SWEETNING

OF
NATURAL GAS

SOUR & SWEET NATURAL GAS

Sour Natural Gas
Natural gases containing H2S are known as sour natural
gases.
Gases from the reservoir contain H2S ranging from barely
detectable amount to more than 0.3% (3000ppm).
Most contracts for sale of natural gas require less than
4ppm of H2S.
Sweet Natural Gas
Natural gases that are free from H2S is known as sweet
natural gases.

ACID GASES
Natural gases containing CO2, H2S and COS are termed
as acid gases as they form acidic solution in presence of
water.
CO2 concentration in the natural gas is generally in the
range of 1 to 4%.

REASONS FOR REMOVAL OF H2S

Emitting a foul odor at low concentrations.

Promote hydrate formation.

Deadly poisonous (at conc. > 600ppm, it can be fatal in

3-5 min.).
Corrosive to all metals normally associated with
transportation, processing and handling systems and may
lead to premature failure.
On combustion, it forms SO2 which is highly toxic and
corrosive.
H2S and other S - compounds can cause catalyst
poisoning in the refinery processes.

REASONS FOR REMOVAL OF CO2

CO2 has no heating value and its removal may be required
for increasing the energy content of the gas per unit
volume.
CO2 is corrosive in presence of water.
For a gas to be sent to the cryogenic plants, the removal
of CO2 may be necessary to prevent solidification of the
CO2.
CO2 promote hydrate formation.

CTRITERIA FOR PROCESS SELECTION

The type and concentrations of the impurities in the gas
and the degree of removal desired.
Selectivity of the acid gas removal, if any.
CO2 to H2S ratio in the gas.
Temperature and pressure at which the sour gas is
available and at which the sweet gas is to be delivered.
Volume of the gas to be processed and its hydrocarbon
composition.
Economics of the process.
The desirability of the S - removal due to environmental
problems or economics.

CLASSIFICATION OF
SWEETENING PROCESSES
Sweetening processes are classified as:
Non-regenerative

Regenerative Processes with recovery of H 2S

Regenerative

Processes

as elemental Sulfur

with

recovery

SWEETENING PROCESSES
Solid bed Sweetening
Processes
The Iron Sponge Process
Molecular Sieves

Absorption
Processes

Physical Absorption
Processes
Water Wash (Aquasorption) Process
Selexol Process
Sulfinol Process

Direct Conversion
Processes
Stretford process

Chemical Absorption
Processes
Alkanol-Amine Processes
Hot Potassium Carbonate
processes

SOLID BED SWEETENING PROCESSES

These are based upon the physical or chemical adsorption
of the acid gases on a solid surface.
The advantages of these processes are:
Simplicity
High selectivity (H2S)
Process efficiency independent of pressure
These processes are best applied to gases with
moderate concentrations of H2S and where CO2 is to
be retained in the gas.

THE IRON SPONGE PROCESS

Sour gas passes through a bed through a bed of wood chips
that have been impregnated with hydrated form of ferric
oxide that has a high affinity for H2S.
The chemical reaction is as follows:
Fe2O3 + 3 H2S

Fe2S3 + 3 H2O

The temperature must be less than 120 oF

Iron oxide is regenerated by passing oxygen/air over the bed
according to the reaction:
Fe2S3 + 3 O2

Fe2O3 + 6 S

THE IRON SPONGE PROCESS

The advantages of the Iron Sponge Process are:
Simplicity.
Absolute selectivity (H2S).
Relatively inexpensive.
The disadvantages of the Iron Sponge Process are:
Difficult and expensive regeneration
Excessive pressure losses through the bed.
Inability to remove large amount of Sulfur.
Sulfur disposal problems (not saleable)

MOLECULAR SIEVES
Synthetically manufactured forms of crystalline sodiumcalcium alumino silicates.
Molecular sieves are porous in structure having very
narrow range of pore sizes and have a very large surface
area.
The pores are formed by the removal of water of
crystallization and are uniform throughout the material.
Several grades of molecular sieves are available, with each
grade corresponding to a very narrow range of pore sizes.

