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Absorption & Adsorption

Dehydration

Prepared by
Archana
Introduction to Natural
Gas
Natural gas is mixture of
hydrocarbons
Methane one carbon atom C1
Ethane two carbon atoms C2
Propane three carbon atoms C3
iso-Butane four carbon atoms i-C4
n-Butane four carbon atoms n-C4
iso-Penatne five carbon atoms i-C5
n-Pentane five carbon atoms n-C5
C6+ all compounds heavier than hexane
(C6)
Inert Compounds
Natural gas often contains inert compounds.
Nitrogen (N2)
Carbon Dioxide (CO2)

Inert compounds are undesirable because they do not


contribute to the heating value of the natural gas.
Trace amounts of contaminants can also be present in
natural gas.

Contaminants are removed to below acceptable


levels.
Hydrogen Sulfide (H2S)
Other sulfur compounds.
Water
The best gas to sell

The best gas to sell, is one without:


Inert Compounds that add volume and
dont contribute to the Heating Value.
Contaminants that could cause damage.
Dangerous Metals like Mercury.
To get it Sales Sweete
Gas ning
Units
Fractionation
Train

To get the best gas to


Acid
sale, Natural Gas is Dehydration Gas
processed and Removal
purified.

Gas
Well

NGL
Condensate Recovery
Mercury
and
Removal
Water Removal

Nitrogen
Removal
To get it

Mercury Acid Gas


Raw Gas Removal Removal

Natural Dew Point Dehydration


Gasoline

Natural Gas
Compression
Gasoline
Mercury Removal

Mercury removal is done through


Activated Carbon Injection
Water & Water Vapor
Contaminant
It is the most common contaminant in
natural gas, usually in range of 8000 to
10,000 ppm by volume ( 400 to 500 lbm
water vapor/MMscf of gas)
Pipeline specifications restrict the water
content to a value no greater than 120 to
160 ppm by volume (6 to 8 lbm/MMscf of
gas)
Typical values are 7 lb/MMscf at dew point
32 F & 1000 psi gas line in Southern U.S
Typical values are 4 lb/MMscf at dew point
20F & 1000 psi gas line in NorthernU.S
Liquid Water & water Vapor Removal from
NG because
Prevent formation of hydrates in processing &
transmission systems
Meet a water dew point requirement of the sales
gas contract

Dew Point: Indirectly indicate the water content


of the natural gas
Dew point: Defined as the temp. at which the gas
is saturated with water vapor at a given
pressure.
Dew Point Depression: The diff. between the dew
point temp. of a gas stream before and after
dehydration is called the dew point depression.
Liquid Water & water Vapor Removal from
NG because
Prevent corrosion
Water Content Determination
Water Content of the gas depend upon
a) Gas Composition: higher gravity gases usually
less water
b) Temperature: Water Content increases with
increasing temp.
c) Pressure: Water Content decreases with
increasing pressure
Methods for calculating water vapor of
natural gases
Partial Pressure Approach (valid upto 60
psia)
Empirical plots ( Mostly used in
Engineering Calculations)
I. Mcketta & Wehe Correlation for Sweet
gases: for sweet natural gases
containing over 70% methane & small
amounts of heavy ends
II. Robinson et al. Correltion for sour gases
III. Campbells Correlation for sweet and
sour gases
Mcketta & Wehe Correlation for Sweet
gases
Robinson et al. Correltion for sour gases
Campbells Correlation for sweet and sour
gases
For CO2
For H2S
HYDRATES IN NATURAL GAS SYSTEMS

Natural gas hydrates are solid crystalline


compounds, resembling ice or wet snow in
appearance , but much less dense than ice.
They are included in general class of
compounds known as clathrates, which have
a structure wherein guest molecules are
entrapped in a cage-like framework of the
host molecules without forming a chemical
bond.
A hydrate is a physical combination of water
and other small molecules to produce a solid
which has an ice-like appearance but
possesses a different structure than ice. , it
cause flow interrupting.
Natural gas hydrates are formed when natural
gas compounds, notably methane, ethane,
propane, iso-butane, hydrogen sulfide,
carbon dioxide, & nitrogen enter the water
lattice & occupy the vacant lattice position,
causing the water to solidify at temperature
considerably higher than the freezing point of
water

There are three recognized crystalline structures


I,II,H

Their formation in gas and/or NGL systems can


plug pipelines, equipment, and instruments.
Water molecules build the lattice and
hydrocarbons, nitrogen, CO2 and H2S occupy the
HYDRATES IN NATURAL GAS SYSTEMS

Smaller molecules (CH4, C2H6, CO2, H2S)


stabilize a body-centered cubic called
Structure I.

Larger molecules (C3H8, i-C4H10, n - C4H10)


form a diamond-lattice called Structure II.

