DESULFURIZATION

Criteria of Process Selection

• Types and concentration of impurities in the gas and the degree of
removal required
• Selectivity of acid gas removal
• Temperature and pressure at which sour gas is available and at which
sweet gas is to be delivered
• Volume of the gas to be processed and its hydrocarbon composition
• CO2/H2S ratio in the gas
• Economics of the process
• Desirability of Sulphur recovery due to environmental
constraints/economics
 Adsorption/Solid Bed Sweetening Processes
• Involves physical/chemical adsorption of acid gases on a solid surface
• Not widely used as liquid absorption processes
• Best applied for gases having moderate concentration of H2S (300 ppm)
• Moderate pressure (50-500 psig)
• Suitable where CO2 is to be retained in the gas
Advantages
• Simplicity
• Higher selectivity towards H2S removal
• Inexpensive
• Process efficiency independent of pressure
Adsorption/Solid Bed Sweetening Processes
Disadvantages
• Difficult and expensive regeneration
• Excessive pressure losses through the bed
• Inability to remove large amount of Sulphur
• Sulphur disposal problem, the process doesn’t produce saleable
sulphur
 Metal Oxide/Iron Sponge Process
• Sour gas is passed through a bed of hydrated form of ferric oxide
• Affinity towards H2S
• Adsorption with chemical reaction : Fe2O3 + 3H2S = Fe2S3 + 3H20
• Operating temperature < 120F and alkaline medium
• > 120 F , leads to loss of water of crystallization of the ferric oxide
• Difficulty in regeneration of bed
• Regeneration of the bed is done by passing oxygen/air over the bed
• Regeneration reaction: Fe2S3 + 3O2 = 2Fe2O3 + 6S
 Iron Sponge Process
• Batch Process involves alternative adsorption and regeneration
• Regeneration of the bed difficult
• Once sulfur covers most of the ferric oxide particles, regeneration become impossible
• Incur excessive maintenance and operating cost
• Continuous process involves simultaneous adsorption and
regeneration (Ferrox process)
• Small amount of air/oxygen is introduced slowly along with the sour gas at
the inlet (if oxygen is introduced quickly, bed may ignite)
• S2+2O2 - 2SO2
• Process give improved performance, higher removal efficiency and better
regeneration
Iron Sponge Process
 Molecular Sieves
• Molecular Sieves
Crystalline form of alkali metal alumino-silicates ( similar to natural clay)
Alkali metals – Sodium or Calcium
High surface area, highly porous with narrow pore size
Pores forms by removal of water of crystallization
Uniform through the material
Narrow pore size , due to which sieves discriminate adsorbates (molecular
size)
Adsorption capacity decreases with increasing temperature
Highly selective in removal of H2S, adsorption capacity increases with
increasing H2S/CO2 ratio
Simultaneous dehydration and sweetening
Regeneration temperature is very high
Adsorption Process
• Component removed through a
combination of sieving and physical
adsorption process.
• Regeneration requires lot of heat
• Bed regenerated by passing preheated
(400-600F)
• Cycle time – 1.5/2 Hrs
• During regeneration, Increase in bed
temperature releases the adsorbed H2S
• Heavier hydrocarbons tends to adsorb
strongly
• Initial investment high
• Sieves prone to poisoning by chemicals
glycols
• Gas stream with CO2, sieves acts as catalyst
and leads to formation of COS, needs
alternates to retard the COS formation
H2S + CO2 = COS + H20
• Regeneration loss : 1-2 %
• Gas is also lost by the adsorption of
hydrocarbons
 Absorption Sweetening Process
• Physical Absorption
• Rely on physical absorption, corrosion and fouling problem minimal
• Fair to good selectivity towards acid gases
• Solvent is recovered by flashing the rich solvent at lower pressure
• No heat or little heat is required for regeneration
• Need for Sulphur recovery as solvent doesn’t alter the acid component
• Most solvent have a relatively high solubility for heavier hydrocarbon
(unsaturated and aromatic components). These component causes
problem in the performance of sulfur recovery processes and yields
contaminated Sulphur
• E.g.:
• Aquasorption process or Water Wash Process - Effective for high pressure gases,
high acid gas content and high H2S to CO2 ratio
• Selexol Process - Use dimethyl ether of polyethylene glycol (DMPEG) as a
solvent.
 Absorption Sweetening Process
• Chemical Absorption
• Involves chemical reaction for absorption of acid gases
• Different Processes
• Alkanol-Amine Processes (MEA, DEA, TEA)
• Prominent and most widely used
• Good reactivity at low cost
• Good flexibility in design and operation
• Carbonate Processes
• Hot Carbonate Process - uses aqueous solution of potassium carbonate
• Modification – Increasing activity of hot potassium carbonate
• Benfield (DEA)
• Catacarb (Amine Borate)
• Giammarco Vetrocoke (Arsenic oxides, Arsenates)
• Holmes-Stretford Process – Coverts H2S to elemental Sulphur
Aquasorption Process
• High Pressure Gas
• High Acid Gas Content
• High H2S/CO2 ratio, Good
selectivity
• Process give partially
sweetened gas, for further
processing
• H2S is three times more
soluble than CO2 in water
• High pressure flash drum –
recovery of hydrocarbon
• Low pressure flash drum –
removal of acid gases and
obtaining lean water for re-
use
Selexol Process
• Solvent - dimethyl ether of
polyethylene glycol (DMPEG)
• Solubility of H2S/CO2 directly
proportional to the partial
pressure
• Solubility of H2S is about 10
times greater than CO2
• Solubility of lighter
hydrocarbon is quite small/
Solubility of higher
hydrocarbon is greater
• Surge tank – to remove
entrained gas
• HP Tank – CH4 and some co2
• LP Tank – CO2 (Max)
• LP Tank - H2S and CO2
(Remaining)
 Alkanol-Amine Process
Commonly used alkanol-amines are:
• Monoethanolamine (MEA) Most widely used
• Diethanolamine (DEA)
• Triethanolamine (TEA)
• Diglycolamine (DEA) or ββ‘ hydroxi-ethanolamine
• Di-isopropanolamine (DIPA)
• Methyldiethanolamine (MDEA)
 Characteristics of Ethanolamines

