Faculty of Chemical Engineering

Universiti Teknologi MARA

Acid Gas Treating

Gas Process Engineering - CGE667

 Introduction

• What are the acid gases (in natural gas)?

• Why are the acid gases a problem?
• What are the acid gas concentrations in natural gas?

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• How much purification is needed?
• What is done with the acid gases after separation
from the natural gas?
• What processes are available for acid gas removal?
 Introduction
• H2S concentrations must be reduced to 0.25 – 0.3
gr/scf (6 -7 mg/m3).
• CO2 concentration must be reduced to a maximum of
3 – 4 %.

Gas Process Engineering - CGE667

• If the gas is to be processed for NGL recovery or
nitrogen rejection, CO2 may have to be removed to
prevent the formation of solids.
• If the gas being fed to an LNG liquefaction facility, then
the maximum CO2 level is about 50 ppmv because of
potential solids formation.
 Introduction

• What happen to CO2 and H2S after their separation

from the natural gas?
 the answer depends on their quantity.

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• For CO2, if the quantities are large, it is sometimes
used as an injection fluid for EOR projects.
• If this option is unavailable, then the gas can be
vented, provided it satisfies the environmental
regulations.
 Introduction
• In the case of H2S, four disposal options are available:
 Incineration and venting, if environmental regulations
regarding SO2 emissions can be satisfied.
Reaction with H2S scavenger

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 Conversion to elemental sulfur.
Disposal by injection into a suitable underground
formation
• The first two options are applicable to trace levels of
H2S.
• The last two options are required if concentrations are too
high to make the first two options feasible.
 Acid Gas Removal Processes

• Four scenarios are possible for acid gas removal from

natural gas:
 CO2 removal from a gas that contains no H2S.

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 H2S removal from a gas that contains no CO2.
 Simultaneous removal of both CO2 and H2S.
 Selective removal of H2S from a gas that contains both
CO2 and H2S.
• CO2 and H2S concentrations vary substantially, no single
processes is superior in all circumstances.
 Acid Gas Removal Processes

Acid Gas Removal Processes

Gas Process Engineering - CGE667

Solvent Absorption Adsorption Membranes

Batch Process

Chemical Physical

Hybrid
 Acid Gas Removal Processes
• Considerations for process selection:
• Types & concentrations of impurities
• The degree of impurities removal required
• The selectivity of acid gas removal required

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• The temperature, pressure, volume and composition of the
gas to be processed
• CO2 to H2S ratio
• Economics and environmental issues
• CO2 removal is normally performed offshore.
• H2S removal is rarely carried out offshore unless
absolutely necessary because of the problem of
handling the rich acid gas stream or elemental sulfur.
Solvent Absorption Processes
Chemical Physical
1. Relatively insensitive 1. Low energy
to H2S & CO2 partial requirements for
pressure. regeneration
Advantages

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2. Can reduce H2S & 2. Can be selective
CO2 to ppm levels. between H2S & CO2.
1. High energy 1. May be difficult to
requirements for meet H2S
generation of solvent. specifications.
2. Generally not 2. Very sensitive to acid
Disadvantages selective between CO2
& H2S.
gas partial pressure.

3. Amines are in water

solution. The treated
gas will be saturated
with water
 Chemical Solvent Absorption
• Amines – compounds formed from ammonia (NH3) by
replacing one or more of the hydrogen atoms with
another hydrocarbon group.
• Replacement of a single hydrogen produces a primary

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amine:
 Chemical Solvent Absorption
• Replacement of a two hydrogen atoms produces a
secondary amine:

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• Replacement of a three hydrogen atoms produces a
tertiary amine:
 Chemical Solvent Absorption
• Primary amines are the most reactive, followed by the
secondary and tertiary amines.
• Sterically hindered amines are compounds in which
the reactive center (the nitrogen) is partially shielded

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by neighbouring groups so that larger molecules
cannot easily approach and react with nitrogen.
 Chemical Solvent Absorption
• Amines removes H2S and CO2 in a two steps process:
 The gas dissolves in the liquid (physical absorption)
 The dissolved gas, which is a weak acid, reacts with the
weakly basic amines.

