9.

8 Hydrate predictions for high CO2/H2S content gases 459

FIGURE 9.7
Hydrate chart for gases containing H2S.
Ref. [1].
460 CHAPTER 9 Natural Gas Dehydration

4. Apply the C3 correction using the insert at the upper left. 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 correction on the left hand scale (1.5
C).
Note: The C3 temperature correction is negative when on the left hand side of the graph and positive on the right
hand side.
TH ¼ 17.5e1.5 ¼ 16
C.

Figure 9.7 was developed based on calculated hydrate conditions using the Peng-Robinson EOS. It has
proven to be quite accurate when compared to the limited amount of experimental data available.
It should only be extrapolated beyond the experimental data base with caution.

9.9 Hydrate inhibition

The formation of hydrates can be prevented by dehydrating the gas or liquid to eliminate the formation
of a condensed water (liquid or solid) phase. In some cases, however, dehydration may not be practical
or economically feasible. In these cases, chemical inhibition can be an effective method of preventing
hydrate formation. Chemical inhibition utilizes injection of thermodynamic inhibitors or low-dosage
hydrate inhibitors (LDHIs).
Thermodynamic inhibitors are the traditional inhibitors (i.e., one of the glycols or methanol),
which lower the temperature of hydrate formation. LDHIs are either kinetic hydrate inhibitors (KHIs)
or anti-agglomerants (AAs). They do not lower the temperature of hydrate formation, but do diminish
its effect. KHIs lower the rate of hydrate formation, which inhibits its development for a defined
duration. AAs allow the formation of hydrate crystals but restrict them to submillimeter size.

9.9.1 Thermodynamic inhibitors

Inhibition utilizes injection of one of the glycols or methanol into a process stream where it can
combine with the condensed aqueous phase to lower the hydrate formation temperature at a given
pressure.
Both glycol and methanol can be recovered with the aqueous phase, regenerated, and reinjected.
For continuous injection in services down to 40
C, one of the glycols usually offers an economic
advantage versus methanol recovered by distillation.
At cryogenic conditions (below 40
C) methanol usually is preferred because glycol’s viscosity
makes effective separation difficult.
Ethylene glycol (EG), diethylene glycol (DEG), and TEG glycols have been used for hydrate
inhibition. The most popular has been EG because of its lower cost, lower viscosity, and lower sol-
ubility in liquid hydrocarbons.
To be effective, the inhibitor must be present at the very point where the wet gas is cooled to its
hydrate temperature. For example, in refrigeration plants, glycol inhibitors are typically sprayed on the
tube-sheet faces of the gas exchangers so that it can flow with the gas through the tubes. As water
condenses, the inhibitor is present to mix with the water and prevent hydrates. Injection must be in a
manner to allow good distribution to every tube or plate pass in chillers and heat exchangers operating
below the gas hydrate temperature.
 9.9 Hydrate inhibition 461

The inhibitor and condensed water mixture is separated from the gas stream along with a separate
liquid hydrocarbon stream. At this point, the water dew point of the gas stream is essentially equal to the
separation temperature. Glycol-water solutions and liquid hydrocarbons can emulsify when agitated or
when expanded from a high pressure to a lower pressure(e.g., JT expansion valve). Careful separator
design will allow nearly complete recovery of the diluted glycol for regeneration and reinjection.
The regenerator in a glycol injection system should be operated to produce a regenerated glycol
solution that will have a freezing point below the minimum temperature encountered in the system.
This is typically 75–80 wt%. The minimum inhibitor concentration in the free water phase may be
approximated by Hammerschmidt’s
K H XI
d¼ (9.23)
MWI ð1  XI Þ
dMWI
XI ¼ (9.24)
KH þ dMWI
where
KH ðglycolsÞ ¼ 2335  4000 and KH ðmethanolÞ ¼ 2335
where:
d ¼ depression of the water dew point or the gas hydrate freezing point,
C
XI ¼ mass fraction of inhibitor in the liquid phase
I ¼ Inhibitor
MWI ¼ molecular mass of inhibitor
The KH range of 2335–4000 for glycols reflects the uncertainty in the value of this parameter. At
equilibrium, such as for a laboratory test, 2335 is applicable.
In some field operations, however, hydrate formation has been prevented with glycol concentrations
corresponding with KH values as high as 4000. This is because hydrate suppression with glycols depends
on the system’s physical and flow characteristics etc., as well as the properties of the gas and the glycol.
Therefore, in the absence of reliable field-test data, a system should be designed for a KH of 2335. Once
the system is operating, the glycol concentration can be reduced to tolerable levels. Equations (9.22) and
(9.23) should not be used beyond 20–25 wt% for methanol and 60–70 wt% for the glycols. For methanol
concentrations up to about 50%, the Nielsen–Bucklin equation provides better accuracy:
d ¼ 72:0 lnðXH2 O Þ (9.25)
where:
d ¼ depression of the water dew point or the gas hydrate freezing point,
C
X ¼ mole fraction in the liquid phase
Note that “xH2O” in Eqn (9.24) is a mole fraction, not a mass fraction.
Once the required inhibitor concentration has been calculated, the mass of inhibitor required in the
water phase may be calculated from 9.25
XR $m H2 O
mI ¼ (9.26)
XL  XR
462 CHAPTER 9 Natural Gas Dehydration

