ENPE 490

A. Veawab

4. GAS PROCESSING
4.1 Natural gas and gas processing operation

Natural Gas

Gas
purification

To
pipeline

Oil

To
refinery

Produced Water

To injection well
for disposal

Production
well

To treatment
facilities for reuse
and discharge

Two types of natural gas:

Associated gas (casinghead gas or oil well gas)
o natural gas comes from oil well (crude oil + natural gas + produced water)
o natural gas is separated from crude oil and produced water at the wellhead
Non-associated gas (gas well gas)
o natural gas comes from gas well (natural gas + produced water) containing little or no
crude oil
Typical natural gas composition of worldwide
vary greatly
Water exists in natural gas, but not shown in the below table. => produced water is removed
at the wellhead.
Canada
(Alberta)

Western
Colorado

Southwest
Kansas

Helium
0.0
0.0
0.5
Nitrogen
3.2
26.1
14.7
Carbon dioxide
1.7
42.7
0.0
Hydrogen sulfide
3.3
0.0
0.0
Methane
77.1
30.0
72.9
Ethane
6.6
0.6
13.4
Propane
3.1
0.3
7.5
Butanes
2.0
0.2
4.0
Pentanes and heavier
3.0
0.3
2.6
Source: Kidnay, A. J., Parrish, W. R., Fundamentals of
2006.

Bach Ho
Miskar
Rio Arriba, Cliffside,
Field
Field
Mexico
Amarillo,TX
Vietnam
Tunesia
0.0
0.0
0.0
1.8
0.2
16.9
0.7
25.6
0.1
13.6
0.8
0.0
0.0
0.1
0.0
0.0
70.9
63.9
96.9
65.8
13.4
3.3
1.3
3.8
7.5
1.0
0.2
1.7
4.0
0.5
0.1
0.8
2.6
0.6
0.02
0.5
natural gas processing. Taylor and Francis group, LLC,

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ENPE 490

A. Veawab

Water

Raw Gas

Helium
Water
Nitrogen
Helium
Carbon dioxide
Nitrogen

Gas
Processing

Carbon dioxide

Hydrogen sulfide
Pipeline gas

Hydrogen sulfide
Ethane
Methane
Propane
Ethane
n-Butane
Propane
i-Butane
n-Butane
Natural gasoline
i-Butane
Pentanes +

Utilization of gas processing products

Methane
Ethane
Propane
Ethane-propane mix
Isobutane

n-Butane
Natural gas liquids
(NGL)
Natural gasoline
Sulfur

Fuel/ feedstock in chemical production (e.g. ammonia and methanol)

Fuel/ feedstock in chemical production (e.g. ethylene, polyethylene)
Petrochemical/ residential/ farm/ transportation
Feedstock in chemical production
Feedstock for methyl tertiary butyl ether (MTBE) production/
feedstock in the production of reformulated gasoline and propylene
oxide
Domestic uses (gasoline)
All hydrocarbon liquefied => ethane, propane, butanes and natural
gasoline
Pentanes + heavier H-C => used in refineries for blending into
gasoline/ feedstock for C5/C6 isomerization/ production of ethylene
Converted from H2S => used for production of sulfuric acid/
manufacture of black gunpowder

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ENPE 490

A. Veawab

Specifications for pipeline quality gas

(vary from place to place)
Major Components
Methane
Ethane
Propane
Butanes
Pentanes and heavier
Nitrogen and other inerts
Carbon dioxide
Total diluents gases
Hydrogen sulfide
Total sulfur
Water vapor
Oxygen
Liquids

Solids

Heating value (gross,

saturated)

Minimum mole%
75
None
None
None
None
None
None
None
Trace components
6-7 mg/m3
115-460 mg/m3
60-110 mg/m3
1.0%
Free of liquid water &
hydrocarbons at delivery
temperature and pressure
Free of particulates in amounts
deleterious to transmission and
utilization equipment
35,400-42,800 kJ/m3

Maximum mole%
None
10
5
2
0.5
3
2-3
4-5

Source: Kidnay, A. J., Parrish, W. R., Fundamentals of natural gas processing. Taylor and Francis group, LLC,
2006.