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• Absorption from the gas phase is governed by the
partial pressure of the H2S and CO2 in the gas.
• Reactions in the liquid phase are controlled by the
reactivity of the dissolved species.
 Basic Amine Chemistry
• Amines are bases – the important aspect is the ability
to form salts with weak acids formed by H2S and CO2.
• When a gas stream is contacted by amine solution, the
acid gases react to form a soluble acid-base complex

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(salt) in the treating solution.
• The reactions are exothermic.
• H2S reacts rapidly with amine (regardless of amine
structure) via a direct proton transfer reaction:

R1R2R3N + H2S ↔ R1R2R3NH+HS-

 Basic Amine Chemistry
• The reaction between amine and CO2 is more complex.
• CO2 reacts via two different mechanisms.
• First: When dissolved in water, CO2 hydrolyses to form

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carbonic acid.

CO2 + H2O ↔ H2CO3 (carbonic acid)

• The carbonic acid slowly dissociates to bicarbonate

H2CO3 ↔ H+ + HCO3- (bicarbonate)

 Basic Amine Chemistry
• The bicarbonate then undertakes an acid-base
reaction with amine:
H+ + R1R2R3N ↔ R1R2R3NH+

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• Overall Reaction is represented as follows:
CO2 + H2O + R1R2R3N ↔ R1R2R3NH+.HCO3-
• The reaction is not as rapid as that of H2S because the
carbonic acid dissociation step to the bicarbonate is
relatively slow.
• The above reactions applies to primary, secondary &
tertiary amines, but example above is for tertiary.
 Basic Amine Chemistry

• A second CO2 reaction mechanism, requires the

presence of labile (reactive) hydrogen in the molecular
structures of the amine.

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• It is called “carbamate formation reaction”
• It occurs only with primary & secondary amines.
• CO2 reacts with an amine molecule to carbamate
intermediate.
CO2 + R1R2NH ↔ R1R2N+HCOO-
 Basic Amine Chemistry

• The carbamate intermediate then reacts with a second

amine molecule to form the amine salt.
R1R2N+HCOO- + R1R2NH ↔ R1R2NCOO- + R1R2NH2+

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• Overall Reaction:
CO2 + 2R1R2NH ↔ R1R2NH2+ + R1R2NCOO-
• The rate of CO2 reaction via carbamate formation is
much faster than the CO2 hydrolysis reaction, but
slower than the H2S acid-base reaction.
 Basic Amine Chemistry

• For primary and secondary amines, little difference

exist between H2S & CO2 reaction rates because of the
availability of the rapid carbamate formation reaction.

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• Therefore, the primary and secondary amines achieve
essentially complete removal of H2S and CO2.
• However, because the tertiary amines have no labile
hydrogen, they cannot form the carbamate.
• Tertiary amines must only react with CO2 via the slow
hydrolysis mechanism.
 Basic Amine Chemistry
• Selectivity for H2S is higher than CO2 when tertiary
amines are used. Therefore, H2S will be removed
completely, and some of the CO2 will slip through with
the gas.

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• In the sterically hindered amine, H2S reaction is not
significantly affected by the amine structure, because
the proton is small and can reach the nitrogen.
• However, CO2 removal can be significantly affected if
the amine structures hinders the fast carbamate
formation reaction and allows only the much slower
bicarbonate formation reaction.
 Basic Amine Chemistry

• For the reactions discussed in the previous slides, high

pressures and low temperatures drive the reactions to
the right.

Gas Process Engineering - CGE667

• High temperatures and low pressures favour the
reverse reaction. This provides a mechanism for
regeneration of the amine solution.
 Amine Process

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 Amine Process Description
• Sour gas enters the bottom of the
contactor at pressures around 1000 psi
(70 bar) and temperatures in the range
of 90°F.

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• The sour gas flows upward,
countercurrent to the lean amine
solution which flows down from the
top.
• Intimate contact between the gas and
amine solution is achieved by use of
either trays or packing in the contactor.
Amine Process Description

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Packing Trays
 Amine Process Description
• The rich amine leaves the bottom of the unit at
temperature around 140°F and enters a flash tank.