where:
I ¼ Inhibitor
m ¼ the mass of inhibitor required in the water phase
X ¼ mass fraction in the liquid phase
L ¼ lean inhibitor
R ¼ rich inhibitor
The amount of inhibitor to be injected not only must be sufficient to prevent freezing of the inhibitor
water phase, but also must be sufficient to provide for the equilibrium vapor phase content of the
inhibitor and the solubility of the inhibitor in any liquid hydrocarbon. Figure 9.8 shows methanol
vaporization loss.
The vapor pressure of methanol is high enough that significant quantities will vaporize. Glycol
vaporization losses are generally very small and are typically ignored in calculations.
Inhibitor losses to the hydrocarbon liquid phase are more difficult to predict. Solubility is a strong
function of both the water phase and hydrocarbon phase compositions. Figure 9.9 shows the solubility

FIGURE 9.8
Methanol vaporization loss chart.
Ref. [1].
 9.9 Hydrate inhibition 463

FIGURE 9.9
Methanol solubility in hydrocarbon liquid phase.
Ref. [1].

of methanol in a paraffinic hydrocarbon liquid as a function of temperature and methanol concen-

tration. Methanol solubility in naphthenic hydrocarbons is slightly less than paraffinic, but solubility in
aromatic hydrocarbons may be four to six times higher than in paraffins.
Solubility of EG in the liquid hydrocarbon phase is extremely small. A solubility of 40 g/m3 of
NGL is often used for design purposes. However, entrainment and other physical losses may result in
total losses significantly higher than this.

EXAMPLE 9.3:
2.83  106 Sm3/day of natural gas leaves an offshore platform at 38
C and 8300 kPa (abs). The gas comes
onshore at 4
C and 6200 kPa (abs). The hydrate temperature of the gas is 18
C. Associated condensate produc-
tion is 56 m3/Standard million cubic meters. The condensate has a density of 778 kg/m3 and a molecular mass of
140. Calculate the amount of methanol and 80 mass% EG inhibitor required to prevent hydrate formation in the
pipeline.
Solution steps:
Methanol
1. Calculate the amount of water condensed per day from Figure 9.2
Win ¼ 850 mg/Sm3.
Win ¼ 152 mg/Sm3.
DW ¼ 698 mg/Sm3.
Water condensed ¼ (2.83  106)(698) ¼ 1975(106) mg/d ¼ 1975 kg/d.
464 CHAPTER 9 Natural Gas Dehydration

2. Calculate required methanol inhibitor concentration:

d ¼ 14
C.
M ¼ 32.
Solving for XI,
XI ¼ 0.255.
XI ¼ 0.275 (use this value in subsequent calculations).
3. Calculate mass rate of inhibitor in water phase (assume 100% methanol is injected).

XR $mH2 O ð0:275Þð1975Þ
m1 ¼ ¼ ¼ 749 kg=d
XL  XR ð1  0:275Þ

4. Estimate vaporization losses from Figure 9.8 at 4
C and 6200 kPa (abs).
 kg=m3
losses ¼ 16:8 06
wt% MeOH
 
daily losses ¼ 1:68106 2:83106 ð27:5Þ ¼ 1310 kg=d

5. Estimate losses to hydrocarbon liquid phase from Figure 9.9 at 4
C and 27.5 wt% MeOH, xMeOH z0.2 mol%
lb mols of condensate per day.





