of hydrocarbons and water condensing in the
The regenerator vent stream flow rate is typically small rela-
incinerator/flare. Condensation in the incinerator/flare may re-
tive to the process stream.
sult in smoking and incomplete combustion and in cold climates
special precautions need to be taken to prevent freezing if the
flare/incinerator is remote from the regenerator. Incinerators/ ENHANCED GLYCOL
flares are used where it is uneconomical to recover the BTEX as CONCENTRATION PROCESSES
a liquid product. Usually incinerators differ from flares in that
they are designed to provide 99% + combustion of the flamma- There are several principles and processes for obtaining
ble components in the feed. Catalytic combustion has been used higher TEG purity than 98.799.0 wt%, which is the TEG purity
in some locations. obtained by regeneration at 204C and atmospheric pressure.
All methods are based on the principle of reducing the effective

20-41
partial pressure of H2O in the vapor space of the glycol reboiler, tion or higher concentrations for a given stripping gas rate. Fig.
and hence obtaining a higher glycol concentration at the same 20-75 shows the approximate lean TEG concentration produced
temperature.The most common method for enhancement of the in an atmospheric pressure stripping column as a function of
glycol concentration is the use of stripping gas in the reboiler stripping gas rate. Lean TEG concentrations above 99.9 wt%
itself or in a packed stripping column below the reboiler. Other have been achieved with stripping gas.
patented or proprietary processes in use to enhance the TEG pu-
rity and thereby achieve a lower water dew point are described OTHER CONSIDERATIONS
below. The processes are illustrated on Fig. 20-74.
Under conventional dehydration conditions, 40 to 60% of
DRIZO methanol in the feed gas to a glycol dehydrator will be absorbed
by the TEG.66 This will add additional heat duty on the reboiler
DRIZO achieves glycol enrichment by means of a stripping and additional vapor load on the regenerator. High methanol
medium which is a liquid at ambient conditions but a vapor at injection rates and slug carryover can cause flooding.
reboiler conditions. The stripping medium is a mixture of C5+
hydrocarbons which may be supplied from external sources or Glycol losses can be defined as mechanical carryover from
internally generated by absorption into the TEG in the contac- the contactor (normally 13 liters/106Sm3 for standard mist
tor and subsequent recovery as a liquid in the regenerator over- eliminator) plus vaporization from the contactor and regen-
head. The condensed hydrocarbons, which contain BTEX com- erator and spillage. Glycol losses, exclusive of spillage, range
ponents absorbed from the gas, are separated from the water in from 7 liters/106Sm3 for high pressure low-temperature gases
a 3-phase separator, vaporized and superheated, and flow to the to as much as 40 liters/106Sm3 for low pressure, high tempera-
lean-glycol stripping column to serve as the stripping medium. ture gases. Excessive losses usually result from foaming in the
The advantage of the DRIZO process is that very high strip- absorber and/or regenerator. Anti-foam agents are sometimes
ping gas rates can be employed without additional hydrocarbon used.
emissions from the regenerator. This can result in TEG purities TEG vaporization losses at the contactor are minimal unless
above 99.99 wt %. In addition, the mixture of hydrocarbons and the gas temperature exceeds about 50C. These losses are more
water form a heterogeneous azeotrope in the partial condenser significant at lower pressures. Tetraethylene glycol (TREG) has
at the top of the regenerator. As a result of this behavior, the been used in some cases to minimize losses in high tempera-
condensing temperature is independent of the stripping rate. ture, low pressure systems. Vaporization losses at the regen-
This is not the case when the stripping medium is natural gas. erator typically result from excessive stripping gas rates and/or
As the hydrocarbons build up in the 3-phase separator, they are inadequate reflux.
drawn off as a liquid stream which can be blended into a crude
oil, condensate or NGL product. Various options to further en-
hance the lean TEG purity are available, such as drying the hy- FIG. 20-75
drocarbon liquid solvent with solid desiccant. In addition to the Effect of Stripping Gas on TEG Concentration
very high TEG concentrations DRIZO is effective in recovering
BTEX components absorbed in the TEG.

COLDFINGER
The COLDFINGER process can be described as a trace
water exhauster for the TEG. A condensing tube bundle (cold
finger) is inserted in the surge tank vapor space. In most ap-
plications, rich TEG from the glycol contactor is used as the
coolant in the COLDFINGER tube bundle. The surge tank op-
erates at reboiler temperature (193204C). The vapor in this
space is water-rich, typically in excess of 50 wt% H2O. Likewise,
the liquid that condenses on the outside of the tube bundle has
a relatively high H2O concentration. It is collected in a trough
below the tube bundle and is removed from the surge tank, typi-
cally being recycled to the rich TEG regenerator feed stream.
The liquid (lean TEG) in the bottom of the surge tank seeks
to restore the equilibrium vapor composition and in doing so,
exhausts its trace water before it reaches the surge-tank outlet
nozzle. Operators of COLDFINGER units have reported lean
TEG concentrations in the 99.2-99.5 wt% range. The COLD-
FINGER process does not use stripping gas.