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A. Veawab

Gas processing:

Transported Raw Gas

Oil/Water/Solid

Phase Separation

Gas Treating

CO2 / H2S

Water

Dehydration
Hydrocarbon Recovery

Sulfur Recovery

Natural Gas Liquids (NGL)

Natural Gasoline

Nitrogen Rejection
Helium Recovery

Sales Gas to Pipeline

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CO2
Elemental Sulfur

ENPE 490

A. Veawab

4. 2 Gas treating
Objective: To remove H2S and CO2
Why remove H2S from natural gas?
H2S is highly toxic.
threshold limit value (TLV) = 10ppm
dead in minutes when H2S >1000ppm
H2S + water => corrosive acid => corrosion of materials
Why remove CO2 from natural gas?
CO2 is nonflammable. => undesirable as a fuel => lower heating value of natural
CO2 + water => corrosive acid => corrosion of materials
How much H2S and CO2 must be removed?
For transportation in a pipeline and residential/ industrial use
down to 6-7 mg/m3 H2S (see pipeline specification)
down to a maximum of 2-3 mol%CO2
For a cryogenic process (low temperature) (e.g. nitrogen rejection or NGL recovery)
CO2 must be removed to prevent formation of solid
How the removed H2S and CO2 are disposed (or utilized)?
For the large quantities of the removedCO2 => Used as an injection fluid in Enhanced Oil
Recovery (EOR)
For the removed H2S:
Trace concentration of H2S => Incineration and venting (providing that SO2 emissions
meet regulatory standard)
High concentration of H2S => Conversion to elementary sulfur
What are common technologies for gas treating?
Gas absorption into liquid (solvent) => most used onshore
Gas permeation through membrane => suitable for offshore => smaller footprint/ lighter
weight compared to gas absorption
***safest and most environmentally friendly => no chemicals used
Gas adsorption onto adsorbent (solid)
***adsorbent (molecular sieve)=> nonhazardous and disposable in landfill
***Inlet condition of natural gas stream to gas treating process => ambient temperature/ 3001,000 psi (20-70 bar)

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A. Veawab

Gas absorption into liquid: (amines)

Acid gas

Condenser
Treated gas
Lean amine

Reflux
accumulator

Lean cooler

Absorber

Cross heat
exchanger

Regenerator

Gas

Reboiler

Sour gas
Flash tank

Filter

Liquid

Reclaimer
Waste

Chemicals used:
Absorption solvents (amines => monoethanolamine (MEA), diethanaolamine (DEA),
methyldiethanolamine (MDEA), diglycolamine etc.)
Corrosion inhibitor (heavy metals => vanadate, antimony, copper etc.)
Sodium carbonate or sodium hydroxide (for solution reclamation)
Wastes or discharges:

Amine solution containing corrosion inhibitor + heat stable salts

Reclaimer waste
o heat stable salts + absorption solvent + corrosion inhibitor
o approx. 0.003 m3 of reclaimer waste per tonne of CO2 removed in a commercial FG
Econamine process
Waste from solution filtration => filter sludge, filter bag, cartridge, used activated carbon
Removed CO2 and/or H2S
BTEX (benzene, toluene, ethylbenzene, and xylene may-be stripped out of rich-amine and
vented from regenerator) <= amine has affinity of BTEX.
CO2 and/or H2S (leakage from process equipment)
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A. Veawab

Operation:
Gas absorption
Feed gas containing acid gas (H2S and/or CO2) enters the absorber at the bottom while lean
amine (aqueous solution) containing small content of acid gas enters the absorber at the top.
Gas and solution are in contact. => acid gas is absorbed into solution. => Solution becomes
loaded with acid gas (called rich amine).
Rich amine leaves the absorber and passes through a flash tank where the dissolved
hydrocarbons in the rich amine are flashed off due to the reduction in pressure.
Rich amine is sent to a rich-lean heat exchanger to raise its temperature and then sent to a
regenerator where the removed acid gas is stripped off by mean of heat.
Rich amine enters the regenerator at the top and flows downward against the flow of a hot
vapor mixture of steam + amine + acid gas. => acid gas is stripped and flows upward with
the hot vapor mixture to the top of the regenerator and eventually leaves the regenerator.
The hot vapor mixture (steam + amine + acid gas) is sent to a condenser to reduce its
temperature and recover/recycle water + amine to the regenerator, while acid gas exists the
process.
Reclaiming of degraded amine solution
As amine solution is re-circulated within the process, it is gradually degraded in the presence of
oxygen. => form heat stable salts (carboxylic acid anion = formate, acetate, thiosulphate,
thiocyanate, oxalate, sulphate, etc.)
Thermal reclaiming = to remove heat-stable salts (organic acid)
Circulate a slipstream of 1-3% of the circulating amine solution to a reclaimer
Add sodium carbonate or sodium hydroxide (base) to neutralize the heat-stable salts
Heat the solution mixture in the reclaimer => vaporize water and amine vapor => leave heat
stable salts in the liquid bottom

