PGE 403 Natural Gas Engineering

3-GAS HYDRATE

3.1 Introduction

Natural gas hydrates are two or multi-component non-stoichiometric

crystalline compounds where one of the components is always water.
Gas hydrates exist due to the ability of water molecules to form a
lattice structure, through hydrogen bonding, stabilized by small,
non-polar gas molecules. By the inclusion of the gaseous component,
the structure, which alone is thermodynamically unstable,
becomes stabilized.

Gas molecules are physically enclosed in the cavities of the water

lattice, and they are released from the cavities only under
appropriate circumstances, when the water lattice breaks down. Thus,
the gas components filling the cavities are not directly bonded to
the water molecules of the framework. It is for geometrical reasons
that they cannot leave the hydrogen-bonded water molecule lattice
until it collapses.

Gas hydrates of interest to the hydrocarbon industry are composed

of water and the following eight molecules:

Methane Carbon dioxide

Ethane Nitrogen
Propane Hydrogen
sulphide iso-Butane normal-Butane

Hydrates normally form in one of the small, repeating crystal

structures. Structure I (sI), a body-centered cubic structure and
forms with natural gases containing molecules smaller than propane.
Structure II (sII), a diamond lattice within a cubic framework, forms
when natural gases or oils contain molecules larger than ethane but
smaller than pentane. Structure H (sH) has been found recently. sH
hydrates are unique since they form in the presence of a light gas
such as methane and molecules typically in oils and condensates.
Several sH formers such as methylcyclopentane, methylcyclohexane,
neohexane, and adamantane are indigenous to petroleum. Preliminary
studies demonstrate the possible occurrence of sH hydrate as the most
stable hydrate structure for certain
multi-component systems.

Table 3.2 provides a hydrate structure summary for sI, sII and sH.
The "small" cavities of all structures are pentagonal dodecahedra
12
(5 ) formed by the water molecules. The "large" cavities of sI are
tetradecahedra, formed by 2 opposing hexagons and 12 pentagons
situated between them (51262); in sII they are hexadecahedra,
constructed from 4 hexagons and 12 pentagons (51264). Structure H
has a second dodecahedron, the 435663 cavity, which is built of
three quadrates, six pentagons and three hexagons. The largest
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cavity, the 51268 cavity, is built of twelve pentagons and eight

hexagons.
Figure 3.3 depicts the five cavities of hydrate structures5.
Each of the cavities in either structure may contain only one guest
molecule. The cavity occupied is a function of the size ratio of the
guest molecule within the host cavity. Table 4.3 shows the size ratio
6
of several common gas molecules within each of the four cavities .
Note that a size ratio approximately 0.9 is necessary for the
stability of a simple hydrate, given by the superscript "†". When the
size ratio exceeds unity, the molecule will not fit within the
cavity and the structure will not form. When the ratio is
significantly less than 0.9 the molecule cannot lend stability to the
cavity to cause formation. Table 3.3 indicates which of the gaseous
compounds found in typical petroleum mixtures may enter hydrate
cavities.
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Table 3.2 Some physical constants of hydrate structures.

Property Structure I Structure II Structure H
Number of H2O molecules/unit cell 46 136 34
12
Number of 5 cavity 2 16 3
12 2
Number of 5 6 cavity 6 - -
12 4
Number of 5 6 cavity - 8 -
3 6 3
Number of 4 5 6 cavity - - 2
12 8
Number of 5 6 cavity - - 1
12
Diameter of 5 cavity, Å 5.0 5.0 5.0
12 2
Diameter of 5 6 cavity, Å 5.8 - -
12 4
Diameter of 5 6 cavity, Å - 6.47 -
3 6 3
Diameter of 4 5 6 cavity, Å - - 5.0
12 8
Diameter of 5 6 cavity, Å - - 9.0