STRIPPING GAS
Stripping gas is by far and away the commonly used tech-
nique for enhancing the lean TEG concentration. The stripping
gas is typically dehydrated natural gas often taken from the
fuel gas system. In rare cases, the stripping gas may be an inert
gas, e.g. N2. Stripping gas can be introduced directly into the re-
boiler through a sparge tube in the lean TEG or it can be intro-
duced in a countercurrent stripping column installed below the
reboiler. The latter method provides more effective stripping
which results in lower rates for a given lean TEG concentra-

20-42
Glycol losses in CO2 dehydration systems can be significant- dewpoint requirements, simultaneous control of water and hy-
ly higher than in natural gas systems particularly at pressures drocarbon dewpoints, and special cases such as oxygen contain-
above about 6200 kPa (abs). This is due to the solubility of TEG ing gases, etc. In processes where cryogenic temperatures are
in dense phase CO2. Glycerol67 is much less soluble in the vapor encountered, solid desiccant dehydration usually is preferred
phase and has been used successfully as a desiccant in some over conventional methanol injection to prevent hydrate and
CO2 dehydration systems. ice formation. Solid desiccants are also often used for the drying
and sweetening of NGL liquids.
Glycol becomes corrosive with prolonged exposure to oxy-
gen. A dry gas blanket on the glycol surge tank will help elimi- Desiccants in common commercial use fall into one of three
nate oxygen absorption. Special precautions should be taken if categories:
oxygen is in the gas to be dehydrated. Thermal decomposition
of TEG can become a problem if TEG is heated to temperatures G
 els alumina or silica gels manufactured and condi-
above 200C. tioned to have an affinity for water.

A low pH accelerates decomposition of glycols. Bases such as A


 lumina a manufactured or natural occurring form of
triethanolamine, borax, or sodium mercaptobenzothiazole may aluminum oxide that is activated by heating.
be added to maintain pH, but they should be added sparingly. Molecular Sieves manufactured or naturally occur-
ring aluminosilicates exhibiting a degree of selectivity
SOLID DESICCANT DEHYDRATION based on crystalline structure in their adsorption of natu-
ral gas constituents.
There are several solid desiccants which possess the physi-
cal characteristic to adsorb water from natural gas. These des- Silica Gel is a generic name for a gel manufactured from
iccants generally are used in dehydration systems consisting of sulfuric acid and sodium silicate. It is essentially pure silicon
two or more towers and associated regeneration equipment. See dioxide, SiO2. It is used for gas and liquid dehydration and hy-
Fig. 20-76 for a simple two-tower system. One tower is onstream drocarbon (iC5+) recovery from natural gas. When used for hy-
adsorbing water from the gas while the other tower is being re- drocarbon removal, the units are often called HRUs (Hydrocar-
generated and cooled. Hot gas is used to drive off the adsorbed bon Recovery Units) or SCUs (Short Cycle Units). When used
water from the desiccant, after which the tower is cooled with for dehydration, silica gel will give outlet dewpoints of approxi-
an unheated gas stream. The towers are switched before the on- mately 50C.
stream tower becomes water saturated. In this configuration,
Alumina is a hydrated form of alumina oxide (Al2O3). It is
part of the dried gas is used for regeneration and cooling, and
used for gas and liquid dehydration and will give outlet dew-
is recycled to the inlet separator. Other streams may be used if
points of about 68C. Less heat is required to regenerate alu-
they are dry enough, such as part of the residue gas.
mina and silica gel than for molecular sieve, and the regenera-
Solid desiccant units generally cost more to buy and oper- tion temperature is lower. Molecular sieves give lower outlet
ate than glycol units. Therefore, their use is typically limited water dewpoints.
to applications such as high H2S content gases, very low water
Molecular sieves are a class of aluminosilicates. They pro-

FIG. 20-76
Example Solid Desiccant Dehydrator Twin Tower System

20-43
duce the lowest water dewpoints and can be used to simultane- the desiccant will be at the top of the bed and will not affect
ously sweeten and dry gases and liquids. Their equilibrium wa- the effluent dewpoint when adsorption is resumed. In addition,
ter capacity is much less dependent on adsorption temperature upflow heating helps to strip any contaminants from the top of
and relative humidity. They are usually more expensive. the bed extending desiccant life. Regeneration gas flow during
the cooling period may be upflow if the gas is completely free
Molecular sieve dehydrators are commonly used upstream of water, which saves two switching valves per tower. If the
of deep recovery NGL extraction plants, typically cryogenic cooling gas contains water, cooling flow should be downflow to
turbo-expander processes, as well as LNG liquefaction plants. avoid preloading of the desiccant at the bottom of the bed with
These plants operate at very cold temperatures and require water.
very dry feed gas to prevent formation of hydrates. Dehydration
to a 100C dewpoint is possible with molecular sieves. Water Design
dewpoints less than 100C can be accomplished with special
design and strict operating parameters. The first step is to determine the bed diameter, which de-
pends on the superficial velocity. Too large a diameter will re-
Fig. 20-77 presents the important properties of commercial quire a high regeneration gas rate to prevent channeling. Too
solid desiccants. Fig. 20-7868 shows static equilibrium capac- small a diameter will cause too high a pressure drop and dam-
ity vs. relative humidity for various new desiccants. This is for age the sieve. The pressure drop is determined by a modified
comparison only. Adsorption capacity depends on other param- Ergun69 equation, which relates pressure drop to superficial
eters besides relative humidity, and design values should be velocity as follows:
obtained from desiccant suppliers. Fig. 20-79 shows water-ad-
sorption isotherms for 4A molecular sieve in contact with air. P
This gives the relationship of static-equilibrium water capacity = B V + C V 2