MOLECULAR SIEVE DESULFURIZATION PROCESS

C

C
o

C
o

PARAMETERS AFFECTING THE

ADSORPTIVE CAPACITY
The adsorptive capacity of molecular sieves for H2S
decreases with increasing temperature.
The adsorptive capacity of molecular sieves for H2S
increases with increasing H2S/CO2 ratio.
Increasing contact time is favorable to H2S removal up to a
point, beyond which there is no effect.
The effect of pressure was found to be quite small,
however, about 450 psia was identified as optimum
pressure.

MOLECULAR SIEVES
The advantages of the molecular sieves are:
Molecular sieves remove components through a
combination of a sieving and physical adsorption process.
Because of their narrow pore sizes, they discriminate
among the adsorbates on the basis of their molecular sizes.
The sieves possess highly localized polar charges on their
surface that act as adsorption sites for polar materials.
They are highly selective in the removal of water, H2S and
other sulfur compounds from natural gas. Hence, they offer
a means of simultaneous dehydration and desulfurization.

MOLECULAR SIEVES
The Disadvantages of the molecular sieves are:
Molecular sieves are also prone to poisoning by several
chemicals such as glycols, methanol, corrosion inhibitors etc.
Unsaturated hydrocarbon components such as olefins and
aromatics tend to be strongly adsorbed and are not released
during regeneration.
Initial capital investments are high.
Regeneration requires a lot of heat.
For gas streams containing CO2, carbonyl sulfide may form as
shown in the following reversible reaction:
H2S + CO2 = COS + H2O
Molecular sieves tend to catalyze this reaction.

CHEMSWEET
Chemsweet is a batch process used for the removal of H2S
from natural gas.
Chemicals used are a mixture of zinc oxide, zinc acetate,
water, and a dispersant to keep solid particles in
suspension.
Natural gas is bubbled through the solution where H2S
reacts with zinc oxide.
Though several reactions take place in solution, the net
result is that zinc oxide reacts with H2S to form zinc
sulfide and water.

CHEMSWEET
Chemsweet can treat gas streams with small H2S
concentration and has been operated between
pressures of 75 and 1,400 psig.
Mercaptan concentrations in excess of 10% of the
H2S concentration in the gas stream can cause a
problem. Some of the mercaptans will react with
the zinc oxide and be removed from the gas. The
resulting zinc mercaptides [Zn(OH)RH] will form a
sludge and possibly cause foaming problems.

PHYSICAL ABSORPTION PROCESSES

These processes rely upon physical absorption of
acid components as the gas sweetening
mechanism.

PHYSICAL ABSORPTION PROCESSES

The advantages of these processes are:
These processes offer fair to good selectivity.
Corrosion and fouling problems are generally
minimal.
The solvent used is generally recovered by flashing
the acid component-rich solvent in flash tanks at
successively lower pressures. Thus, little or no heat
is required for regeneration.
Some processes offer simultaneous dehydration.

PHYSICAL ABSORPTION PROCESSES

Most solvents have a high solubility for heavier
hydrocarbons, particularly unsaturated and aromatatic
components. These components are very detrimental to
the performance of most sulfur recovery processes and
may yield an unsuitable, contaminated sulfur as the
product. So, for sour gases containing heavy
hydrocarbons (heptanes plus) or unsaturated and aromatic
hydrocarbons, particular care must be taken during the
regeneration step to prevent their entry into the acid gas
stream that is to be sent to a sulfur recovery unit.
A sulfur recovery unit is required, since these processes
do not alter the acid components chemically in any
manner.

WATER WASH PROCESS

SELEXOL PROCESS FOR A LOW H2S TO

CO2 RATIO

SULFINOL PROCESS
The Sulfinol Process is used to remove H2S, CO2, COS,
CS2, mercaptans and polysulfides from natural gas.
Sulfinol is a mixture of Sulfolane (a physical solvent),
water and either DIPA or MDEA (both chemical
solvents).
It is this dual capacity as both a physical and a chemical
solvent that gives Sulfinol its advantages.

