1

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?
• 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?

Gas Process Engineering - CGE667

 Introduction
• H2S concentrations
3
must be reduced to 0.25 – 0.3
gr/scf (6 -7 mg/m ).
• CO2 concentration must be reduced to a maximum
of 3 – 4 %.
• 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.
Gas Process Engineering - CGE667
 Introduction
• What happen to CO2 and H2S after their
separation from the natural gas?
 the answer depends on their quantity.
• 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.

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 Introduction
• In the case of H2S, four disposal options are available:
 Incineration and venting, if environmental regulations
regarding SO2 emissions can be satisfied.
 H2S scavenger
 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.
Gas Process Engineering - CGE667
 Acid Gas Removal Processes

• Four scenarios are possible for acid gas removal

from natural gas:
 CO2 removal from a gas that contains no H2S.
 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.
Gas Process Engineering - CGE667
 Acid Gas Removal Processes
Acid Gas Removal Processes

Solvent Absorption Adsorption Membranes

Batch Process

Chemical Physical

Hybrid
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 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
• 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.
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 Solvent Absorption Processes
Chemical Physical
1. Relatively 1. Low energy
insensitive to H2S & requirements for
CO2 partial pressure. regeneration
Advantages
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
selective between
Disadvantages CO2 & H2S.
acid gas partial
pressure.
3. Amines are in
water solution. The
Gas Process Engineering - CGE667
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 amine:

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

• Replacement of a three hydrogen atoms produces

a tertiary amine:

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 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 by neighbouring groups so that larger
molecules cannot easily approach and react with
nitrogen.

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 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.
• 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.
Gas Process Engineering - CGE667
 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 (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-
Gas Process Engineering - CGE667
 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
carbonic acid.

CO2 + H2O ↔ H2CO3 (carbonic

acid)
• The carbonic acid slowly dissociates to bicarbonate

H2CO3 ↔ H+ + HCO3-
(bicarbonate)
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 Basic Amine Chemistry
• The bicarbonate then undertakes an acid-base
reaction with amine:
H+ + R1R2R3N ↔ R1R2R3NH+
• 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 &
Gas Process Engineering - CGE667

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.
• 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-
Gas Process Engineering - CGE667
 Basic Amine Chemistry

• The carbamate intermediate then reacts with a

second amine molecule to form the amine salt.

R1R2N+HCOO- + R1R2NH ↔ R1R2NCOO- +

R1R2NH2+
• 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.
Gas Process Engineering - CGE667
 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.
• 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
Gas Process Engineering - CGE667

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.
• 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
Gas Process Engineering - CGE667

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

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 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.
• 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
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contactor.
 Amine Process Description

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

• In the flash tank, the pressure is reduced to 75 -

100 psig to remove (flash) any dissolved
hydrocarbons.
Gas Process Engineering - CGE667

• The dissolved hydrocarbon s are generally used

 Amine Process Description

• The rich amine then

passes through a heat
exchanger and enters
the solvent regenerator
(stripper) at
temperatures in the
range of 180 - 200°F.

Gas Process Engineering - CGE667

 Amine Process Description

• The steam generated at the

bottom flows upward
through either trays or
packing, where 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
Gas Process Engineering - CGE667

recovery.
 Amine Process Description
• A stream of lean amine
is removed from the
stripper, cooled to about
110°F, and re-enters the
contactor at the top.

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 Operating issues of Amine Process
• Corrosion – some of the major factors that affect
corrosion are:
 Amine concentration (higher concentration favour
corrosion)
 Oxygen concentration
 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.
Gas Process Engineering - CGE667
 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.
• 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.
Gas Process Engineering - CGE667
 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 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.
Gas Process Engineering - CGE667
• 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.
• 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
Gas Process Engineering - CGE667
carbon steel can be used.
Gas Process Engineering - CGE667
 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.
• 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.
Gas Process Engineering - CGE667
 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 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.
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 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:
Permeation Permeability Membrane
= X X Partial Pressure
rate Coefficient 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.
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 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
 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.
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 Membrane
• Disadvantages:
• Clean feed: Pre-treatment of the feed to the
membrane to remove particulates and liquids is
generally required.
• 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.
Gas Process Engineering - CGE667
 Batch Processes

• When the quantity of sulfur to be removed is small,

the processes discussed previously are
uneconomical and small-scale batch processes
are used.
• These processes generally use a non-regenerable
scavenger:
• Solid-based (e.g. iron oxides and zinc oxides)
• Liquid-based (e.g. nitrites, caustic scrubbing, aldehydes)
• The most widely used scavengers are those that
utilise iron oxides, especially iron sponge.
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 Batch Processes

• Advantages of batch processes:

 Relatively low capital cost when compared to generative
processes.
 The affinity for sulfur-containing gases is largely
independent of the operating pressure.
• Disadvantages of batch processes:
 Uninterrupted operation requires two or more contact
towers, so that at least one tower is on stream when
another is being re-charged).

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 Iron Sponge
• Iron Sponge consists of wood chips impregnated
with hydrated ferric oxide (Fe2O3) and sodium
carbonate to control the pH.
• The chips are dumped into the vertical contact
tower through the manway at the top.
• They rest on the perforated support plate.
• Process gas enters at the top of the vessel and is
distributed by an inlet gas diverter.
• It passes through and reacts with the sponge and
leaves as a sweet gas at the bottom of the vessel.
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Iron Sponge

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 Iron Sponge
• The sweetening reactions form ferric sulfide, Fe2S3.
Fe2O3 + H2S = Fe2S3 + H2O

• The sponge is regenerated by taking it offline and

passing air through it.
• The oxygen in the air reacts with the sulfide and form
elemental sulfur and returns the iron to the oxide.