Eq 20-14
L
to the operating temperature and gas dew-point temperature.
Although the chart is based on an air-water system, it also can Constants for Equation 20-11 are:
be used for natural gas. Particle Type B C
The continuous process requires two (or more) vessels with 3.2mm bead (4x8 mesh) 0.0693 3.75 x 107
one on-line removing water (in adsorption) while the other is 3.2mm extrudate 0.0893 5.23 x 107
being regenerated. Generally a bed is designed to be on-line in 1.6mm bead (8x12 mesh) 0.1881 5.74 x 107
adsorption for 8 to 24 hours. When the bed is taken off-line, the 1.6mm extrudate 0.2945 8.86 x 107
water is removed by heating to 190C315C, depending on the
desiccant used and the performance specification (i.e., 190C Fig. 20-80 was derived from Equation 20-14 by assuming
for silica gel and up to 315C for molecular sieve, with alumina a gas composition and temperature and setting the maximum
gel and activated alumina falling in between). The regeneration allowable P/L equal to 7.5 kPa/m. The design pressure drop
gas used to heat the bed is usually a slipstream of dry process through the bed should be about 35 kPa. A design pressure drop
gas. The regeneration gas is returned to the process after it has higher than 55 kPa is not recommended as the desiccant is frag-
been cooled and the free water removed. Any heat source can be ile and can be crushed by the total bed weight and pressure drop
used to heat the regeneration gas including waste heat from en- forces. Remember to check the pressure drop after the bed height
gines and turbines, but fired heaters are the most common heat has been determined. Once the allowable superficial velocity is
source. This is an important design consideration since heat is estimated, calculate the bed minimum diameter (i.e., Dminimum),
often a major operating cost. and select the nearest standard diameter (i.e. Dselected):
4q
0.5
Gas flow during adsorption is typically downflow. This al- Dminimum = Eq 20-15
lows higher gas velocities (thus smaller diameter towers) since 60 V
max
bed fluidization is avoided. Regeneration gas flow is upflow dur-
m
ing the heating period. In this way, any residual water left on q =
60 Eq 20-16

FIG. 20-77
Typical Desiccant Properties

Approx. Minimum
Bulk
Heat Capacity, Moisture Content
Desiccant Shape Density, Particle Size
kJ/(kg K) of Effluent Gas
kg/m3
(mg/kg)
Alumina Alcoa F200 Beads 770 7x14 Tyler mesh 1.00 68C dew point
3.2 mm/4.8 mm/6.4 mm
Activated Alumina UOP A-201 Beads 735 36 mesh or 58 mesh 0.92 510 ppmv
Mole Sieve Grace Davison 4A Beads 675720 48 mesh or 812 mesh 0.96 0.1 ppmv (101C)
Molecular Sieve UOP 4A-DG Extrudate 640705 3.2 mm/1.6 mm pellets 1.00 0.1 ppmv
Mole Sieve Zeochem 4A Beads 720735 48 mesh or 812 mesh 1.00 0.1 ppmv
Silica Gel Sorbead R Beads 785 5x8 mesh 1.05 51C dew point
Silica Gel Sorbead H Beads 720 5x8 mesh 1.05 51C dew point
Silica Gel Sorbead WS Beads 720 5x8 mesh 1.00 51C dew point

20-44
Obtain the corresponding superficial velocity, Vadjusted as fol-
FIG. 20-78
lows:
Static Equilibrium Capacity vs. Relative Humidity
Dminimum 2

for Selected Solid Desiccants46 Vadjusted = Vmax Eq 20-17
Dselected

The next step is to choose an adsorption period and calculate
the mass of desiccant required. Eight to twelve hour adsorption
periods are common. Periods of greater than 12 hours may be
justified especially if the feed gas is not water saturated. Long
adsorption periods mean fewer regeneration cycles and longer
sieve life, but larger beds and additional capital investment.
During the adsorption period, the bed can be thought of as
operating with three zones. The top zone is called the satura-
tion or equilibrium zone. The desiccant in this zone is in equilib-
rium with the wet inlet gas. The middle or mass transfer zone
(MTZ) is where the water content of the gas is reduced from
its inlet concentration to <1 ppmv. The bottom zone is unused
desiccant and is often called the active zone. If the bed operates
too long in adsorption, the mass transfer zone begins to move
out the bottom of the bed causing a breakthrough. At break-
through, the water content of the outlet gas begins to increase
and will eventually reach feed gas water content when the MTZ
is completely displaced.
Both water capacity and the rate at which solid desiccants
adsorb water decline as the material ages. The object of the de-
sign is to install enough desiccant such that after three to five
years, the mass transfer zone will be at the bottom of the bed at
the end of the adsorption period.
In the saturation zone, molecular sieve is expected to hold
approximately 13 kg of water per 100 kg of sieve. New sieve

FIG. 20-79
UOPTM Adsorbents
4A-DG MOLSIV TM Pellets Water Adsorption Isotherms

20-45
will have an equilibrium capacity near 20%; 13% represents Molecular sieve bulk density is 675735 kg/m3 for spherical
the approximate capacity of a 35 year old sieve. This capacity particles and 640705 kg/m3 for extruded cylinders.
needs to be adjusted when the gas is not water saturated or the
temperature is above 24C. See Fig. 20-81 and 20-82 to find the Even though the MTZ will contain some water (approxi-
correction factors for molecular sieve. To determine the mass of mately 50% of the equilibrium capacity), the saturation zone
desiccant required in the saturation zone, calculate the amount is estimated assuming it will contain all the water to be re-
of water to be removed during the cycle and divide by the effec- moved.
tive capacity. The length of the mass transfer zone can be estimated as
Wr follows:
SS =
(0.13)(CSS)(CT ) Eq 20-18 LMTZ = (Vadjusted/640 )0.3 (Z) Eq 20-20

