Natural gas dehydration

Introduction

Natural gas dehydration is the process of

water removal associated with natural gases.

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 Source of Water Content in Gas
• Water vapor in gas streams depend upon
certain condition prevailing in the reservoir
– Temperature
– Pressure
– Amount of free water produced with gas.
• Water content in gas is sometime due to the
aqueous solution used in gas sweetening
process.
 Why Gas is Dehydrated?
• To ensure smooth transmission of sale gas.
• To prevent condensation at low points which cause to
reduce the flow capacity of gas.
• To prevent HYDRATES formation which can plug lines
and retard the flow of gaseous hydrocarbon streams.
• Water can condense in the pipeline, causing slug flow
and possible erosion and corrosion.
• Water vapor increases the volume and decreases the
heating value of the gas.
• Sales gas contracts and/or pipeline specifications often
have to meet the maximum water content of 7 lb H2O
per MMscf.
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Dew Point & Dew Point Depression
• Dew point is the temperature at which the
water vapor or hydrocarbon begin to
condense at constant pressure conditions.
• Dew point is used to show the saturation
temperature of water vapor content of gas.
• Dew-point depression is the extent to which
the water vapor content in a gas has been
reduced at constant pressure.
• Liquid water accelerates corrosion in the
presence of H2S and CO2.

H2O + H2S = H2SO4

H2O + CO2 = H2CO3

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 Hydrates and its formation
• Solids formed by the physical combination of water
and other small molecules of hydrocarbons.
• Hydrates are icy hydrocarbon compounds of about
10% hydrocarbons and 90% water and grow as
crystals.
• Hydrates formed due to
– Free water present in Gas at dew point.
– Low temperature.
– High pressure.

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WATER CONTENT DETERMINATION
• The water content of a gas is a function of pressure,
temperature, composition and salt content of the free water.
The effect of composition increases with pressure.
• For most gas systems the McKetta and Wehe
(1958) chart, generated from empirical data,
provides the standard for water content
determination. This chart can be used to
predict the saturated water content of sweet,
pipeline quality natural gas.
• Used for acid gas concentrations less than
about 30%,
McKetta and Wehe (1958) chart,
• For higher acid gas concentrations (above
50%), particularly at higher pressures, existing
methods can lead to serious errors in
estimating water contents (Hubbard, 1993).
• An appropriate method has been introduced
by Wichert and Wichert (2003).
Campbell’s correlation
3. How far may a 0.6 gravity gas at 2,000 psia
and 100°F be expanded without hydrate
formation?
HYDRATE INHIBITOR
 METHODS USED TO INHIBIT HYDRATE
FORMATION
Hydrate formation in natural gas is promoted by high-
pressure, low temperature conditions and the presence of
liquid water. Therefore, hydrates can be prevented by the
following:

1. Raising the system temperature and/or lowering the

system pressure (temperature/pressure control)

2. Injecting a chemical such as methanol or glycol to depress

the freezing point of liquid water (Chemical injection)

3. Removing water vapor from the gas liquid–water drop out

that is depressing the dew point (dehydration).
Temperature/Pressure Control
• Down hole regulators or chokes.
• Indirect heaters.

Chemical Injection
1. Thermodynamic inhibitor
2. Kinetic inhibitor

Methanol and glycols are the most commonly used chemicals, although
others (such as ammonia) have been applied to lower the freezing point
of water, thus reducing (or preventing) hydrate formation.

The application of hydrate inhibitors should be considered for such cases:

• A system of gas pipelines, where the problem of hydrate formation is of short
duration.
• A system of gas pipelines which operate at a few degrees below the hydrate
formation temperature.
• Gas gathering systems found in pressure-declining fields.
• Gas lines characterized by hydrate formation in localized points.
 Hydrate inhibition in gas piping
Depends upon two factors:
• The amount of water which can condense
from the gas as it cools
• The hydrate temperature reduction, which is
the difference in temperature at which
hydrates will start to form and the lowest
temperature the gas can reach
Injection of inhibitor
Glycol injection system
 Methanol and glycol
Glycol and methanol injection are compared by
considering
• Temperature effects
• Injection techniques
• Potential downstream problems and
• Recovery economics

•
 Regeneration of inhibitor
• 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.
• The minimum inhibitor concentration in the free water phase may
be approximated by Hammerschmidt’s