Normal paraffin molecules larger than n-


C4H10 do not form Structure I and II hydrates
as they are too large to stabilize the lattice.
However, some iso paraffins and cyclo alkanes
larger than pentane are known to form Structure
H hydrates.
Hydrates
Hydrate Number: The number of water molecules associated with each molecule of the g

component included in the hydrate is known as the hydrate number.
No specific hydrate number can be given for a particular hydrate

The limiting hydrate number, a theoretical quantity determined using the size of the g
& the size of the voids in the water lattice
Hydrate molecules can typically be represented as
Methane: .O Nitrogen: O
Ethane:.O Carbon dioxide: O
Propane: .O Hydrogen Sulfide: O
Isobutane:.O
*Normal butane does form hydrate, but it is very unstable. Paraffins higher than butane
hydrates

.
The conditions which affect hydrate formation are:
1- Primary Considerations
Gas or liquid must be at or below its water dew point or
saturation condition.
To allow water droplet condensation. No hydrate
formation is possible if free water is not present
Temperature: Low temp., at or below the hydrate
formation temperature for a given pressure & gas
composition
Pressure: High operating pressures, that may raise the
hydrate formation temperature to the operating
temperature
2- Secondary Considerations:
Mixing or agitation, or pressure pulsations, or high
velocities
Presence of small seed crystal of hydrate
Kinetics
Physical site for crystal formation such as a pipe elbow,
orifice, thermowell, or line
Salinity.
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21
Hydrate Phase Behavior
Phase equilibrium diagram for gas-water-hydrate system

Hydrates exists in the pressure-temp. region


above the hydrate curve ABCD. Below the
hydrate curve, & to its right , no hydrates
can form
Above the vapor pressure curve HFCI, the
hydrocarbon exists in the liquid state
Towards the left of the line EBFG, water
exists in the solid form as ice. On the right
of EBFG, water will be in the liquid state
The hydrate curve become vertical at the
point where it intersects the hydrocarbon
vapor pressure curve. This intersection, C,
therefore represents the maximum hydrate
forming temperature
Hydrate forming conditions for natural gas
components. (after Campbell, 1984a)
Hydrate formation (Approximate method for sweet
gases)
This
is graphical procedure. The data presented in the GPSA
charts do not account for the presence of S &
It can divided into two categories (Ikoku, 1984).
Category I:
Hydrate formation due to a decrease in the temperature (or
pressure) with no sudden expansion (or compression), such
strings & surface lines
Category II:
Hydrate formation due to sudden expansion, such as in flow
orifices, chokes, & back-pressure regulators

* Next page figure for category II are used for determining t


expansion, without hydrate formation of a gas with a given
Hydrate formation of category I
Hydrate formation of category II
Determination of hydrate formation
temperature & Pressure

Katz et al. Method (1959)


Trekell-Campbell method for high
pressure gas (1966)
McLeod-Campbell Method for very
high pressure sweet gas
Katz et al. Method (1959)

It uses vapor-solid equilibrium ratio, , first proposed by Carso


=

Where y= mole fraction of hydrocarbon in the gas on a water-f


= mole fraction of hydrocarbon in the solid on a water-free bas
This method account for the &
It is very reliable up to pressure about 1000 psia
equal to for gases that are non-hydrate formers.
For hydrocarbons heavier than butanes, , is
Hydrate will form when the following equation is satisfied:
Sum() =1.
* *Calculation of the hydrate forming condition is similar to the
calculation for multi-component mixtures
Steps for determining the hydrate temperature at
a given system pressure

1. Assume a hydrate formation temp.
2. Determine for each component
3. Calculate for each component
4. Sum the values of
5. Repeat steps 1-4 for additional assume
temperatures until the summation of
1
Vapor-solid equilibrium constant for
a) methane & n-butane
Vapor-solid equilibrium constant for
propane
Vapor-solid equilibrium constant for iso-butane

Vapor-solid equilibrium constant for
Trekell-Campbell method for high pressure gas