Waste of environmental concern

Amine
Heavy metal corrosion inhibitor
BTEX
H2S leakage

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A. Veawab

Waste management
Minimization of amine waste:
Background
Amine solution are degraded by reaction with CO2, oxygen, sulfur or other impurities =>
form heat stable salts and amine degradation products.
Heat stable salts / amine degradation products reduce process performance and induce
operational problems (e.g. corrosion and foaming).
In practice, when these products reach 10% of the active amine solution, two choices =>
o Solution change-out => add new amine solution + discharge amine waste
o Purification of amine solution => minimize new amine solution added + minimize
amine waste discharged
Preferred choice => purification of amine solution (RECYCLE/REUSE)
Purification methods
1. Mechanical filtration
Remove suspended solids and sludge from amine solution (5-10 microns)
Two types of filters:
Surface filter => collect solids on the surface of filter media
Depth filter => trap solids inside the structure of media
Examples of filters => string-wound cartridge, cotton sock, pressed cloth
Continuously flow a side stream of amine solution (10-20% of total solution flow)
Installed at the lean side of the downstream of the lean amine cooler
Waste product = filter sludge, filter bags and cartridge (hazardous) => LANDFILL
2. Activated carbon adsorption
Remove high molecular weight organics => amine degradation products
Use adsorption
Continuously flow a side stream of amine solution (10-20% of total solution flow)
Installed at the lean side of the downstream of the lean amine cooler
Waste product = spent carbon and filter water product (hazardous) => LANDFILL
3. Thermal reclaiming
Remove heat-stable salts + solids + nonvolatile compounds
Use distillation to separate volatiles (amine + water) from relatively nonvolatile compounds
(heat-stable salts)
Continuous flow of side stream of amine solution (0.5-2% of the total flow) from regenerator
reboiler

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Use steam-heated reclaimer (kettle)

Amine + Water

Steam (in)

Feed Solution

Waste

Condensate (out)

Operation:
o Apply heat to boil amine solution => amine + water are vaporized. => amine solution
becomes much more concentrated (e.g. from 20% to 68% wt MEA) => heat-stable
salts (having higher boiling point than amine solution) may precipitate as solid
crystals.
Waste product = amine sludge (containing salt, nonvolatile organics, amine, corrosion
inhibitor, other additives => WELL INJECTION, INCINERATION, LANDFILL

4. Ion exchange
Remove ionized compounds => heat-stable salts
Use ion exchange resin (packed in a column)
Based on reversible exchange of ions between a liquid (amine solution) and a solid (resin)
Anion resin has preference to bind with positive charge ion/ cation resin binds with ion.
For example:
To remove Cl- from amine solution => use anion resin containing OH(OH-) on resin + amine solution + Cl- (Cl-) on resin + amine solution + H2O
To regenerate resin for reuse => add or wash the resin with excess amount of caustic
soda (OH-)
(Cl-) on resin + OH- (OH-) on resin + Cl*** to remove cations (e.g. Na+) => use cation ion exchange resin***

In practice, for amine purification => remove both cations and anions => use multiple packed
beds connected in series
First column: => use a cation resin bed to remove Na+
Second, third.. => use anionic resin beds to remove Cl- and other heat-stable salts
(acetate, formate, etc.)
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A. Veawab

Waste product = aqueous stream containing removed heat-stable salts => WELL
INJECTION, LANDFILL
Amine Solution (Cl-)

Anion Resin

OH-

OHCl-

Amine Solution (OH-)

5. Electrodialysis
Remove ionized compounds => heat-stable salts
Use current and ion-selective membrane to move ions from one solution chamber to another
Operation => work the same way as described in Page 56 (treatment of produced water)
Waste product = brine containing removed heat-stable salts => WELL INJECTION/
LANDFILL
Concentrated Salt

Clean Amine Solution

Cathode ( - )

Anode ( + )
M+

XM+

XM+

M+
X-

M+

Cation Exchange membrane

Anion Exchange membrane

Cation Exchange membrane

M+

3
63

Amine Solution (Heat Stable Salts)

M+
XM+
X-

Anion Exchange membrane

X-

ENPE 490

A. Veawab

4.3 Gas dehydration

Objective: To remove water from gas stream
Why water must be removed from gas stream?
For pipeline:
To reduce pipeline corrosion
To prevent line blockage caused by hydrate formation
For gas and liquid products:
To meet gas and liquid product specification
o Max. water in sales gas = 4-7 lb/MMscf (60-110 mg/Sm3)
o Max. water in liquid product = 10-20 ppmw
For hydrocarbon recovery:
(Gas stream that leaves acid gas treating (using absorption into amine solution) is water
saturated.)
To prevent hydrate formation in the cryogenic section of hydrocarbon recovery
o Max. water should be 0.1 ppmv.
What are common technologies for gas dehydration?
Gas absorption into liquid (solvent)
Gas adsorption onto adsorbent (solid)

Gas absorption into liquid

Solvents used for the absorption of water vapor in natural gas should have:

High affinity for water and a low affinity for hydrocarbons => prevent the undesirable
removal of gas products
Low volatility at absorption temperature => minimize vaporization loss of solvent
Good thermal stability => prevent decomposition of solvent during regeneration (at
elevated temperature)