Table 3.3 Ratio of molecular diameters to cavity diameters for some

molecules forming sI and S;; hydrates
(Molecular diameter)/(Cavity diameter)
Cavity type Structure I Structure II
12 12 2 12 12 4
Molecule Guest diameter (Å) 5 5 6 5 5 6
*
Ne 2.97 0.604 0.516 0.606 0.459
† †
Ar 3.8 0.772 0.660 0.775 0.599
† †
Kr 4.0 0.813 0.694 0.816 0.619
† †
N2 4.1 0.833 0.712 0.836 0.634
† †
O2 4.2 0.853 0.729 0.856 0.649
† †
CH4 4.36 0.886 0.757 0.889 0.675
† †
H2S 4.58 0.931 0.795 0.934 0.708
†
CO2 5.12 1.041 0.889 1.044 0.792
†
C2H6 5.5 1.118 0.955 1.122 0.851
†
C3H8 6.3 1.276 1.090 1.280 0.971
†
i- C4H10 6.5 1.321 1.128 1.325 1.005
*
n-C4H10 7.1 1.443 1.232 1.447 1.098
†
Indicates the cavity occupied by the simple hydrate former.
* Indicates that a molecule will not form hydrates as a single component, because
it is too small (or too large) to stabilize a cavity.
Note: If a molecule enters the small cavities of a structure, it will also enter
the large cavities.

3.2 PREDICTIONS OF CONDITIONS FOR HYDRATE FORMATION

Hydrate formation can be divided into two categories:

1) hydrate formation due to a decrease in temperature
(or increase in pressure) with no sudden expansion(or
compression), such as in flow strings and surface lines;
2) hydrate formation due to sudden expansion, such as in flow-
provers, orifices, chokes, and back- pressure regulators.
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3.3 METHODS OF HYDRATE PREVENTION

Fundamentally there are four ways to prevent hydrates from

forming:

1. Reducing the pressure below that of the hydrate formation

for the given temperature;
2. Maintaining the temperature of the gas flow above the
hydrate formation temperature for the given pressure;
3. Reducing the dew point of water vapor in the gas flow below
the operating temperature
(drying the gas);
4. Introducing various substances (alcohols, electrolytes) into
gas flow, which lower the hydrate formation pressure.

3.3.1 Vapor-Solid Equilibrium Ratio Method

The Vapor-Solid Equilibrium Ratio (K-value) method is an early

method for calculating hydrate- forming conditions using vapor-
6,10,11. Katz et al. reasoned that
solid equilibrium constants
hydrates were the equivalent of solid solutions and not mixed
crystals. They postulated that hydrate-forming conditions could
be calculated from empirically determined vapor-solid equilibrium
constants:

y
(4.4)
K s=
xs

where
y = mole fraction of a hydrocarbon in the gas on a water-free basis.
xs = mole fraction of the hydrocarbon in the
solid on a water-free basis.
The hydrate forming conditions should satisfy:

y
=1 (4.5)
K vs
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This procedure is like the dew point calculation for complex gas
mixtures. K-charts for methane, ethane, propane, iso-butane, normal-
butane, hydrogen sulfide, carbon dioxide, and nitrogen are available
for predicting the hydrate-forming points from gas composition
12
Poetmann et.al. utilized CSMHYD hydrate prediction program to
calculate vapor-solid equilibrium ratios for structures I and II for
various natural gas systems. From the generated, charts were
constructed for each natural gas component. Structure I charts
consist of methane, ethane, carbon dioxide, and hydrogen sulfide.
Structure II consists of the same component as Structure I with the
addition of propane, iso-butane, and normal-butane. Polynomial
regression analysis was used to curve fit the computer generated Kvs
values for both structures. These equations can be programmed and
used to predict the hydrate forming conditions for natural gases.

3.3.2 Hydrate Control through Water Removal (Dew Point Lowering)

Except in arctic conditions, the maximum water content of gas is
specified as 4 lbm/MMSCF; typically the water content is 2.25
lbm/MMSCF. After the free water is separated from the gas stream,
two processes are commonly used to lower the dew point by removing
dissolved water. In the first process, contacting the gas with a
compound, typically tri-ethylene glycol (TEG), which removes water
through hydrogen bonding, lowers the water concentration. In the
second process, the gas is contacted with a solid, such as molecular
sieve, alumina or silica gel, which selectively adsorbs water.
In general solid desiccants are placed in parallel packed bed
adsorbers through which gas is passed.
One adsorber is used to remove water from the gas while the parallel
unit is being regenerated at high temperature or cooling. In recent
years molecular sieves have gained popularity due to their advantages
of providing extremely low dew points, high adsorption of water
and unlike silica gel, they are not damaged by liquid water.