Provides corrections to the katz et al. method to extend its


higher pressures
Account for the negative effect of the presence of non-hydr
molecules that are too large to fit into the voids in the water
It uses methane as a reference gas
The additive effect of other hydrate forming gases , , , &
at different pressures is determined from graphs
Non-hydrate formers are grouped together into the pentane
Again using the figures to determine the hydrate depression
presence of non-hydrate forming gases as a function of the
pentane plus, & mole % pentane on the basis of the gas frac
Trekell-Campbell temperature displacement
chart for hydrate formers at 1000 psia
Trekell-Campbell temperature displacement
chart for hydrate formers at 2000 psia
Trekell-Campbell temperature displacement
chart for non-hydrate formers (Pentane
plus) at 1000 psia
Preventing Hydrate
Formation
The permanent solution for hydrate
problems is dehydration of the gas to
the sufficiently low dew point.
Commonly used dehydration Process
Absorption Dehydration using a liquid
dessicant
Adsorption Dehydration using a solid
dessicant
Simultaneous dehydration and gas-
liquid separation by expansion
Preventing Hydrate Formation at wellsite
Heating the gas stream, so that it
becomes undersaturated, and
maintaing flowlines and equipment
at tem. Above hydrate point
Case: Where liquid water is present
and the flowlines and equipment can
not be maintained above hydrate
temp.
Inhibiting hydrate formation by
injecting additives that depress both
hydrate and freezing temp.
Hydrate Inhibition by Additive Injection
Most common additives
o Methanol
o Ethylene Glycol (EG)
o Diethylene Glycol (DEG)

Methanol is used the most


Gas Dehydration

Process of removing water vapour from a gas


stream to lower the temp. (Dew point ) at which
water will condense from the stream
Most gas contracts specify a max. Value for the
amount of water vapor allowable in the gas
Dehydration to dew point below temp. prevent
hydrate formation and corrosion from condensed
water
If acid gases CO2 and H2S present in the gas
stream, they will form acid with the condensed
water
Methods of dehydration

Absorption Dehydration
Adsorption dehydration (Solid-Bed
dehydration)
Absorption Dehydration

Absorption Dehydration of natural gas is done by


contacting the gas with a hygroscopic(Absorbing
Moisture) liquid
Liquid Dessicant should possess:
High Absorption Efficiency
Easy and Economic regeneration
Non-Corrosive and non-toxic
No operational problems when used in high conc.
No interaction with the hydrocarbon portion of
the gas, & no contamination by acid gases
Common Dessicant
Ethylene Glycol (EG)
Diethylene Glycol (DEG)
Triethylene Glycol (TEG)
Tetraethylene Glycol

Uses of TEG is more because of lower vapor losses and


better dew point depression
Glycol offer a superior dew-point depression
TEG used for sweet as well as sour gases
TEG effect a dew-point depression of 40 to 140 degree
for operating conditions ranging from 25-2500 psig and
40-160 F
Glycol Dehydration
Glycol Dehydration System Consists of
A. Scrubber
B. Glycol-gas Contactor (Absorber)
C. Mist Eliminator
D. Gas-Glycol heat exchanger (Glycol Cooler)
E. High-Pressure Filter
F. Glycol Pump
G. Low-Pressure flash Separator
H. Surge Tank
I. Stripping Still
J. Reboiler
Process Flow
Process Flow Scheme
Wet gas first sent to scrubber to remove any liquid water & HCs,
sand, drilling mud, & other solid matter
These impurities must be thoroughly removed , because they may
lead to foaming. Flooding, poor efficiency, higher glycol losses, and
maintenance problems in the Glycol-Gas contactor (Absorber)
Mist Eliminator provided at scrubber outlet to ensure good gas
cleaning
Clean gas sent upward through Glycol-gas Contactor (Absorber),
counter current to the flow of Glycol
Absorber consists several trays and act as equilibrium separation
stages where water vapor from the gas is absorbed by the glycol.
Glycol contactors usually have 6-12 trays
Glycol usually absorbs about 1 scf gas/gal at 1000 psig absorber
pressure
The gas encounters leaner and leaner glycol as it rises through the
contactor
Glycol Dehydration Process
Dry gas from the top of the gas-glycol contactors flows
through the external gas-glycol heat exchanger (Glycol
cooler)
Gas cools the hot regenerated glycol before it enters the
contactor.
Cooling of hot regenerated glycol increases its absorption
capacity and decreases its tendency to flash in the
contactor
After this heat exchange cooled glycol enters the absorber
from the top and dry gas leaves the dehydration system
Other alternative of cooling of hot regenerated glycol :
The dry gas passes over a glycol cooling coil inside the
contactor instead of the external gas-glycol heat
exchanger
Glycol Reconcentration
System
Wet glycol from bottom of the glycol-gas contactor is first
sent to high-pressure filter to remove any solids that may
have been acquired by it from the gas stream.
The energy of the high-pressure glycol is used to drive the
glycol pump, which pumps the dry regenerated glycol to the
contactor.
From the pump, the wet glycol flows to a low-pressure flash
separator, where any dissolved or entrained gas is removed
The separated gas is used either as fuel gas for the reboiler,
or is vented to the atmosphere.
Glycol from the bottom of the flash separator is sent to heat
exchanger coils in the glycol surge tank
To preheat glycol by heat exchange with the hot, dry
regenerated glycol from the glycol regenerator
Preheated wet glycol is then sent to the stripping
still.
Stripping still is a tower packed with ceramic saddle-
type packing
Stripping still is mounted on the top of reboiler
The glycols flows downward through the packing.
That acts as equilibrium stages for glycol-water
separation
from stripping still glycol flows downward into the
reboiler.
Water vapor liberated from the glycol in the reboiler
passes upward through the packing, providing heat
and picking up some water from the wet glycol
flowing downwards.
The water vapor leaves the unit from top of the still
column through the atmospheric reflux condenser
In the reboiler, Glycol is heated to approx.
350-400F to reconcentrate it to 99.5% or
more.
Some stripping gas added to reboiler to
reconcentrate the glycol to 99.5 % or more
The reconcentrated glycol is sent to the
shell side of the heat exchanger, which also
serves as a surge tank
Regenerated glycol is cooled by heat
exchange with the wet glycol stream
From the pump, it passes through the shell
side of the glycol-gas heat exchanger(glycol
cooler), into the to of the absorber
Adsorption Dehydration or
Solid-bed Dehydration
Works on principle of adsorption
Adsorption involve a form of adhesion
between surface of the solid desiccant and
water vapor in the gas
A solid desiccant is used for the removal of
water vapor from a gas stream
Some solid desiccant dehydrate gas down
to 1ppm. Widely used in cryogenic
processing
Initial cost for solid bed dehydration unit is
more than the glycol unit