• Once the required inhibitor concentration has been calculated, the mass of inhibitor required
in the water phase may be calculated from Eq

where:
I =Inhibitor
m = the mass of inhibitor required in the water phase
X =mass fraction in the liquid phase
L =lean inhibitor
R =rich inhibitor
100 MMscf/d of natural gas leaves an offshore platform at
100°F and 1200 psia. The gas comes onshore at 40°F and
900 psia. The hydrate temperature of the gas is 65°F.
Associated condensate production is 10 Bbl/MMscf. The
condensate has an API gravity of 50 and a MW of 140.
calculate the amount of methanol and 80 wt% EG inhibitor
required to prevent hydrate formation in the pipeline.

For methanol
For EG
 KINETIC INHIBITORS AND ANTI-
AGGLOMERATORS
• A kinetic inhibitor is a polymeric chemical that, when added to
production stream, will not change the hydrate formation
temperature but will delay the growth of hydrate crystals.
• These chemicals are polymeric and include N-vinylpyrrolidone (5
ring), saccharides (6 ring}, and Nvinylcaprolactam (7 ring).

• An anti-agglomerator is an alkyl aromatic sulphonate, a quaternary

• ammonium salt, or an alkyl glycoside surfactant.
• When added to a production stream with a continuous oil phase,
this chemical will minimize hydrate crystals from agglomerating or
growing in size.
DEHYDRATION PROCESS
 Gas Dehydration Processes

Absorption Gas
Adsorption Refrigeration Permeation

Calcium Lithium Physical

Glycols Chemisorptions
Chloride Chloride Adsorption

MEG Activated alumina

(C2H6O2) “Al2O3”

DEG
(C4H10O4) Silica Gel “Sio2”

TEG Molecular sieves

(C6H1404) “zeolites”

TREG
(C8H18O5)

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 Refrigeration Dehydration Process
• Refrigeration process remove heavy
hydrocarbons and also reduce water content of
the natural gas streams.
• Cold gas can carry less water than warm gas.
• A typical refrigeration process can easily reduce
the water content of a gas stream down to 1
lb/MMCF level.
• One big advantage of this process is that it can
produce a gas that meets both the hydrocarbon
dew point and water content specifications.
37
 Flow diagram for a refrigeration plant unit with
glycol injection and recovery

Pakistan Petroleum Limited m_haris@ppl.com.pk

 Adsorption Dehydration Process
• Solid desiccant is used for the removal of
water content from a gas stream.
• Most widely used adsorbents today are
– Activated alumina
– Silica gel
– Molecular sieves (zeolites) .

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 Desiccant for Adsorption Dehydration
• Activated alumina - Excellent all purpose desiccant for drying air
and most other gases with high relative humidity.

• Silica gel - Desiccant silica gel is a very effective desiccant for drying
compressed air/gas streams, especially natural gas. Silica gel
features excellent adsorption for high relative humidity gas.

• Molecular sieve - Most effective for applications with low

inlet flows and low relative humidity, (Less than 30-35%RH).
Can achieve the lowest dew points possible to -120°F
•

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 Molecular Silica
Properties Clay CaO CaSO4
Sieve Gel

Capacity of adsorption in low

Excellent Bad Average Excellent Good
concentrations of H2O

Rate of adsorption Excellent Good Good Bad Good

Water capacity @ 77° F, 40% HR High High Medium High Medium
Separation by molecular sizes Yes No No No No

Capacity of adsorption @ high

Excellent Bad Bad Good Bad
temperatures

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 Flow diagram for Adsorption process Gas
Dehydration unit with two towers.

Pakistan Petroleum Limited m_haris@ppl.com.pk

 Absorption Dehydration
• Liquid Desiccants in stream of raw natural gas
serve to 'steal' the water out of the gas
stream.
– This operation is called absorption.
• There are numbers of liquids that can be used
to absorb water from natural gases such as
calcium chloride, lithium chloride and glycols.

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 Absorbent Selection
• The liquid that is most desirable to use for commercial dehydration
purposes should possess the following properties
– Strong affinity for water
– High boiling points
– Low cost.
– Noncorrosive
– Low affinity for hydrocarbons and acid gases.
– Thermal stability.
– Easy regeneration
– Low viscosity.
– Low vapor pressure at the contact temperature
– Low solubility in hydrocarbon.
– Low tendency to foam and emulsify.

