be expanded to atmospheric pressure without hydrate forma- Nitrogen is assumed to be a non-hydrate former and is also

tion. assigned a K-value of infinity.

Conditions predicted by Fig. 20-19 through 20-21 may be sig-
nificantly in error for compositions other than those used to derive
the charts. For more accurate determination of hydrate formation
conditions, the following procedures should be followed. In addi-
tion, Fig. 20-20 and 20-21 do not account for liquid water and liquid
The Kvs values are used in a “dewpoint” equation to deter-
mine the hydrate temperature or pressure. The calculation is
iterative and convergence is achieved when the following ob-
jective function (Eq 20-4) is satisfied.
i=n

∑ (yi / Kvs )
hydrocarbons present or formed during the expansion. These can
= 1.0 Eq 20-4
have a significant effect on the outlet temperature from the pres-
sure reduction device. i=1

Hydrate Prediction Based on Composition Prudence should be exercised when some higher molecular
for Sweet Gases weight isoparaffins and certain cycloalkanes are present as
Several correlations have proven useful for predicting hy- they can form Structure H hydrates.
drate formation of sweet gases and gases containing minimal Example 20-7 — Calculate the pressure for hydrate
amounts of CO2 and/or H2S. The most reliable ones require a formation at 50°F for a gas with the following composition.
gas analysis. The Katz method14,15 utilizes vapor solid equilib-
Mole at 300 psi at 400 psi
rium constants defined by the Eq 20-3. Component Fraction
y in Gas Kvs y/Kvs Kvs y/Kvs
Kvs = Eq 20-3
xs Methane 0.784 2.04 0.384 1.75 0.448
Ethane 0.060 0.79 0.076 0.50 0.120
WARNING: Not good for pure components – only mixtures.
Propane 0.036 0.113 0.319 0.072 0.500
The applicable K-value correlations for the hydrate forming
Isobutane 0.005 0.046 0.109 0.027 0.185
molecules (methane, ethane, propane, isobutane16, normal bu-
tane17, carbon dioxide, and hydrogen sulfide) are shown in Fig. n-Butane 0.019 0.21 0.090 0.21 0.090
20-23 to 20-29. Normal butane cannot form a hydrate by itself Nitrogen 0.094 * 0.000 * 0.000
but can contribute to hydrate formation in a mixture. Carbon dioxide 0.002 3.0 0.001 1.9 0.001
For calculation purposes, all molecules too large to form hy- Total 1.000 0.979 1.344
drates have a K-value of infinity. These include all normal par- * Infinity Interpolating linearly, Σy/Kvs = 1.0 at 305 psia
affin hydrocarbon molecules larger than normal butane.

FIG. 20-19
FIG. 20-18
Pressure-Temperature Curves for
Conditions for Hydrate Formation for Light Gases Predicting Hydrate Formation

20-13