SULFINOL PROCESS
Sulfinol with DIPA (Sulfinol-D) is used when complete
removal of H2S, CO2 and COS is desired.
Sulfinol with MDEA (Sulfinol-M) is used for the
selective removal of H2S in the presence of CO2, with
partial removal of COS.
Both Sulfinols can reduce the total sulfur content of
treated gas down to low ppm levels.

SULFINOL PROCESS
The advantages of Sulfinol are:
Low energy requirements.
Low foaming and noncorrosive nature.
High acid gas loadings.
Some removal of trace sulfur compounds.
The disadvantages of Sulfinol are:
Higher heavy hydrocarbon co-absorption.
Reclaimer sometimes required when removing
CO2.

CHEMICAL ABSORPTION
These processes rely upon Chemical
absorption of acid components as the gas
sweetening mechanism.

THE ALKANOL AMINE PROCESSES

The alkanol-amine processes are the most prominent and widely
used processes for H2S and CO2 removal.
They offer good reactivity at low cost and good flexibility in
design and operation.
Some of the commonly used alkanol-amines for absorption
desulfurization are: Mono-ethanol amine (MEA), Di-ethanol
amine (DEA), tri-ethanol amine (TEA), Di-glycol amine (DGA),
Di-iso-propanol amine (DIPA), and Methyl-diethanolamine
(MDEA).
Among these, MEA and DEA processes are the most widely
used.

MONO-ETHANOL AMINE (MEA)

MEA offers the highest removal capacity on a unit
weight or unit volume basis, which implies lower solution
circulation rates in a sweetening plant.

MEA

is

chemically

stable

(minimal

solution

degradation).
The reaction rate of H2S with MEA is greater than that of
CO2. The process is considered to be almost non-selective
in its removal capacity for H2S and CO2.
MEA is able to remove acid gases to pipeline
specifications and even beyond.

MONO-ETHANOL AMINE (MEA)

MEA suffers from relatively high solution losses primarily
due to two reasons:
It has a relatively high vapor pressure that causes greater
vaporization losses.
It reacts irreversibly with carbonyl sulfide and carbon
disulfide.

DI-ETHANOL AMINE (DEA)

DEA is not as reactive as MEA, so H2S removal to
pipeline specifications may cause problems in some cases.
Its reactions with carbonyl sulfide and carbon disulfide
are slower and lead to different products, so filtration
problems are less.
Its vapor pressure is lower, therefore vaporization losses
are less.
Thus, DEA can be advantageous to use in some cases.

TRI-ETHANOL AMINE (TEA)

TEA has lesser reactivity and problems are
encountered in sweetening the gas to pipeline
specifications.

OTHER AMINES
DGA has found application in recent years. It has
the same reactivity as DEA and a reasonably low
vapor pressure.
DIPA is also able to treat gas to pipeline
specifications and is used in the Sulfinol process.
MDEA has received renewed attention because it
has a fairly good selectivity for H2S, so CO2 can
be retained in the gas and it offers some energy
saving in the regeneration step.

SOLUTION CONCENTRATIONS
For MEA, an approximately 15% concentration (by
weight) solution is generally used.
DEA is used in 20-30 % or more concentration.
DIPA and MDEA are typically used in 30-50%
concentration in aqueous solution.
DGA is

used

in

concentration range.

the

40-70%

by

weight

SOLUTION CONCENTRATIONS
Some plants use a mixture of a glycol and an
amine for simultaneous dehydration and
desulfurization.
Generally, a solution containing 10 to 30% by
weight MEA, 45 to 85% by weight TEG
(triethylene glycol), and 5 to 25% by weight
of water is used. This process removes both
CO2 and H2S besides dehydrating the gas.