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 Glycols & their Comparison
• Organic compounds known as glycols
approximate the properties that meet the
commercial application criteria.
• There are a few types of glycol usually used in
industry with their advantages and
disadvantages like EG, DEG, TEG and TREG.

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 Physical Properties MEG DEG TEG TETRA EG

Formula C2H6O2 C4H10O4 C6H14O4 C8H18O5

Molecular Weight, g/mol 62 106.12 150 194.2
Boiling Point @ 760 mm Hg, °C (°F) 197 (387) 245 (473) 288 (550) 329 (625)
Decomposes
Vapor Pressure at 20°C (68°F) mm Hg 0.06 0.002 <0.01 <0.01
Density, (g/cc) @ 20°C (68°F) 1.115 1.118 1.125 1.124
Freezing Point, °C (°F) -13.4 (7.9) -9.0 (16) -4.3 (24) -4 (25)
Pour Point, °C (°F) <-59 (<-75) -54 (-65) -58 (-73) -41 (-42)
Viscosity, cP @ 25°C (68°F) 16.9 35.7 49.0 58.3
Surface Tension, dynes/cm @ 25°C (77°F) 48 44.8 45.5 44.0
Refractive Index @ 20°C (68°F) 1.430 1.447 1.455 1.459
Specific Heat @ 25°C (77°F) Btu/lb/°F 0.58 0.55 0.52 0.52
Flash Point, °C (°F) 116 (241) 154 (310) 177 (350) 202 (395)
Heat of Formation, Btu/lb@ 25°C (77°F) -93 -131 -171 -212
Heat of Vaporization, Btu/lb@ 25°C (77°F) 369 234.4 179 139

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• TEG is a colorless, odorless viscous liquid with
molecular formula C6H14O4
• TEG is one of the best glycol frequently used
in industry.
• DEG is lower in cost than TEG but DEG has a
larger vapor pressure hence larger losses also.
• TETRA EG is more viscous than TEG, high
viscosity translates into higher pumping costs.

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1. TEG is regenerated more easily to a concentration of 98–99% in an
atmospheric stripper because of its high boiling point and
decomposition temperature.

2. TEG has an initial theoretical decomposition temperature of 404◦F,

whereas that of diethylene glycol is only 328◦F (Ballard, 1966).

3. Vaporization losses are lower than monoethylene glycol or

diethylene glycol. Therefore, the TEG can be regenerated easily to the
high concentrations needed to meet pipeline water dew point
specifications.

4. Capital and operating costs are lower.

 Glycol Dehydration
• Glycol dehydration units generally contains a
contactor, a flash tank, heat exchangers, a
regenerator, filters, surge tank, inlet & outlet
separators and a glycol circulation pump.
• The dehydration process can be divided into
two parts
– Gas dehydration
– Glycol regeneration.

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 Efficiency of Dehydration Plant
• Efficiency of a dehydration process is
evaluated by the water contents or dew-point
of wet gas.

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 Glycol Degradation
• Degradation of the glycol starts at about 410 ˚F.
• Causes of glycol degradation is
– Sulfur compounds.
– Soot deposits
– Salty water evaporation
– Hydrocarbons in Glycol
• To avoid glycol degradation
– Maintain the Temperature at 400˚F
– Effective filtration is necessary to avoid sulfur
compounds and other contaminants in glycol
– Firebox is required to be checked periodically
 Foaming
• Glycol has strong tendency of foaming
• Foaming increase the glycol losses through
carryover in the absorber and flash separator
• To lower the tendency of foaming formation
– Demister pads are installed in the absorber and
flash separator.
– Chemical injection (Anti foam agents) in a limited
quantity is used.
 pH Control
• Check the glycol pH periodically and keep in
the range 7.3 to 8.5.
• Uncontrolled pH make the glycol sour
• The addition of boras, ethanolamine, or other
alkaline chemical can control the pH.
• Too high pH is undesirable because it can
increase the tendency of solution to foam.
 Corrosion
• Pure glycol solutions are themselves
essentially non corrosive to carbon steel.
• Corrosion is accelerated by the presence of
other compounds (Oxidation of glycol,
thermal degradation of glycol, reaction with
sulfur compounds in gas stream, particulates
in lean glycol, chlorides (sodium, calcium)

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Sizing of glycol systems