(Ss)(4) Where: Z = 0.52m for 3mm sieve


LS = 0.26m for 1.5mm sieve
(D2)(bulk density) Eq 20-19
The total bed height is the summation of the saturation zone
and the mass transfer zone heights. It should be no less than
FIG. 20-80 the vessel inside diameter, or 1.8m, whichever is greater.
Allowable Velocity for Mole Sieve Dehydrator Now the total bed pressure drop is checked. The P/L for the
selected diameter, Dselected, is adjusted using Equation 20-14 or
the following approximation:
Vadjusted 2
(P/L)adjusted (7.5 kPa/m) Eq 20-21
Vmax

The result is multiplied times the total bed height (LS +
LMTZ) to get the total design pressure drop, which should be 35
55 kPa. This is important, because the operating pressure drop
can increase to as much as double the design value over three
years. Too high a pressure drop plus the bed weight can crush
the sieve. If the design pressure drop exceeds 55 kPa, the bed
diameter should be increased and the sieve amount and vessel
dimensions recalculated.
A second method uses Equation 20-17, but replaces the
saturation capacity of 13% with an effective desiccant capac-
ity which includes the MTZ effect, temperature, and relative
humidity corrections. When using this method, an effective ca-
pacity of 810% is typically assumed. This method is adequate
for most planning and feasibility calculations.
To estimate the total cylindrical length of a tower, add a
minimum of 1.0 m to the bed height, which provides the space
for an inlet distributor and for bed support and hold-down balls
under and on top of the sieve bed.

Regeneration Calculations
The first step is to calculate the total heat required to desorb
FIG. 20-81 the water and heat the desiccant and vessel. A 10% heat loss is
assumed.
1 Mole Sieve Capacity Correction for
Relative Water Saturation
FIG. 20-82
Mole Sieve Capacity Correction for Temperature

20-46

kJ transfers to the bed, vessel steel, and heat loss to atmosphere;
Qw = 4200 (kg of water on bed) Eq 20-22
kg and the balance leaves with the hot gas.

The regeneration-gas flow rate is calculated from Equation
1.0 kJ
Qsi = (kg of sieve) (Trg Ti) Eq 20-23 20-29 below. A typical average heat capacity for regeneration gas
kg K is 2.7 kJ/kg C. The temperature, Thot, is 28 C above the temper-

ature, Trg, to which the bed must be heated. The temperature, Tb,
0.5 kJ is the bed temperature at the beginning of regeneration, which is
Qst = (kg of steel) (Trg Ti) Eq 20-24
kg K the same as the dehydration-plant feed temperature.

The heating time is usually 50% to 60% of the total regen-
Qhl = (heat loss) = Qw + Qsi + Qst)(0.10) Eq 20-25 eration time which must include a cooling period. Fig. 20-83
shows a typical temperature profile for a regeneration period
The temperature, Trg, is the temperature to which the bed (heating and cooling). For 8 hour adsorption periods, the regen-
and vessel must be heated based on the vessel being externally eration normally consists of 4 1/2 hours of heating, 3 hours of
insulated (i.e., no internal insulation which is usually the case). cooling and 1/2 hour for standby and switching. For longer pe-
This is about 28 C below the temperature of the hot regenera- riods the heating time can be lengthened as long as a minimum
tion gas entering the tower. pressure drop of 0.23 kPa/m is maintained to ensure even flow
distribution across the bed.
The weight of the vessel steel is estimated from the equa-
tions below. Equation 20-25 is the ASME Section VIII Div. 1

m rg = Qtr/(Cp(Thot Tb) (heating time)) Eq 20-29
equation in terms of the vessel inside diameter. It is based on
a maximum tensile stress of 130 MPa (i.e., the ASME 2001 The superficial velocity of the regeneration gas is calculated
maximum allowable tensile stress for SA516 Grade 70 steel at from Equation 20-30 for which q is calculated from Equation
343 C and a welded-joint efficiency of 1.0). This is 134 MPa at 20-16.
315 C. The design pressure, Pdesign, is usually set at 110% of the 4q
V = Eq 20-30
maximum operating pressure. The value of 3.2 mm in Equation (D2)
20-26 is the corrosion allowance in inches. The term 0.75Dbed
accounts for the weight of the tower heads. The value of 0.91 The calculated superficial velocity can not be less than the
mm provides the space for the inlet distributor and support and value that corresponds with a minimum bed pressure drop of
hold-down balls. 0.23 kPa/m. This can be determined from Fig. 20-84, which was
derived from Equation 20-14 by assuming a gas composition
t (mm) = (1000 DbedPdesign) / and temperature and setting P/L equal to 0.23 kPa/m. If the
((2x130,000 = 260,000 kPa) 1.2Pdesign) Eq 20-26 calculated velocity is less than this, the regeneration gas rate,
rg, must be increased by multiplying it by the ratio Vmin/V, and
m
ass of steel (kg) = 29.8 (t + 3.2)
M
(LS + LMTZ + 0.75 Dbed + 0.91)Dbed Eq 20-27 the period of regeneration should be decreased by multiplying
it times the ratio V/Vmin. Equation 20-14 may also be used to
For determination of the regeneration gas rate, calculate calculate Vmin using a P/L equal to 0.23 kPa/m.
the total regeneration load from Equation 20-28.
Qtr = (2.5)(Qw + Qsi + Qst + Qhl) Eq 20-28 FIG. 20-84
The 2.5 factor corrects for the change in temperature dif- Minimum Regeneration Velocity for
ference (in out) across the bed with time during the heating Mole Sieve Dehydrator
period. It assumes that 40% of the heat in the regeneration gas