REACTIONS FOR THE ETHANOLAMINES

Formation of a bisulfide of the ethanolamine on reaction
with H2S.
RNH2 + H2S

RNH4S + heat

In aqueous solution, with CO2, the carbonate salt of the

ethanolamine is formed. This is a slower reaction.
RNH2 + H2O + CO2

RNH3HCO3 + heat

THE REACTIONS WITH MEA, DEA AND

TEA
For MEA and DEA, with CO2, the carbamate salt of the
ethanolamine is formed.
2RNH2 + CO2

RNHCO-2 + RNH+3 + heat

TEA does not have this reaction with CO2.

SPLIT-STREAM AMINE PROCESS

A comparison of a MEA and DGA system

for treating 100 MMscfd of natural gas.

GENERAL OPERARTING PROBLEM

Corrosion
Solution degradation
Foaming

CORROSION
The presence of acid gas constituents causes
corrosion.
Impossible to eliminate but can be minimized or at
least limited, by proper design and operation.
Corrosion will be more severe at places where the
highest concentrations of acid gases encounter the
highest temperatures like amine-amine heat
exchanger, stripping column and reboiler.

SOLUTION DEGRADATION
Amine solution will slowly oxidize when exposed to air
or oxygen, product are generally considered to cause
corrosion problems.
Oxidation can be minimized by use of an inert blanket on
amine storage containers and surge drums.
MEA reacts with carbonyl sulfide or carbon disulfide to
form an insoluble salt, results in loss of MEA unless the
solution is reclaimed. This reaction can be reversed by
placing the MEA in a basic solution and heating.

 Degradation product can remove H2S and/or CO2 but

they are not as effective as original ethanol amine and
for this reason a loss in solution activity.

FOAMING
Foaming in an amine sweetening process can
result in a number of different problems.
Plant gas through put may be severely reduced.
Sweetening efficiency may be decreased to the
point that pipeline specifications cannot be met.
Amine losses may be significantly increased.

 Materials that can cause foam problems:

Suspended solids.
Condensed hydrocarbons.
Amine degradation products.
Foreign material such as corrosion inhibitors, valve
grease or even impurities in makeup water.
The use of an amine reclaimer in combination with
proper solution filtration will help to solve many
foaming problems.

THE HOT CARBONATE PROCESSES

The basic hot carbonate process uses an aqueous solution of
potassium carbonate. A highly concentrated solution is used to
improve process performance.
Temperature is kept high to keep the potassium carbonate and the
reaction products, KHCO3 and KHS, in solution.
Both the absorber and regenerator are operated at high temperatures
of about 230-240F, which results in considerable savings in heat
exchange and heating equipment.
The process requires relatively high partial pressures of CO 2 and
cannot be used for gas streams that contain only H2S.
It is also difficult to treat gas to pipeline specifications with this
process.

REACTIONS

The reactions takes place in the carbonate process are:

K2CO3 + CO2 + H2O
K2CO3 + H2S

2KHCO3

KHS + KHCO 3

Reactions (1) & (2) proceed in two steps:

The first step is hydrolysis of the potassium carbonate:
K2CO3 + H2O

KOH + KHCO 3 3

Potassium hydroxide formed reacts with CO 2 to form potassium

bicarbonate:
KOH + CO2

KHCO3

Potassium hydroxide formed reacts with H 2S to form potassium

bisulfide
KOH + H2S

KHS + H2O 5

REACTIONS
Carbonate process has the advantage that both carbon
disulfide and carbonyl sulfide can be removed
without significant solution degradation.
Carbonyl sulfide will hydrolize as follows:
COS + H2O
CO2 + H2S
6
Product reacts with potassium carbonate according to
reaction 1 & 2

REACTIONS
Carbon disulfide hydrolyzes to form COS and H2S
CS2 + H2O

COS + H2S

H2S reacts as per reaction 2.