Examples of common solvents used for gas dehydration

Glycol
Ethylene glycol (EG)
Diethylene glycol (DEG)
Triethylene glycol (TEG) => most commonly used***
Tetraethylene glycol (TREG)
Propylene glycol

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ENPE 490

A. Veawab

Process flow diagram of typical glycol dehydrator unit

Flash gas
Dry gas

Water vapor

Lean
glycol

Flash
tank

Glycol
dehydrator

Rich
glycol

Filter

Wet gas
Liquid

modified from A. J. Kidnay and W.R. Parrish, Fundamentals of Natural Gas Processing, CRC Press Taylor &
Francis Group ( 2006).

Operation:
Wet gas (natural gas + water vapor) passes through an inlet scrubber to remove solids and
liquid.
Then, the wet gas enters a glycol dehydrator and flows upward against the stream of lean
glycol (containing little or no water) flowing downward. After absorbing water vapor, the
lean glycol becomes rich glycol (containing water) and leaves the dehydrator from the
bottom. The dry gas leaves the dehydrator from the top.
The rich glycol passes through the top section of the regenerator where the rich glycol is
preheated and at the same time, helps reduce the temperature of the stripped water vapor.
The preheated rich glycol enters a flash tank to flash off the dissolved gas and passes through
a heat-exchanger to be further heated before entering the regenerator.
In regenerator, the rich glycol is heated so that the water vapor is liberated, flows upward and
leaves the regenerator top. The rich glycol becomes hot-lean glycol.
The hot-lean glycol is cooled by a heat exchanger before entering the dehydrator.

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A. Veawab

Waste or discharge
Solvent (e.g. ethylene glycol => toxic to humans => one of regulated toxic pollutants)
BTEX in spent solvent and in vapor stream from glycol regenerator
(BTEX are regulated as hazardous (or toxic) air pollutants under Clean Air Act => source emits
more that 10 tons per year of any one pollutant or 25 tons per year total)
Methods to minimize BTEX emissions from glycol regenerator
1) Adjust plant operating conditions to minimize the concentration of BTEX in glycol
absorber off gas (e.g. reduce solvent circulation rate)
2) Maximize the amount of BTEX flashed in the flash tank => use low-pressure, hightemperature flash conditions)
3) Burn the BTEX- containing gas stream leaving regenerator before venting => flare or
incineration
4) Use adsorption of BTEX on a carbon adsorber
5) Condense BTEX from regenerator vapor stream and recover BTEX as a liquid product
=> efficient cooling and condensation
Example of condensation technology for BTEX recovery => R-BTEX process (>95% recovery
of BTEX as a salable liquid)
Process flow diagram of R-BTEX
Cooling tower
vent gas
Rich TEG

Fan

Cooling water
BTEX
stripper
Regenerator
offgas

Reflux
water

Condenser
vent gas

3-Phase
accumulator

Organic
product

Cooling
tower
Stripping
air
Cooling water
blowdown

BTEX stripper
bottom pump

Circulating water
pump

Redrawn from A. Kohl and R. Nielsen Gas Purification 5 th edition, Gulf Professional Publishing, Texas (1997).
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ENPE 490

A. Veawab

Operation:
Reduce temperature to condense BTEX

Hot regenerator offgas (water vapor + BTEX) is introduced to the BTEX stripper at the
bottom and flows upward against a flow of reflux water (relatively colder than the
regenerator offgas). => the hot regenerator offgas becomes cooler.
The regenerator offgas is further cooled by rich TEG and cooling water, then sent to a phase
accumulator to separate gas, organics (BTEX) and water.
Water is recycled back to the BTEX stripper as the reflux water.
Warm reflux water is sent to the cooling tower to reduce its temperature.

Estimate the amount of BTEX absorbed into a glycol solution

Treat BTEX as benzene => higher aromatics than benzene are present in much smaller
amounts
Use the Kremser-Brown equation:
1 = +1 +1

Where:

+1
+1 1

y1 = mole fraction of benzene in outlet gas

yn+1 = mole fraction of benzene in inlet gas
A = absorption factor = L/VK
L = lean glycol solution flow rate
V = gas flow rate
K = equilibrium constant
N = number of theoretical tray

EXAMPLE:
Pressure = 1,000 psia
Temperature = 80oF
Feed gas benzene content (yn+1) = 0.1 mol%
Gas flow rate (V) = 10 MMscfd = 26,350 lb mol/day
Glycol concentration = 98 wt% TEG
Glycol molecular weight = 130.9
Glycol flow rate (L) = 71 lbmol/day (based on 3 gal TEG per lb water removed)
Equilibrium constant (K) = 0.012
Number of theoretical tray (N) =3
Find y1 =?

67