FIG. 20-83
Inlet and Outlet Temperatures During Typical Solid
Desiccant Bed Regeneration Period

20-47
General Comments Vadjusted = (758 m/h)(2.21/2.25)2 = 731 m/h (Equation
20-17)
The regeneration cycle frequently includes depressuring/
repressuring to match the regeneration gas pressure and/or ( P/L)adjusted = 7.5(731/758)2 = 7.0 kPa/m (Equation
to maximize the regeneration gas volume to meet the velocity 20-21)
criterion. In these applications, the rate of depressuring or re-
2. Estimate the amount of water to be removed from the
pressuring should not exceed 350 kPa per/minute. Some appli-
feed per cycle for each bed. Base this on a 24-hour cycle
cations, termed pressure swing adsorption, regenerate the bed
consisting of 12 hours adsorbing and 12 hours regener-
only with depressurization and sweeping the bed with gas just
ating (heating, cooling, standby, and valve switching).
above atmospheric pressure, but this is not used in gas dehy-
From Fig. 20-4, the water content at 4140 kPa (abs) and
dration applications.
38C is 1410 mg/Sm3 (1410 kg/106 Sm3). The water con-
Moisture analyzers for very low water contents require care tent at a dew point of 101C is essentially zero, so the
to prevent damage to the probes. When inserted into the beds, water removed is the following:
sample probes and temperature probes must be installed to
w
 = (1410 kg/106 Sm3)(2.85 106 Sm3/day)/(24 h/day)/
reach the center of the gas phase.
= 167 kg/h of water removed
Solid desiccant towers are insulated externally or possibly
Wr = (167 kg/h) (12 h) = 2004 kg water removed per
internally. Internal refractory requires careful installation and
12-hour drying period or 24-hour cycle per bed.
curing, usually before the desiccant is installed. It saves en-
ergy but the greatest benefit is it can dramatically reduce the 3. Determine the amount of sieve required and the bed
required heating and cooling times. This is often an important height based on a sieve bulk density of 720 kg/m3. Since
benefit for systems where regeneration times are limited. The the feed gas is water saturated, the relative humidity is
primary disadvantage is the potential for wet gas bypassing the 100%, so CSS is 1.0 from Fig. 20-81. From Fig. 20-82, CT is
desiccant through cracks and defects in the insulation during 0.93 at 38C. Applying the equations:
the adsorption cycle.
SS = (2004)/((0.13)(1.0)(0.93)) = 16 576 kg of
Example 20-14: 2.85 106 Sm3/day of natural gas with a mo- sieve for each bed (Equation 20-18)
lecular weight of 18 is to be processed for ethane recovery in a
turbo-expander plant. It is water saturated at 4140 kPa (abs) LS = (16 576)(4)/(3.1416 (2.3)2 (720)) = 5.54 m
and 38C and must be dried to 101C dew point. Determine bed height (Equation 20-19)
the water content of the gas, and the amount of water that must LMTZ = (731/640)0.3 (0.52) = 0.54 m for
be removed; and do a preliminary design of a molecular-sieve mass-transfer zone (Equation 20-20)
dehydration system consisting of two towers with down-flow
adsorption in one tower and up-flow regeneration in the other. LS + LMTZ = 5.54 + 0.54 = 6.08 m of sieve for each bed
Use 4A molecular sieve of 3.2 mm beads (i.e., 4x8 mesh). The
The total sieve = (6.08/5.54)(16 576)
regeneration gas is part of the plants residue gas, which is at
= 18 192 kg for each bed
4140 kPa (abs) and 38C and has a molecular weight of 17. The
bed must be heated to 260C for regeneration. 4. Check the bed design and pressure drop which is the P/L
calculated in Step 1 times the total bed height calculated
Solution Steps in Step 3: (7.0 kPa/m)(6.08 m) = 42.6 kPa which meets the
1. Determine the bed diameter and the corresponding P/L criteron of not exceeding 3555 kPa
and V. First determine the maximum superficial velocity 5. Calculate the total heat required to desorb the water
from Equation 20-14. Let the maximum P/L be 7.5 kPa/ based on heating the bed and vessel to 260C. First cal-
m. culate the weight of steel from Equation 20-26 and 20-27.
z = 0.93 from Fig. 23-8 for 17.4 mole weight which is con- Let the design pressure, Pdesign, be 110% of the operating
servative pressure:
Pdesign = (4140)(1.1) = 4554 kPa (ga)
 = (18 mole weight) (4140 kPa (abs))/((8.3145)
(311.15 K) (0.93)) = 31 kg/m3 (Equation 23-2) (1000) (2.25) (4554)
t= 
= 40.3 mm (Equation 20-26)
 = 0.015 mPa s (Fig. 23-27) 260 000 1.2 (4554)
Mass of steel = (29.8) (40.3 + 3.2) (5.54 + 0.54
Vmax = [(7.5 kPa/m)/(3.75 107)/(31 kg/m3)]1/2 + (0.75) (2.25) + 0.91) (2.25) = 25 310 kg
[(0.0693/3.75 107) (0.015 mPa s)/ (Equation 20-27)
(31 kg/m3)/2] = 758 m/h (Equation 20-14),
rewritten in terms of V Qst = (25 310 kg) (0.5 kJ/kg C)
(260C 38C) = 2 809 000 kJ (Equation 20-24)
m = [(2.85 10 Sm /day)/((24 h/day)(23.646
6 3