3.3.3 Hydrate Control through Use of Chemicals

Frequently inhibitors are injected into processing lines as a
means of hydrate control by both the breakage of hydrate hydrogen
bonds and the competition for available water molecules. The more
frequently used inhibitors are strong polar fluids, such as
methanol, the ethylene glycols, and ammonia, arranged in order of
decreasing usage frequency. Of the above three chemicals, the uses
of methanols and the ethylene glycol are pervasive. While ammonia
is more than twice as effective as methanol, it is onlyused in
cases of severe hydrate blockage, due to the reaction of NH3 with
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CO2 in the gas to form plugs of solid ammonium carbonate,

bicarbonate and carbamate. The handling of ammonia is also an
important safety consideration. The use of inhibitors shifts the
three-phase (Lw-H-V) equilibrium curve to higher pressures and
lower temperatures.
The theoretical principles of inhibition of hydrate formation have
13
been discussed in several papers. Hammerschmidt proposed the
first empirical equation to find the required concentration of an
inhibitor X, in an aqueous solution, for lowering the hydrate
formation temperature by a given amount,

KX
T= (4.5)
100M - MX

where
M = inhibitor's molecular weight,
K = constant, depending on the
type of solution.
PGE 403 Natural Gas Engineering

Experimentally determined values of K and molecular weights of

inhibitors are given in Table 3.6.
Table 3.6 Physical constants of inhibitors.
Component Molecular weight K-value
Methanol 32 2335
Ethylene Glycol 62.07 2700
Diethylene Glycol 106.12 4000
Triethylene Glycol 150.17 5400

Whether methanol or a glycol is used for hydrate depression,

there are three possible phases into which
the inhibitor may distribute.
1.the aqueous phase where the hydrate inhibition occurs,
2.the vapor hydrocarbon phase, where the inhibitor may be
lost, as in the usual case of methanol injection, and
3.the liquid hydrocarbon phase, which has appreciable
solubility for both methanol and glycols.
Depending upon the temperature and pressure, all three of the
fluid phases may be present, or either the vapor or the liquid
hydrocarbon may be missing.
 PGE 403 Natural Gas Engineering

3.4 GAS Hydrate Formation:

Natural gas hydrates are flammable crystalline

compounds formed by the chemical combinations of natural gas
and water under pressures and temperatures considerably above
the freezing point of water. In the presence of free water,
hydrates will form when the temperature of the gas is below a
certain temperature called the hydrate temperature. Hydrate
formation should not be confused with the condensation of water
from a natural gas. Condensation occurs when the temperature
is at or below the dew point temperature at a fixed pressure.
Free water obtained under such conditions is essential to
formation of hydrates. However, hydrates at the same pressure
occurs at or below the hydrate temperature. That is, hydrate
temperature would be below and perhaps the same as, hut never
above the dew point temperature.While conducting tests or
producing the gas well at any time, the engineer should avoid
the formation of hydrates. Hydrates may choke the flow string,
surface lines and well testing equipment. Hydrate formation in
the flow string would result in a lower value for measured
wellhead pressures. Also,hydrate formation would result in
lower measured gas flow rates.In some cases, they may
completely block flow lines and surface equipment.

The conditions contributing to hydrate formation are:

1. Low temperature. Temperatures below the hydrate
temperature for the pressure and gas composition
considered.
2. High pressure. High operating pressures that increase the
"hydrate formation" temperature
3. High velocities
4. Gas must be at or below its water dew point with free
water present
5. Presence of H„S and of C 0 7 , since these gases are
more soluble in water than hydrocarbons. They
increase the temperature at which the hydrate will
form.
6. Presence of a small hydrate crystal
7. Pressure pulsations
8. Any type of agitation
9. Impurities in the water (brine, alcohol etc.) affect the
hydrate forming temperature
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3.4.1 Causes of hydrate formation:

1. Sudden pressure drop - chokes, orifices

2. Decrease in temperature with no sudden pressure drop-flow
strings and surface lines.
Decrease in temperature lowers the solubility of water in
gas, which causes free water drop-out from the natural gas.

3.4.2 Hydrate Formation by Sudden Pressure Drop:

- Chokes, orificies, back pressure regulators-

Sudden expansion in one of these devices is accompanied

by a temperature drop which may cause hydrate formation.
Figures A-13 to_ A-17 in ERCB Manual can be used to approximate
the conditions for hydrate formation. Unfortunately these
figures are for sweet natural gases, which means that the
presence of CO- and H~S will enhance the formation of
hydrates.

