"OIL AND GAS PROCESSING PLANT DESIGN 2002

AND OPERATION TRAINING COURSE"

Page 1
DGEP/SCR/ED/ECP "GAS SWEETENING PROCESSES"

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AND OPERATION TRAINING COURSE"
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DGEP/SCR/ED/ECP "GAS SWEETENING PROCESSES"

1. GENERAL 4
2. GAS SWEETENING PROCESSES 4
2.1. chemical absorption 4
2.2. Physical Absorption 25
2.3. Physico-Chemical Absorption 28
2.4. Physical Adsorption 31
2.5. Cryogenic Fractionation 32
2.6. Permeation (Membrane) 33
2.7. Direct conversion to sulfur 38
2.8. Polishing treatment for H2S Removal 38
2.9. Guideline for the gas sweetening process selection 40
3. BIBLIOGRAPHY 41

APPENDIX

Figure XI-B.1 Chemical formulas of alknolamines

Figure XI-B.2 Alkanolamine general Process Flow Diagram

Figure XI-B.3 MEA Sweetening Process Flow Diagram

Figure XI-B.4 MEA Reclaimer scheme

Figure XI-B.5 Boiling point - Condensation versus composition for Aqueous MEA
solutions at 0.7 bar g.

Figure XI-B.6. Fluor Econamine Process (DGA) Flow Diagram of BAB gas plant

Figure XI-B.7 DGA Reclaimer Unit Scheme

Figure XI-B.8 NGL2 ADIP Unit for Utility Gas Sweetening of UMM SAID

Figure XI-B.9 EAP Activated MDEA Process Flow Diagram

Figure XI-B.10 UOP Amine Guard (UCARSOL Solvent) Process Flow Diagram

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Figure XI-B.11 MDEA regeneration Process Flow scheme

Figure XI-B.12 BENFIELD Simplified Base Process Flow Diagram

Figure XI-B.13 SHELL SULFINOL Simplified Process Flow Diagram

Figure XI-B.14 RYAN/HOLMES simplified Process Flow Diagram

Figure XI-B.15 Typical CH4/CO2 Distillation Profiles

Figure XI-B.16 CO2/ETHANE vapor-liquid equilibrium

Figure XI-B.17 Cryogenic bulk CO2 Removal Simplified Process Flow Diagram

Figure XI-B.18 Spiral Wound membrane element

Figure XI-B.19 Hollow Fiber membrane element

Figure XI-B.20 One Stage Membrane System Block Diagram

Figure XI-B.21 Two Stage Membrane System Block Diagram

Figure XI-B.22 PEREZ COMPANC Membrane Plant Simplified Process Flow Diagram

Figure XI-B.23 KVAERNER Hollow Fiber Membrane System plant Simplified Process
Flow Diagram

Figure XI-B.24 CYNARA Hollow Fiber Membrane System plant Process Flow Diagram

Figure XI-B.25 Sweetening processes for gas containing CO2 only (no H2S)

Figure XI-B.26 Sweetening processes for gas containing CO2 and H2S

Figure XI-B.27 H2S selective absorption from gas containing H2S and CO2

Table XI-B.1a) Physical properties of pure alkanolamines (ethanolamines)

Table XI-B.1b) Advantages and disadvantages between different amines

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DGEP/SCR/ED/ECP "GAS SWEETENING PROCESSES"

1. GENERAL

Natural Gas (from a natural reservoir or associated to a crude production) can contain acid gas
(H2S and/or CO2).
The Gas Sweetening Process aims to remove part or all of the acid gas that the natural gas
contains for different reasons as follows:

 For safety reason, to remove the H2S content of the natural gas stream.
 To satisfy a Sales Gas specification : H2S content of the Sales Gas must be below 4 ppm
V (about 5.7 mg of H2S/Sm3 of gas or 0.25 grains of H2S/100 SCF of gas).

CO2 content must be adjusted to allow the Sales Gas to fit with the required range of gross
calorific value (GCV).

 To allow a downstream process to work properly. This is the case for a cryogenic process
(the CO2 can freeze at temperatures around -70 deg.C).
 To decrease the H2S content of a gas used in a crude cold stripping.
 For Enhance Oil Recovery (EOR) by CO2 injection (CO2 is removed from the gas and
injected the oil reservoir).