Sm3kmole))] (18 kg/kmole) = 90 400 kg/h Qw = (4200 kJ/kg) (2004 kg water)
= 8 417 000 kJ (Equation 20-22)
q = (90 400 kg/h)/(31 kg/m ) 3

= 2916 m3/h (Equation 20-16) Qsi = (18 192 kg) (1 kJ/kg C)


(260C 38C) = 4 039 000 kJ (Equation 20-23)
Dminimum = [(4(2916 m3/h))/
( 758 m/h)]1/2 = 2.21 m (Equation 20-15) Qhl = (2 809 000 + 8 417 000 + 4 039 000)
(0.10) = 1 527 000 kJ (Equation 20-25)
Round off upward to 2.25 m diameter, for which V and P/L
are adjusted as follows: Qtr = (2.5) (2 809 000 + 8 417 000 + 4 039 000
+ 1 527 000) = 41 980 000 kJ (Equation 20-28)

20-48
6. Calculate the flow rate of regeneration gas using Equa- Operating performance should be monitored periodically to
tion 20-29. Let the heating time be 60% of the total regen- adjust adsorption cycle length so that adequate dehydration is
eration period. obtained. Performance tests are scheduled on a routine basis,
ranging from monthly during early operations to six months or
(60%) (12 hr) = 7.2 hours heating longer. The size of the unit and frequency of regeneration cycles
m
rg = (41 980 000 kJ)/((2.7 kJ/kg C) also affect the timing of performance tests.
(288C 38C) (7.2 h)) = 8638 kg/h
(Equation 20-29) Refluxing
Refluxing is a phenomenon that begins during the early
7. Check that the P/L 0.23 kPa/m at 228C. heating stages in the regeneration of mol sieve adsorption beds.
Assume z = 1.0. It is more common in systems where the regeneration is ac-
complished with high pressure gas, usually at or near feed gas
= ((17 mol weight)(4140 kPa (abs))/((8.3145)
pressure. At the beginning of the regeneration cycle, the hot gas
(273 + 288)(K) (1.0)) = 15.1 kg/m3
picks up moisture and hydrocarbons as it flows upward through
q = (8638 kg/h)/(15.1 kg/m3) the bed. This gas cools as it travels upward through the bed and
= 572 m3/h of hot regeneration gas (Equation 20-16) eventually reaches saturation at some point. Any cooling that
takes place after saturation will result in the condensation of
Rearranging Equation 20-12: liquid water and hydrocarbons. This condensation is typically
V = 4q/D2 = ((4)(572)/((3.14)(2.25)2) = 144 m/h. more prevalent at the vessel wall and on the vessel head at the
top of the vessel. This temperature variance between the bot-
= 0.023 mPa s (Fig. 23-27) tom of the bed and the top of the vessel results in significant
condensation on the bed, at the side walls and the top section
P/L = (0.0693) (0.023) (144) + (3.75 107)
of the vessel.
(15.1) (144)2 = 0.347 kPa/m (Equation 20-14)
As the regeneration cycle continues, the temperature of the
This is safely above the minimum value of 0.23 kPa/m need- vessel walls and the desiccant near the top of the bed increases.
ed to prevent channeling. The results in re-vaporization of the condensed liquids, first the
hydrocarbons and then the water. Certain components of the
8. The design results are summarized as follows: binders used in 4A sieve are somewhat soluble in liquid water.
This solubility depends on the pH, temperature, and length of
Number of vessels: two
time that free water is in intimate contact with the adsorbent.
Vessel design pressure and temperature: Some of the soluble binder components can ion exchange with
4554 kPa (ga) and 315C the zeolite and/or combine with anions in the liquid water to
form solid when the water evaporates. This condition is made
Vessel dimensions: 2.25 m (2250 mm) ID by worse when contaminants such as amine or glycol are present
6.99 m (6990 mm) tan to tan due to carryover from an improperly designed inlet separator.
Weight of molecular sieve: 2 x 18,192 kg These salts can cement the remaining molecular sieve pellets or
beads together forming a solid mass that will restrict gas flow
Regeneration gas rate: 8331 kg/h (2.78 105 Sm3/day) through the bed and reduce water capacity. Occasionally the
solid salts form as a crust on the top of the bed or build-up along
Regeneration gas temperature: 288C
the vessel walls. Over time molecular sieve beds operating in
Cycle time: 24 hours, 12 hours adsorption, this manner may exhibit broken particles, dust, increased pres-
12 hours regeneration sure drop, channeling and premature breakthrough.
Heating time: 7.2 hours Refluxing can be minimized by utilizing a two-step regener-
ation cycle where the bed is first heated to approximately 93C
This example is based on the assumption that the regenera- with a lower temperature regeneration gas (approx. 121C).
tion gas is not recycled back to the feed gas. If the regeneration Once the bed and vessel walls have reached the desired temper-
is recycled back the the feed gas, as illustrated on Fig. 20-76, ature, the regeneration gas temperature is increased to 288
the amount of regeneration gas must be added to the inlet gas. 315C and the heating cycle is completed as normal. This two-
This is an iterative calculation. A good assumption is to assume step process minimizes the opportunity for refluxing because
that the regeneration gas rate is 10% of the feed rate. there is a small temperature difference between the bottom and
Bottom bed support typically includes three to five layers of top of the bed when the bulk of the water desorption begins.
inert ceramic balls in graduated sizes (smallest on top). On top Lower regeneration pressures are also helpful in preventing re-
of the bed, a hold-down screen is provided, again covered with fluxing. These techniques increase the heating time required
a layer of ceramic balls. In some cases, a layer of less expensive in the regeneration cycle and if the cycle time is limited they
desiccant can be installed on the top of the bed to catch con- may be difficult to implement. Several mol sieve manufacturers
taminants such as free water, glycol, hydrocarbons, amines, etc. have developed mol sieves that are more resistant to reflux-
This may extend the bed life. Good inlet separation of entrained ing. As always, effective inlet gas separation is imperative for
contaminants is absolutely essential for long desiccant life. trouble-free operation of an adsorption dehydration system.