Examples 3.4.1:

• How much may a 0.8 gravity gas at 1000 psia and 100 F
be expanded without hydrate formation, assuming
presence of free water?
From Fig.A-15, the intersection of 1000 psia and 100°F
gives the final pressure of 440 PSPAfrom the X-axis.

• How much may a 0.8 gravity gas at 800 psia and

100°F be expanded without hydrate formation,
assuming presenceof free water.

From Fig.A-15, we see that 800 psia and 100°F line

do not intersect. This means that the gas may be
expandedto atmospheric pressure without hydrate
formation.
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3.4.3 Hydrate Formation by Decrease in temperature:

- flow strings, surface lines -

A decrease in the temperature in the flow strings

will lower the solubility of water in natural gas. Thus
free water drop out will occur from the natural gas
stream.The hydrate temperature depends on the pressure and
composition,reflectedby its gravity of the gas.Fig.A-12 in
ERCB Manual gives approximate values of the hydrate
temperature as a function of pressure and specific
gravity.Hydrates will form whenever temperature and
pressure plot to the left of the hydrate formation line for
the gas in question. Again,this figure is applicable only
for sweet gases.

Examples3.4.3:

1) A gas of specific gravity 0.8 is at a pressure of 1000

psia.

To what extent can the temperature be lowered

without hydrate formation, assuming presence of
free water?

From Fig.A-12, using 0.8, we determine the hydrate

temperature as 66 F. THus below 66 F, hydrates may form.

2) A gas of gravity 0.8 is at a temperature of 50 F.

What is the pressure above which hydrates could be
expected to form assuming presence of free water?

From Fig.A-12 X = 0 . 8 and T = 50°F, we read P = 275

psia. Thus hydrates may form at or above 275 psia.

1. Natural gas must exist at or below dew poin&pressure with

liquid water present. If there is no free water there is no
possibility of hydrate to form.
2. Low temperatures at or below the hydrate fromation
temperature for a given pressure and gas composition.
3. High operating pressures that may raise the hydrate
formation temperature to the operating temperature.
PGE 403 Natural Gas Engineering

Secondary factors are:

1. High velocity and agitation or pressure pulsation.
2. Presence of smallseed of hydrate crystal
3. Presence of H2S and CO2 aids hydrate formation beause
these acid gases are more soluble in water than
hydrocarbons.

3.4.4 Prediction of hydrate formation

3.4.4.1 Approximate method for sweet gases:

The figures Given as 2..... . - 2. ... can be used as an

approximation (Fig. 5-11-5-16 of Kumar)
These charts do not account for the presence of H2S and CO2.

Hydrate formation occurs if,

a. due to a decrease in temperature (or increase in
pressure) with no sudden expansion (or compression)
such as flow in surface lines
b. due to sudden expansion such as in chokes, orifices,
back pressure regulators

For hydrate of type I (fig 5-11 of Kumar) can be used to

predict the approximate temperature and pressure conditions
for hydrate formation (5- 12 to 5-l6 of Kumar) for hydrate of
Type II.

Example 3.4.4.1

• 0.65 gravity gas is at 500 psia and 100 oF.

To what value the temperature can be reduced
without hydrate formation?

From Fig . 2. (Fig 5-1 J/Kumar) hydrates wil form at

or below 54°F.
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Example 3.4.4.1

• How far can the pressure be lowered.without expecting

hydrate formation for a 0.685 gravity gas if it is
initially at (a) 1500 psia and IOO0F
(b) 1000 psia and 100 oF.

(a)From fig 2.... Fig 5-12'of Kumar) for 065 gravity gas
intersection of 1500 psia with 100 F curve-gives a final
pressure of 490 psia. Similarly from fig 2. ... ( fig.5-
13, of Kumar) for 0.7 gravity gas final pressure is 800
psia. By interpolation for 0.685 gravity gas can be
expander! without hydrate formation up to a pressure
of 753.5 psia.
(b) Using figured... (Fig 5-12 and 13)

The 100°F initial temperature curve does not intersect 1000

psia line for 0.6 and 0.7 gravity gas. So gas at these
condtions can be expanded to anv pressure without hydrate
formation.

2. Katz el al method:
3. Trekell-Campbell method for high pressure gas
4. Mc Leod-Campbell method for very high pressure sweet gas
5. Equation of state method.

For the discussion of these methods and examples read pages

189-287 of S. Kumar
"Gas Productin Engineering"