Mechanisms of adsorption:
Physical: used in gas dehydration.
Water forms an extremely thin film
that held to the desiccant surface by
forces of attraction
Chemical : it involves chemical
reaction, termed as Chemisorption
limited use in gas processing
Properties of physical
adsorbent
Large surface area for high capacity.
Surface area of commercial adsorbent
500-800 m2/gm
High mass transfer rate i.e. high rate of
removal
Easy, economic regeneration
Small resistance to gas flow. Low
pressure drop
High mechanical strength
Cheap, non-corrosive, non-toxic,
Adsorbent type
Alumina:
o Least expensive adsorbent
o Produces excellent dew point
depression
o Require much more heat for
regeneration
o Tendency to adsorb heavy
hydrocarbons
o Difficult to remove adsorbed HCs
during regeneration
Adsorbent
Gel: Silica Gel and silica-Alumina
Gel
o Can dehydrate gas to as low as
10ppm
o Greatest ease of regeneration
o Adsorb heavy HCs but release them
during regeneration
o Can handle sour gases
o Gel are useful when H2S is less than
5-6%
Adsorbent
Molecular Sieves
o Alkaline and subject to attack by acids
o Special-acid resistant available for very
sour gases
o Pore size is narrow, tend not to adsorb
heavy HCs
o Regeneration temp very high
o Can produce water content as low as
1ppm
o Can offer means of simultaneous
dehydration & desulfurization
Adsorption dehydration (Solid-Bed
dehydration)
Essential component
Inlet gas separator
Two or more adsorption tower filled with
a solid desiccant
High-temp. heater to provide hot
regeneration gas
Regeneration gas cooler to condense
water from the regeneration gas
Regeneration gas separator to remove
condensed water from the regeneration
gas
Piping, manifolds, switching valves and
Process Description
The adsorption process is cyclic
Multiple desiccant beds are used in cyclic
operation to dry the gas on a continuous
basis
For efficient desiccant performance and for
a longer desiccant life, the inlet gas
stream is thoroughly cleaned to remove
all liquids and solids
In each dehydrator three functions
performed
o Adsorbing or gas drying cycle
o Heating or regeneration
Contd....
The clean gas flows downward during
dehydration through one adsorber
Simultaneously other adsorber is being
regenerated
Gas flow is downward for dehydration in the
adsorber tower to lessen bed disturbance for
high gas velocity
Regeneration gas is sent upward through the
adsorber to ensure thorough regeneration of
the bottom of the bed
Sometimes, only the inlet(top) part of the tower
is recharged with desiccant
Desiccant bed may be rearranged or gas flow
Adsorption Regeneration
Cycle
Regeneration consists two parts
Heating
Cooling
First regeneration gas heated to a temp. of 400-600 F
& is sent to desiccant bed
Subsequently, the hot regenerated bed is cooled by
letting the regeneration gas bypass, or by completely
shutting off the regeneration gas heater
This cooling gas is sent downward through the bed, so
top of bed may adsorb any water from the gas
hot regeneration gas & cooling gas sent to
regeneration cooler to remove any adsorbed water
There are three basic sources of
regeneration gas in gas dehydration

1. Inlet gas
2. A closed cycle separated from the
stream being dehydrated
3. Dry effluent gas from the unit
Dehydration by Expansion
Refrigeration
Can be achieved in case of sufficient
pressure drop
Gas stream is cooled by adiabatic
expansion through choke
Two Techniques:
With hydrate inhibitor
Without hydrate inhibitor

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