2. GAS SWEETENING PROCESSES

The different Gas Sweetening Processes to be applied depend on the quality and quantity of acid
gas contaminants to be removed:

 CO2 when this is the sole contaminant of the gas

 H2S when this is the sole contaminant of the gas
 CO2 and H2S simultaneously
 Selective removal of H2S when both CO2 and H2S are present in the gas

The existing processes are as follows:

 Chemical Absorption
 Physical Absorption
 Physico-chemical Absorption
 Physical Adsorption
 Cryogenic Fractionation
 Permeation (membrane)
 Direct conversion to sulfur

2.1. chemical absorption

Several chemical solvents are available for gas sweetening processes, almost all of them being
based on alkanolamine products. They are all used under form of aqueous solutions.

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The main alkanolamine products used in the gas sweetening industry are as follows :

 Mononethanolamine or MEA
 Diglycolamine ( ) or DGA
 Diethanolamine or DEA
 Diisopropanolamine or DIPA
 Methyldiethanolamine or MDEA

As an alternative to alkanolamine products, an alkaline salt is also used :

 Hot Potassium Carbonate or HPC or Hot Pot

Chemical formulas of alkanolamines are shown in figure XI-B.1. Main properties of these products
are shown in table XI-B.1a).
Chemical absorption process is based on a contact between the gas to be treated (feed gas) and
an aqueous solution containing one of the above solvents. Acid gas in the feed gas is a weak acid
which reacts with the alkanolamine (alkaline product) or alkaline salt (in the case of potassium
carbonate) to give bisulfide (with H2S) and bicarbonate (with CO2).
The chemical reaction (chemical absorption) takes place in a fractionation column (absorber or
contactor) which is equipped with trays or packing. The gas enters the column at the bottom tray
(or at the bottom part of the packing). The aqueous solution enters the column at the top tray (or at
the top section of the packing).
There is a heat of reaction between the solvent and the acid gas during this absorption, which is
exothermic. The treated gas exits the unit at a higher temperature than the feed gas. This implies
that the treated gas water content will be higher than the feed gas water content. As a
consequence should a dehydration of the gas be also required, this unit will be always installed
downstream of the sweetening unit.
The alkanolamine salt is then re-transformed into alkaline solution in a regeneration section and
the cycle is repeated again.

2.1.1. Description of an Amine process

This process flow scheme varies little, regardless of the aqueous amine solution used as the
sweetening agent. Slight modifications can appear linked to the type of amine which is selected
and to the optimization of the scheme for specific purposes.
The general process flow for an amine sweetening plant is shown in figure XI-B.2.
The feed gas (sour gas) containing H2S and/or CO2 always must enter the plant through an Inlet
Separator (or feed gas knock-out drum) to remove free liquids and/or entrained solids.

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DGEP/SCR/ED/ECP "GAS SWEETENING PROCESSES"

Inlet Separator
Objective
Catch liquid entrainments (water and hydrocarbon condensate and mist) to prevent entries of
contaminants in the amine system

Characteristics
Generally vertical drum equipped with Demister pad to prevent liquid droplets carry-over

Alternatives
Cartridge filter-separator

The gas from this separator enters the bottom of the Absorber and flows upward trough the
column in intimate counter-current contact with the aqueous amine solution (lean solution). In the
column the chemical reaction between the amine and the feed gas acid gas occurs and the
amine solution absorbs the acid gas. The chemical reaction (due to the heat of reaction between
the amine and the acid gas) is exothermic. It will raise the temperature of the gas.
Treated gas (lean gas or sweet gas) leaves the top of the column and the amine solution loaded
with acid gas (rich solution) leaves the bottom of the column.

Absorber
Objective
Acid gas removal from feed

Characteristics
- Fractionation column equipped with trays (generally around 20) or packing beds (generally 2 or
3 beds).
- The column must be equipped with pressure differential instrument to monitor the differential
pressure across the trays (or beds)
. sharp P increase indicated foaming
. slow P indicated tray (or bed) fouling
- The column generally is fitted with three (3) level glasses at bottom to detect the real level in the
bottom where there is foaming or oil layer
- Lean solution inlet temperature = at least feed gas temperature + 5 deg.C to avoid hydrocarbon
condensation. Higher lean solution inlet temperatures will result in lower acid gas pickup up by
the solution and higher water losses (treated gas higher temperatures).