Fe2S3 + 3O = Fe2O3 + 3S
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 Batch Versus Amine Process

• The batch and amine processes are used widely in

the gas industry.
• Amines are preferred when the lower operating cost
(the chemical cost for batch processes is prohibitive)
justifies the higher equipment cost.
• The key is sulfur content of the feed gas.
• Below 20 lb/day, batch processes are more
economical, and
• Over 100 lb/day amine processes are preferred.
Gas Process Engineering - CGE667
 Sulfur Content
Can be
Gas translated
Flowrate in directly from ppm
scf/day or percent

lb S  scf  lb mol gas  mol H2S  lb S 

     
day  day  scf  mol gas  mol H2S 

1 lb-mol of gas contains MW of S = 32

379.49 ft of gas

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 Example 1
Which sweetening process (batch or amine) is suitable
for the following gas stream?
Q= 1000 Mscfd; H2S concentration = 200 ppm.

lb S  10 6  1  200  32 
  
  6  
day  1  379.49  10  1 

 17.0

Less than 20 lb S/day. So, batch process is suitable

Gas Process Engineering - CGE667
 Batch process
• Important Design Parameters
 Bed Diameter and Height
 Daily Chemical Requirement
 Bed-Life
• For validation
 Check contact time by determining the space velocity
or actual cubic feet per hour (acfh) of the bed. This
should be less than 180 acfh/ft3 for low H2S contents
and 90 acfh/ft3 for over 50 gr/100 scf gas. (To convert
ppmv H2S to grain H2S/100 scf, devide by 15.9)
 Check the heat effect. The sulfur deposition should be
less than 15 gr/min ft2 of bed area.
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 Batch process
To calculate bed diameter

1. Calculate actual gas flow rate, Qa

19.63  Q  (T  460 )  Z
Qa 
(P  Patm )

Q in MMscf; T in °F; Z= compressibility factor

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 TABLE A1: Standard Atmosphere
Altitutde Temperature Pressure Density(lb/ft
(ft) (°F) (psia) 3)

0 59.0 14.696 0.0765

1000 55.4 14.173 0.0743
2000 51.9 13.664 0.0721
3000 48.3 13.172 0.0700
4000 44.8 12.693 0.0679
5000 41.2 12.228 0.0659
6000 37.6 11.777 0.0639
7000 34.1 11.341 0.0620
8000 30.5 10.916 0.0601
9000 27.0 10.506 0.0583
10000 23.4
Gas Process Engineering - CGE667
10.108 0.0565
 Batch process
To calculate bed diameter

2. Calculate bed cross-sectional area (Qa

/superficial velocity)

3. From the bed cross-sectional area, you can

get bed diameter.

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 Batch process
To Calculate Daily Chemical Requirement

Iron Sponge: IS = 0.0133 (Q) (ppmv H2S) ft3/day

Chemsweet: CS= 0.248 (Q) (ppmv H2S) lb/day
Sulfa-Check: SC = 0.0474 (Q) (ppmv H2S) gal/day

Gas Process Engineering - CGE667

 Batch process
To calculate bed-life

1. Calculate the volume of reactant, RV (in ft3)

2
RV  0.7854 (ID ) (L)

2. Calculate the bed-life

Iron Sponge: BL = RV/IS days
Chemsweet: BL = RV/CS days
Sulfa-Check: BL = RV/SC days
Gas Process Engineering - CGE667
 Batch process
To check contact time

acfh
Space velocity 
RV
*** acfh = actual cubic feet per hour

To check heat effect

S Deposition  (scf/min) (gr H2S/scf)/(bed area)

Gas Process Engineering - CGE667
 Example 2
For the following gas stream,
100 Mscfd; H2S concentration = 100 ppm. P = 200
psig, T = 80°F, elevation = 1000ft, Z = 0.955.

a) Select bed diameter for iron sponge process

(assume superficial velocity = 2.5 ft/min)
b) Check contact time and heat effect (assume bed
height = 5 ft)
c) Determine the bed-life
Gas Process Engineering - CGE667
 Answer to Example 2
a)
Patm = 14.173 at 1000 ft elevation

19 .63 Q T  460 Z 

Qa 
P  Patm

19 .63 0.180  460 0.955 

Qa   4.72 acfm
200  14 .173
4.72
Bed cross - sectional area   1.89 ft 2
2 .5

Bed diameter  1.5 ft

Gas Process Engineering - CGE667
 Answer to Example 2
b)
Checking contact time:

RV  0.7854 (ID )2 (L)  (0.7854 )(1.5)2 (5)  8.84 ft 3

acfh 4.72  60
Space velocity    32 acfh/ft 3
RV 8.84

OK because < 180

Gas Process Engineering - CGE667

 Answer to Example 2
b)
Checking heat effect:

100 ppmv  100/15.9  6.3 gr H2S/100 scf

(scf/min)( gr H2S/scf)
S deposition 
bed area

(100,000/2 4  60)(6.3/10 0)
  2.3 gr H2S/min ft 2 bed
1.89

OK because less than 15 gr H2S/min ft2

Gas Process Engineering - CGE667

bed
 Answer to Example 2
c)
Daily Chemical Requirement

IS  0.0133(Q)( ppmv H2S )

3
 0.0133(0.1 )(100 )  0.1333 ft / day
Bed Life
BL  RV/IS
 8.84/0.133  66 days
Gas Process Engineering - CGE667