MEA
• Highest reactivity Highest removal capacity
• Lowest molecular weight
• Highest removal capacity on a unit weight basis Lower circulation rates
 Characteristics of Ethanolamines

MEA
• Chemically stable Minimal solution degradation
• Reaction rate of H2S is greater than CO2
• Process is non-selective towards H2S/CO2, even CO2 is rapidly and completely removed
 Characteristics of Ethanolamines

MEA
• High vaporization losses due to high vapor pressure limits operating
temperature
• Reacts irreversibly with carbonyl sulfide and carbon disulfide leads to build up
of solids Requires efficient filtration
 Characteristics of Ethanolamines

DEA
• Less reactive than MEA Causes problem in achieving pipeline specification
• Reaction with carbonyl sulfide and carbon disulfide is slower leads to different
product not build up of solids Less filtration problem
• Low vapor pressure Less vaporization losses
 Characteristics of Ethanolamines

TEA
• Completely replaced by MEA and DEA, due to lesser reactivity and difficulty in
achieving pipeline specification
 Characteristics of Ethanolamines

DGA
• Recently found many applications
• Reactivity as DEA
• Low vapor pressure
 Alkanol-Amine Process
Solution Concentration
• MEA : 15 % by weight
• DEA : 20 - 30 % by weight
• DIPA and MDEA : 30 - 50 % by weight
• DGA : 40 - 70 % by weight

Mixture of glycol and amine used for simultaneous de-hydration and desulfurization

• MEA : 10 – 30 % by weight
• TEG : 45 - 85 % by weight
• H2O : 5 - 25 % by weight
 Alkanol-Amine Process
Chemical Reactions
ABSORPTION
• Ethanolamine reacts with H2S to give bisulfide of ethanolamine
RNH2 + H2S = RNH4S + heat
• MEA and DEA reacts with CO2 to give carbamate salt of ethanolamine
(TEA does not react with CO2)
2 RNH2 + CO2 = RNHCO2- + RNH3+
• Ethanolamine reacts with CO2 in aqueous solution to give carbonate
salt of ethanolamine (Slower reaction)
RNH2 + CO2 + H20 = RNH3HCO3 + heat
 Alkanol-Amine Process
Differences Dehydration vs sweetening
• Absorber contains more trays
• More filtration and heat exchanger is required
• Reflux requirement are greater
• Operating conditions are different
 Alkanol-Amine Process
• Sour gas enters the contactor tower and rises through the descending
amine solution
• Purified gas flows from the top of the tower
• The amine solution, carrying absorbed acid gases, leaves the tower for the
heat exchanger or optional flash tank
• Rich amine is heated by hot regenerated lean amine in the heat exchanger.
• Rich amine is further heated in the regeneration still column, by heat
supplied from the re-boiler. The steam rising through the still liberates water
and CO2 , regenerating the amine.
• Steam and acid gases separated from the rich amine are condensed and
cooled, respectively, in the reflux condenser.
 Alkanol-Amine Process
• Condensed steam is separated in the reflux accumulator and returned to
the still. Acid gases may be vented, incinerated, or directed to a sulfur
recovery system.
• Hot regenerated lean amine is cooled in a solvent aerial cooler and
circulated to the contactor tower, completing the cycle.
• A variety of heat sources can be used for the still re-boiler – direct fired,
waste heat, hot oil, and steam systems.
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 230-240°F, which results in considerable savings in heat
exchange and heating equipment.
The process requires relatively high partial pressures of CO2 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 2KHCO3 1
K2CO3 + H2S KHS + KHCO3 2
Reactions (1) & (2) proceed in two steps:
• The first step is hydrolysis of the potassium carbonate:
K2CO3 + H2O KOH + KHCO3 3
• Potassium hydroxide formed reacts with CO2 to form potassium
bicarbonate:
KOH + CO2 KHCO3 4
• Potassium hydroxide formed reacts with H2S 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
 2-10 psig
Normally operates
at about 230 F

Gas –Gas
Exchanger

Bottom temp.
Scrubber
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 Anthraquinone Disulfonic Acid (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 NaHS + NaHCO3
4NaVO3 + 2NaHS + H2O 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 Solution return pump
Gas
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+ + ½ 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 + H2O
The overall reaction was separated into two steps:
A highly exothermic combustion reaction in which H2S
reacts with air to form SO2
H2S + (3/2) O2 SO2 + H2O, ∆H (77°F) = -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 (77°F) = - 41300 Btu
 CLAUS PROCESS
The side reactions involving hydrocarbons, H2S, 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
450°F and passing them through a catalyst chamber.
• Then again cooling the gases to less than 320°F to
condense the sulphur.
• Again repeating the reheating, catalytic reaction and
cooling sequence.
GENERAL OPERARTING PROBLEM
• Corrosion
• Solution degradation
• Foaming