The absorber column operates at the feed gas pressure. A minimum pressure of 4/5 b.a is required
to make the process feasible and operable. There is no limitation on high pressure as far as the
process is concerned. The only limitation relates to the thickness of the still plates to form the body
of the column (anticipated construction problems for thickness above 150 mm).
Feed gas temperature must be positive (high freezing point of the amine solutions). However high
temperatures will affect the performances of the unit. Should the feed gas be at high temperature,

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an inlet cooler (using air or water) or a gas/gas exchanger (using the hot treated gas as heating
medium) will be provided. This equipment will be installed upstream of the inlet separator.
The top of the absorber can be equipped with additional trays (2 to 4) to accommodate a water
wash section. The injected water will remove the amine carried over with the treated gas. It is
injected at the top tray and completely withdrawn at last tray of the water wash section.
The treated gas is then handled by a separator (or Treated Gas KO Drum) to collect entrained
liquid before being routed to the downstream facilities.

Treated Gas KO Drum

Objective
Dry the treated gas by removing entrained amine

Characteristics
Vertical drum equipped with Demister pad

Alternative
Cartridge filter-separator

The rich solution from the Absorber is then let down and generally routed to the Amine Flash
Drum. This drum (which operating pressure is between 7 and 15 b.a) allows to remove a portion of
acid gas which evolves from the solution by the pressure let-down effect. The acid gas stream from
the Amine Flash Drum is routed either to the fuel gas pool of the facilities or to the acid gas
disposal system.

Amine Flash Drum

Objective
Removal of dissolved gas and entrained liquid hydrocarbons upstream the amine/amine heat
exchanger and the regenerator

Characteristics
- Generally horizontal three-phase drum (liquid hydrocarbons skimming system is required
- Should be operated at minimum pressure (for a better degassing of the solution)
- Liquid retention of 10 to 20 minutes have been used

The rich solution from the Amine Flash Drum then passes through an Amine/Amine Heat
Exchanger. This heat exchanger serves as a heat conservation device and lowers the total heat
requirements for the process. The rich solution is heated by the regenerated solution (lean
solution) coming from the regenerator.

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Amine/Amine Heat Exchanger

Objective
Preheat the rich solution to the regenerator

Characteristics
- Shell and tube exchanger with rich solution tube side/lean solution shell side
- Minimum vaporization should take place in the exchanger (tube side) to prevent
erosion/corrosion due to mixed flow
- Velocity must be limited to 1 m/s
- Should several exchanger be required, they will be stacked vertically with the rich solution
entering at the lower part of the bottom exchanger so any liberated gas will be removed in the
upward flow of amine solution
- Lean solution inlet temperature between 110 to 130 deg.C
- Rich solution outlet temperature between 90 and 110 deg.C

Alternative
Plate frame exchanger. This type of exchanger offers larger surface areas and higher heat
transfer rates in a small volume. It is however more susceptible to fouling

Then the rich solution is let down to the operating pressure of the Regenerator (generally between
1.2 and 2 b.a) also called stripper is a fractionation column (with trays or packing) with a condenser
(using water or air as cooling medium) and a reboiler.

Regenerator
Objective
Regenerate the rich amine by stripping of the acid gas

Characteristics
- Fractionation column equipped with trays (generally around 20) or packing beds (generally 2 or
3 beds).
- The column must be equipped with pressure differential instrument to monitor the differential
pressure across the trays (or beds)
. sharp P increase indicated foaming
. slow P indicated tray (or bed) fouling/plugging
- Demister pad can be installed at the top to reduce amine loss caused by physical entrainments

The Regenerator trapout product feeds the Reboiler which is a shell and tube exchanger (using
hot oil or steam as heating medium).

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Reboiler
Objective
Heat up the rich solution to produce the energy to reverse the chemical reaction to free acid gas
from the amine solution and to generate steam to strip acid gas from solution. The stripping
efficiency is controlled by the overhead reflux ratio.