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• In the flash tank, the pressure is reduced to 75 - 100
psig to remove (flash) any dissolved hydrocarbons.
• The dissolved hydrocarbon s are generally used as a
plant fuel
Amine Process Description

• The rich amine then

passes through a heat
exchanger and enters the

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solvent regenerator
(stripper) at
temperatures in the
range of 180 - 200°F.
 Amine Process Description

• The steam generated at the

bottom flows upward through
either trays or packing, where

Gas Process Engineering - CGE667

it contacts the rich amine and
strips the acid gases from the
liquid that flows down.
• The vapour , which consists
mostly of acid gases and
water vapour, exit the top of
the stripper and is generally
processed for sulfur recovery.
Amine Process Description
• A stream of lean amine is
removed from the
stripper, cooled to about
110°F, and re-enters the

Gas Process Engineering - CGE667

contactor at the top.
Operating issues of Amine Process
• Corrosion – some of the major factors that affect
corrosion are:
 Amine concentration (higher concentration favour corrosion)
 Oxygen concentration

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 Heat stable salts (higher concentrations promote corrosion)
• Heat Stable Salt (HSS) – Amines react with CO2 and
contaminants, including O2, to form organic acids.
These acids then react with the basic amine to form
HSS. These salts are heat stable and accumulate in the
amine solution.
Operating issues of Amine Process

• Solution Foaming – can results in poor vapour-liquid

contact, poor solution distribution, and solution
holdup with resulting carryover and off-spec gas.

Gas Process Engineering - CGE667

• Among the causes of foaming:
• Suspended solids
• Liquid hydrocarbons
• Surface active agents (such as those contain in inhibitors)
• Amine degradation products including Heat Stable Salts.
• Foaming problem is cured by an addition of antifoam.
 Physical Absorption
• In amine process, acid gases are removed in two steps:
Physical absorption followed by chemical reaction.
• In processes such as Selexol or Rectisol, no chemical

Gas Process Engineering - CGE667

reaction occurs and acid gas removal depends entirely
on physical absorption.
• Should be considered when:
• The partial pressure of the acid gas in the feed gas is greater
than 50 psi.
• The heavy hydrocarbon concentration in the feed gas is low.
• Selective removal of H2S is required.
 Physical Absorption
• Little energy is required for regeneration.
• The solvents are regenerated by:
• Multi-stage flashing to low pressures.

Gas Process Engineering - CGE667

• Regeneration at low temperatures with an inert stripping gas.
• Heating and stripping of solution with steam/solvent vapours.
• Capable of simultaneously dehydrating the gas,
whereas amine processes produce a water saturated
product stream that must be dried.
• The solvents are relatively non-corrosive, so carbon
steel can be used.
 Adsorption
• Absorption versus adsorption?
• Absorption: A separation process involving the transfer of
a substance from a gaseous phase to a liquid phase
through the phase boundary.

Gas Process Engineering - CGE667

• Adsorption: The process by which gaseous components
adhere to solids because of their molecular attraction to
the solid surface.
• Acid gases, as well as water, can be removed by physical
adsorption on a porous materials (e.g. zeolites).
• Applications are limited because water displaces acid gases
on the adsorbent bed.
• Will be discussed further in the gas dehydration chapter.
 Membrane
• Membranes are thin polymer-based barriers that allow
preferential passage of certain substances over others.
• The membranes consist of an ultra-thin polymer film
on top of a thin porous substrate.

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 Membrane
• Gas separation through membranes relies on the
principle that gases dissolve in and diffuse through the
membrane polymers.
• Certain gases will permeate through a membrane at a

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faster rate than others due to the difference in
solubility and diffusion ability of those gases through
the membrane.
• The difference in gas permeability rates through the
membrane provides the basis for the separation.
• In other words, membranes separate gases by the
difference in the rates at which the gases diffuses
across the film.
 Membrane
• Fast gases collect in the permeate stream, and slow
gases remain in the non-permeate stream.
• The permeation flow rate of any gas is given by:

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Permeation Permeability Membrane
rate
= Coefficient
X X Partial Pressure
Area Across Membrane

• When the difference in the permeation coefficient is

large, good separation of the gases can be achieved.
• When the difference is small, separation is difficult and
expensive because multiple stages are needed.
Membrane
• Two types of configurations: Hollow fiber, and Spiral
wound

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Hollow Fiber Spiral Wound
 Membrane
• Advantages:
 Low capital investment when compared with solvent system.
 Ease of operation: process can run unattended.
 Ease of installation: Units are normally skid mounted

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 Simplicity: No moving parts for single-stage units.
 No Chemicals needed
 Good weight and space efficiency
• Attractive for offshore applications because of
unattended operation, no chemicals needed or
generated and good weight and space efficiency.
 Membrane
• Disadvantages:
• Clean feed: Pre-treatment of the feed to the membrane
to remove particulates and liquids is generally required.

Gas Process Engineering - CGE667

• Gas compression: Because pressure difference is the
driving force for separation, considerable compression
may be required for either or both the residue and
permeate streams.
• Generally higher hydrocarbon losses than solvent
systems.