2:83  106 Sm3 56 m3 778 kg 1 kg mol
¼ 881 kg mol=d
d 106 Sm3 m3 140 kg

kg mol methanol ¼ (881)(0.002) ¼ 1.76 kg mols/d.

kg methanol ¼ (1.76)(32) ¼ 56 kg/d.
Total methanol injection rate ¼ 749 þ 1310 þ 56 ¼ 2115 kg/d.
Methanol left in the gas phase can be recovered by condensation with the remaining water in downstream chilling
processes. Likewise, the methanol in the condensate phase can be recovered by downstream water washing.
80 wt% EG
1. Calculate required inhibitor concentration.
d ¼ 14
C M ¼ 62.
Solving for XI, XI ¼ 0.28.
2. Calculate mass rate of inhibitor in water phase.

ð0:28Þð1975Þ
mI ¼ ¼ 1063 kg=d
ð0:8  0:28Þ

9.9.2 Low dosage hydrate inhibitors

LDHIs can provide significant benefits compared to thermodynamic inhibitors including:
• Significantly lower inhibitor concentrations and therefore dosage rates. Concentrations
range from 0.1 to 1.0 mass percent polymer in the free water phase, whereas alcohols can be
as high as 50%
• Lower inhibitor loss caused by evaporation, particularly compared to methanol.
• Reduced capital expenses through decreased chemical storage and injection rate requirements;
and no need for regeneration because the chemicals are not currently recovered. These are
especially appropriate for offshore where weight and space are critical to costs.
 9.10 Natural gas dehydration methods 465

• Reduced operating expenses in many cases through decreased chemical consumption and
delivery frequency.
• Increased production rates, where inhibitor injection capacity or flow line capacity is limited.
• Lower toxicity.

9.9.3 Kinetic hydrate inhibitors

KHIs were designed to inhibit hydrate formation in flow lines, pipelines, and downhole equipment
operating within hydrate-forming conditions, such as subsea and cold-weather environments.
Their unique chemical structure significantly reduces the rate of nucleation and hydrate growth
during conditions thermodynamically favorable for hydrate formation, without altering the thermo-
dynamic hydrate formation conditions (i.e., temperature and pressure). This mechanism differs from
methanol or glycol, which depress the thermodynamic hydrate formation temperature so that a flow
line operates outside hydrate-forming conditions.

9.9.4 KHIs compared to methanol or glycols

KHIs inhibit hydrate formation at a concentration range of 0.1–1.0 mass percent polymer in the free
water phase. At the maximum recommended dosage, the current inhibition capabilities are 2
C of
subcooling in a gas system and 7
C in an oil system with efforts continuing to expand the region of
effectiveness. For relative comparison, methanol or glycol typically may be required at concentrations
ranging 20–50 mass percent, respectively, in the water phase.

9.10 Natural gas dehydration methods

Dehydration of natural gas is the removal of the water that is associated with natural gases in vapor
form. The natural gas industry has recognized that dehydration is necessary to ensure smooth operation
of gas transmission lines. Dehydration prevents the formation of gas hydrates and reduces corrosion.
Unless gases are dehydrated, liquid water may condense in pipelines and accumulate at low points
along the line, reducing its flow capacity. Several methods have been developed to dehydrate gases on
an industrial scale.
The three major methods of dehydration are (1) direct cooling, (2) adsorption, and (3) absorption.
Molecular sieves (zeolites), silica gel, and bauxite are the desiccants used in adsorption processes.
In absorption processes, the most frequently used desiccants are diethylene and TEGs. Usually, the
absorption/stripping cycle is used for removing large amounts of water, and adsorption is used for
cryogenic systems to reach low moisture contents.
Natural gas usually contains water, in liquid or vapor form, at source or as a result of sweetening
with an aqueous solution. Operating experience and thorough engineering have proved that it is
necessary to reduce and control the water content of gas to ensure safe processing and transmission.
Removal of the water vapor that exists in solution in natural gas requires a more complex treatment.
This treatment consists of dehydrating the natural gas, which is accomplished by lowering the dew
point temperature of the gas at which vapor will condense from the gas. There are several methods of
dehydrating natural gas. The most common of these are liquid desiccant (glycol) dehydration and solid
desiccant dehydration.