Characteristics
- Generally kettle type reboiler. Square tube pitch pattern is recommended
- Regenerated solution outlet temperature is only function of operating pressure and amine
strength
- Reboiler duty controlled by heating medium rate (steam or hot oil)
- Tube skin temperature <145 deg.C to avoid amine degradation
- Space to be provided below the bundle to have a good natural circulation and leave room for
sludge deposit
- Liquid layer above the bundle high enough to prevent localized drying and overheating (150 to
200 mm height)
- Sufficient vapor volume above the liquid level to have no solution entrainments

This Reboiler can be a direct fired heater. In this case precaution must be taken to avoid local
overheating of the solution (this would lead to formation of corrosion by-products and amine
excessive vaporization ).
The regenerated solution from the Reboiler (at its bubble point at the operating pressure of the
Regenerator) at temperatures generally between 110 and 130 deg.C, is then routed back to the
Amine/Amine Exchanger.
The top product of the Regenerator is a water vapor/acid gas mixture. This stream is handled by
the Condenser where the water vapor is condensed to generate reflux to the Regenerator. It uses
ambient available cooling medium (water or air). Classical shell and tube exchanger (water
cooling) or air cooler (air cooling) are used for this purpose.
A Reflux Drum (or Regenerator Overhead Drum) is provided to collect the condensed water and
acid gas from the condenser. The acid gas stream from the Reflux Drum is routed to the acid gas
disposal system. Water from the Reflux Drum is handled by Reflux Pumps (generally two reflux
pumps: one in operation and one stand-by) and routed back to the top of the Regenerator.
Reflux ratios between 0.9/1 to 3/1 mole of water per mole of acid gas are generally used to make
the process to work properly.

Reflux drum
Objective
- Recover as stripper reflux the water condensed in the condenser
- Catch possible condensed hydrocarbons

Characteristics
- Vertical or horizontal drum equipped with Demister pad
- Temperature as low as possible to minimize amine concentration and water entrainments to
downstream facilities (for example Sulfur recovery unit)
- Oil skimming facilities to be provided

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The temperature of the lean solution leaving the Amine/Amine Exchanger is generally still far
above the feed gas inlet temperature. Lean solution high temperatures will result in lower acid gas
pickup up by the solution and higher water losses (treated gas higher temperatures). A final Lean
Solution Cooler is then provided (using water or air as cooling medium) to cool the solution.
Circulation Pumps (generally 2 x 100 % or 3 x 50 %) are provided to send the cooled lean
solution back to the Absorber.
In large units, the amine pumping system can include first a set of Booster Pumps and then the set
of Circulation Pumps. The objective of the booster pumps is to feed the main pumps without NPSH
problems.
Pumps can be driven by electric motors or turbines (gas or steam turbines). Rich solution let down
from the Absorber pressure to the Amine Flash Drum pressure can be done through hydraulic
turbine (instead of J-T valve). Power recovered on the shaft of the hydraulic turbine can be used to
drive a Circulation Pump.
Solid impurities such as iron sulfide, iron oxide, sand, pipeline dust must be removed from the
solution in order to prevent erosion and foaming. Filtration of the solution is then mandatory.
The Mechanical Filter (main filter) is normally located on the lean solution stream to the Absorber
after the Amine/Amine Exchanger.

Mechanical Filter (main filter)

Objective
- Removal of the solids from amine solution (lean amine solid content < 100 ppm Wt).

Characteristics
- Generally leaf-type precoat filter ( Filtration mesh : 10  maximum)
- Inlet flow rate : 10 to 20 (for large units) % of the solution circulation rate
- Pressure drop : 1 b maximum

An Activated Carbon Filter can be added downstream of the main filter to remove products not
stopped by the main filter (hydrocarbon, water soluble compounds, unknown foam contributors).
The flow rate to the Activated Carbon Filter can be less than the flow to the main filter.

Activated Carbon Filter

Characteristics
- Liquid velocity through the activated carbon bed would be less than 1cm/s.
- Height of the bed would be above 1.5 m
- Diameter of carbon particles would be 1/8 to 1/4 (4x10 mesh)
- Density of about 300 kg/m3
- Pressure drop : 1 b maximum
- The life of the activated carbon bed is at least 1 year.

Should a Carbon Filter be provided, a downstream additional filter (Polishing Filter) must be
installed to remove particles of carbon.

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