COS hydrolyzes as per reaction 6.
Mercaptans reacts with potassium carbonate solution to
form mercaptides
K2CO3 + RSH
RSK + KHCO3

Normally operates
at about 230 F

2-10 psig

Gas Gas
Exchanger
Scrubber

Bottom temp.
230-240 F

PROCESS CONCERNS
Corrosion.
Erosion.

CORROSION
Severe corrosion of carbon steel in several areas.
This corrosion occurred where the conversion to bicarbonate
was high and where CO2 and steam were released by
pressure reduction.
Remedy Corrosion inhibitors includes arsenic and
vanadium salts as well as dichromates.
Stainless steel is recommended for reboiler tubes.
Control valves and solution pumps should also be of stainless
steel, particularly those parts which encounter the carbonate
solution such as impellers and inner valves.

CORROSION
The absorber and stripper can be made of carbon steel.
When CO2 is the only acid gas constituents, potassium
dichromate will serve as an effective corrosion inhibitors
(but from 1000 to 3000 ppm).
If sufficient quantity of H2S is present, formation of the
potassium bisulfide inhibits corrosion to a significant
extent.
In cases where corrosion is a problem with H2S present,
the commercially available film-forming fatty amines are
usually effective as corrosion inhibitors.

EROSION
Occasional pieces of scale and other solid material causes
severe erosion.
Efficient filtration schemes is required, minimizes erosion
problem.
Flashing and cavitation are frequently encountered when
high pressure multi-stage pumps are used for pumping
solution from the low pressure of the stripper to the high
pressure of the absorber.
Single stage, slow speed booster pump of low NPSH
design to serve as a feed pump for high pressure pumps.

HOT CARBONATE PROCESSES

WITH ACTIVATORS
Among carbonate processes, those containing an activator
to increase the activity of the hot potassium carbonate
solution are more popular. Some of these are:
1. Benfield-several activators, usually DEA.
2. Catacarb-amine borates used as activators.
3.Giammarco-Vetrocoke- for CO2 removal, arsenic
trioxide most commonly used; selenous acid and tellurous
acid are also used. For H2S removal, alkaline arsenites and
arsenates (usually KH2AsO3 and KH2AsO4) used.

THE HOLMES-STRETFORD PROCESS

This process converts H2S to elemental sulfur of almost
99.9% purity.
The process is selective for H2S, and can reduce the H2S
content to as low as 1 ppm.
CO2 content remains almost unaltered by this process.
Operating costs are lower and the process has better
flexibility in application, that is, it can be designed for
larger pressure and temperature ranges.

THE HOLMES-STRETFORD PROCESS

The process uses an aqueous solution containing sodium
carbonate and bicarbonate in the ratio of approximately
1:3, resulting in a pH of about 8.5 to 9.5 and the sodium
salts of 2,6 and 2,7 isomers of anthraquinone disulfonic
acid (ADA).

THE HOLMES-STRETFORD PROCESS

The postulated reaction mechanism involves five steps:

Absorption of H2S in alkali

Reduction of ADA by addition of hydrosulfide to a carbonyl

group

Liberation of elemental sulfur from reduced ADA by interaction

with oxygen dissolved in the solution

Reoxidation of the reduced ADA by air

Reoxygenation of the alkaline solution, providing dissolved

oxygen for step (3).

STRETFORD SOLUTION

The Stretford solution consists of following chemicals in a dilute

water solution:
1. Sodium salt of 2,7 ADA. The 2,7 isomer is preferred over 2,6
because of the greater solubility of the former.
2. Sodium meta vanadate. This provides the active vanadium.
3. Sodium potassium tartrate. This is used to prevent the formation
of a complex vanadium-oxygen precipitate that removes
vanadium from solution.
4. A sequestering agent to prevent precipitation of metallic ions
from Stretford solution, such as Chel 242 PN.
5. Sodium carbonate. Used as required to maintain total alkalinity.
6. Sodium bicarbonate added to reduce the absorption of CO2.