Since solid desiccants can produce dust, 1m filters are fre- Calcium Chloride
quently installed at the outlet of the dehydration unit to protect
downstream equipment. Calcium chloride (CaCl2) can be used as a consumable desic-
cant to dehydrate natural gas. Solid anhydrous CaCl2 combines
with water to form various CaCl2 hydrates (CaCl2 XH2O). As

20-49
water absorption continues, CaCl2 is converted to successively all the methanol in the cold decanted methanol water stream
higher states of hydration eventually forming a CaCl2 brine originating in the cold process at feed gas conditions to recircu-
solution. late the methanol to the cold process. The water stream leaving
the stripper contains generally less than 100 ppm wt of meth-
10 to 20 mm CaCl2 pellets are installed in a fixed bed much anol. No heat is required for the process and no atmospheric
like a dry desiccant tower. Gas flow is upflow. The more efficient venting takes place.
designs utilize 34 trays below the solid bed to pre-contact the
gas with the brine solution. This removes a portion of the water Dehydration By Membrane Permeation
from the gas before contact with the solid CaCl2 and increases
unit capacity. One such unit is shown in Fig. 20-85. Membranes can be used to separate gas stream components
in natural gas such as water, CO2 and hydrocarbons accord-
The solid CaCl2 near the bottom of the fixed bed will typi- ing to their permeabilities. Each gas component entering the
cally be CaCl2 4H2O or CaCl2 6H2O and the CaCl2 at the membrane unit has a characteristic permeation rate that is
top of the fixed bed will be anhydrous CaCl2 or CaCl2 H20. In a function of its ability to dissolve in and diffuse through the
this way the gas contacts successively drier CaCl2 as it flows membrane.
upwards and in theory leaves the fixed bed in equilibrium with
the CaCl2 at the top of the bed. The driving force for separation of a gas component in a
mixture is the difference between its partial pressure across
Outlet water contents of 16 mg/Sm have been achieved
3
the membrane. As high pressure feed gas flows into the metal
with CaCl2 dehydrators. Typical CaCl2 capacity is 0.3 kg CaCl2 shell of the membrane unit, the fast components, such as wa-
per kg H2O. Superficial bed velocities are 69m and length to ter and CO2, permeate through the membrane. This permeate
diameter ratio for the bed should be at least 3 to 4:1. stream is collected at a reduced pressure, while the non-perme-
CaCl2 dehydrators may offer a viable alternative to gly- ate stream, i.e., the dry natural gas, leaves the separator at a
col units on low rate, remote dry gas wells. The CaCl2 must slightly lower pressure than the feed.
be changed out periodically. In low capacity high rate units The amount of co-permeation methane and other natural
this may be as often as every 23 weeks. Brine disposal raises gas components is dependent on pressure difference between
environmental issues. In addition, under certain conditions the
CaCl2 pellets can bond together to form a solid bridge in the
fixed bed portion of the tower. This results in gas channeling
and poor unit performance. FIG. 20-86

Example IFPEX-1 Dehydration Process Flow Diagram
Dehydration by Refrigeration
The dehydration of natural gas can also be achieved by
refrigeration and/or cryogenic processing down to 100C in
the presence of methanol hydrate and freeze protection. The
condensed water and methanol streams decanted in the cold
process can be regenerated by conventional distillation or by a
patented process called IFPEX-1.
In the latter process illustrated in schematic form in Fig. 20-
8670 a slip stream of water saturated feed gas strips essentially

FIG. 20-85
Typical CaCl2 Dehydrator

20-50
the feed gas and permeate stream, the surface area of the mem- Special care must be taken in designing the bed supports in
brane and the membrane selectivity. For membrane systems the liquid dehydrator vessels to prevent desiccant loss, desic-
designed to remove CO2 from the gas, the co-permeation of hy- cant damage, and to ensure proper distribution. Layers of ce-
drocarbons can be on the order of 10% of the feed gas stream. In ramic balls are installed in decreasing size from the support
CO2 units, almost all of the water will permeate the membrane screen. The support ball sizes may vary with the type and size
with the CO2. of solid desiccant used but the layers of support balls should
never be graduated in size more than twice the diameter of the
For membrane units designed for dehydration only, the balls being supported.
co-permeation of hydrocarbons is on the order of 1-2%, but a
sweep gas stream is introduced into the permeate side of the The regeneration of solid desiccant beds is very similar to
membrane in order to remove water molecules from the mem- gas dehydrators with the following exceptions:
brane surface and thus increasing the permeation rate. The to-
tal of the co-permeation and sweep gas may be 4-5% of the feed Liquid draining and filling time must be allowed.
stream. Pressuring and depressuring must be done carefully to
If there is no low pressure requirement for the permeate/ avoid bed movement.
sweep gas stream then the gas must be flared or recycled using Adequate bed cooling is required before liquid re-entry
compression. This can significantly increase the cost and com- to minimize flashing.
plexity of a membrane system.
It is important to prevent movement of the bed particles to
prevent attrition that would require premature replacement.
Also, desiccant dust particles can cause downstream plugging,
LIQUID DEHYDRATION equipment damage, and excessive filter maintenance. Liquid
Many liquid streams must be dehydrated to allow further and vapor velocities must be controlled carefully and flashing
processing or meet requirements of a handling chain to a direct of liquids or accelerated blow-down rates that would lift or
consumer. Commercial propane must be dry before entering the float all or portions of the bed should be avoided.
fuel market to prevent freezing problems as the liquid vapor-
Desiccant bed life can be extended by doing several or all of
izes at temperatures below the hydrate point, or even below the
the following activities:
freezing point of any free water that may be present.
Prevent the desiccant particles from moving.
The amount of water that can be in solution with light hy-
drocarbon liquid is very small, even at the saturation point. Ef- Keep contaminants out of the dehydrating portion of
fective drying to very low levels of moisture is usually required. the bed by upstream conditioning or by providing a
The solubility of water in liquid hydrocarbons is presented in sacrificial layer of less expensive desiccant to act as a
Fig. 20-2. The desired maximum moisture level for commercial catcher of any compounds such as amine, glycol or oil.
propane is approximately 10 ppmw. However, liquids exposed
to cryogenic temperatures require virtually all the moisture be Prevent overheating the bed to reduce the formation of
removed. carbon during the regeneration cycle.

The water content in light hydrocarbon liquids can be de- Analyze the heating/cooling regeneration tempera-
termined by using recommended methods in GPA Publication ture cycles to minimize the time the bed is at elevated
2140 (Cobalt Bromide or Freeze Valve methods), or electronic temperatures. This will also minimize energy require-
instruments designed to indicate the moisture content directly. ments.
A typical heating/cooling regeneration temperature cycle plot
Gas Stripping is shown in Fig. 20-83. There are typically four (4) distinct stages
One simple method of dehydrating liquid hydrocarbons is in a normal cycle:
counter current stripping with a dry gas. This method is cur-
Stage 1 First bed-heating stage
rently used to dry condensate produced offshore prior to export
from the production platform. The contactor is usually trayed. Stage 2 Desorption stage
Stripping gas rates depend on the condensate rate, the amount Stage 3 Second bed-heating stage
of entrained water in the condensate, stripper temperature and
pressure. Stage 4 Bed-cooling stage

Advantages of this process are simplicity and low capital For a period of time after the heat source is introduced into
cost. Disadvantages include the requirement for a dry natural a desiccant bed being dehydrated, the bed must be heated to a
gas stream, and the coincidental stripping of some of the vola- temperature where the water will start to be desorbed (Stage 1).
tile hydrocarbons from the condensate. The stripping gas may As the water is desorbed (Stage 2), the bed temperature will usu-
be recycled to the gas dehydration unit or it can be used as fuel ally rise only a few degrees because the regeneration gas heat is
gas. utilized to provide the heat of vaporization of the water being re-
moved. The completion of the water desorption stage is charac-
Solid Desiccant Dehydration terized by a rapid increase in bed temperature measured as the
outlet temperature. At this point the heating may be discontinued
Several solid desiccant processes are available to dry liquid while bed heating will continue from residual heat in the heating
hydrocarbons. cycle (Stage 3). As the unheated regeneration gas stream contin-
Liquid velocity is usually 11.5m/minute through solid des- ues to pass through the bed, the bed will be cooled (Stage 4).
iccant beds with a minimum travel of at least 5 feet to ensure At near ambient pressures, regeneration of silica gel and
good distribution. Direction of flow can be upflow or downflow alumina can be accomplished at 150C. Molecular sieve re-
in the adsorption cycle. quires 260290C to maintain the low dewpoint potential, and

20-51
the higher temperatures may increase desiccant life by provid- Distillation
ing more complete removal of adsorbed hydrocarbons.
Wet NGLs can be dehydrated by distillation in specially de-
Capacity and performance data for new solid desiccants are signed fractionation columns. It will generally suffice to with-
usually presented based on a static test. Under operating condi- draw a sidestream liquid distillate three to four fractionation
tions (dynamic) the performance data may be significantly dif- trays below the top of the distillation column to assure a dry
ferent. Typically the effective capacity at operating conditions is product. Water in the NGL feed is passed overhead and is de-
about one-half of the capacity at equilibrium (static) conditions canted in the overhead reflux drum while reflux is returned
for most solid desiccants. This operating characteristic must be to the top of the column. Some extra costs will be required for
considered when designing a dehydration system and can be in- the sidestream liquid withdrawal and cooling, but this can still
fluenced by careful design and good control of operating param- be the most cost-effective manner to achieve the dehydration
eters such as temperatures, contaminant levels, regeneration of propane and/or butane LPG products to adequate dryness
cycles, and desiccant selection. Solid desiccant manufacturers specifications. The bottoms product of the distillation should be
should be consulted for the most current product information bone dry.
and design criteria.

Molecular Sieve REFERENCES


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20-52
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