CHEMICAL REACTIONS
The overall reaction of the Holmes-Stretford process is the
atmospheric oxidation of H2S to elemental sulfur:
2H2S + O2

2H2O + 2S

The reaction occurs in the following steps:

Na2CO3 + H2S
4NaVO3 + 2NaHS + H2O

NaHS + NaHCO3
Na2V4O9 + 4NaOH + 2S

Na2V4O9 + 2NaOH + H2O + 2ADA

4NaVO3 + 2ADA
(reduced)

2ADA (reduced) + O2

2ADA + H2O

HOLMES-STRETFORD PROCESS

LO-CAT PROCESS

Air Compressor
Inlet gas
scrubber
Acid
Gas

Solution return pump

LO-CAT PROCESS
This process is used for the removal of small amount of
acid gas from a large amounts of the gas and producing
elemental sulphur.
The reactions involved are:
During absorption of H2S
Fe3+ + S2-

Fe2+ + S

During regeneration of catalyst

Fe2+ + O2 + H2O

2OH- + Fe3+

CLAUS PROCESS
In the Claus process H2S was reacted over a catalyst with
air (oxygen) to form elemental sulfur and water.
H2S + 1/2 O2

S + H2 O

The overall reaction was separated into two steps:

A highly exothermic combustion reaction in which H 2S
reacts with air to form SO2

H2S + (3/2) O2

SO2 + H2O, H (77F) = -223100 Btu

A moderately exothermic catalytic reaction in which sulfur

dioxide (SO2) formed in the combustion section reacts with
unburned H2S to form elemental sulfur.

2 H2S + SO2 (3/x) Sx + 2 H2O, H (77F) = - 41300 Btu

CLAUS PROCESS
The side reactions involving hydrocarbons, H 2S,
and CO2 present in the acid gas feed can result in
the formation of carbonyl sulfide (COS), carbon
disulfide (CS2), carbon monoxide (CO) and
hydrogen (H2).

CLAUS PROCESS CONFIGURATIONS

STRAIGHT-THROUGH CONFIGURATION

SIGNIFICANT PART OF THE ELEMENTAL SULPHUR

IS FORMED IN THE RECTION FURNACE

SPLIT-FLOW CONFIGURATION

ELEMENTAL SULPHUR IS NOT PRODUCED IN THE FURNACE.

SULPHUR-RECYCLE CONFIGURATION

The difference among the configuration are in the method used

to produce the SO2 prior to the first conventor.

CLAUS PROCESS
Divided into six primary operation:
1. Combustion.
2. Gas Cooling.
3. Reaction of H2S and SO2.
4. Condensation of elemental Sulphur.
5. Reheating of Reactor feeds.
6. Incineration of the tail gas.

PROCESS DESCRIPTION
Burning the H2S to SO2 in the reaction furnace.
Cooling the reacting gases to condense out the sulphur
formed.
Reheating the reactants SO2 and H2S to approximately
450F and passing them through a catalyst chamber.
Then again cooling the gases to less than 320F to
condense the sulphur.
Again repeating the reheating, catalytic reaction and
cooling sequence.

REHEATING METHODS
The methods commonly used are:
a) Reheating by means of auxiliary burners.
Best Recovery.
Most Expensive.

b) Reheating indirectly by means of outside gases and/or

reaction gases.
Good Recovery.

c) Reheating by means of hot gas by-passes. Good

Recovery.
Cheapest.

DIRECT HEAT METHODS

ACID GAS FIRED INLINE BURNER

DIRECT HEAT METHODS

FUEL-GAS FIRED INLINE BURNER

DIRECT HEAT METHODS

HOT GAS BYPASS (FIRST PASS)

INDIRECT HEAT METHODS

STEAM REHEATER

INDIRECT HEAT METHODS

FUEL-GAS FIRED INDIRECT HEATER

INDIRECT HEAT METHODS

GAS-GAS HEAT EXCHANGER

THREE-STAGE SULFUR PLANT