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UNIT-4

SWEETENING OF NATURAL GAS

SOUR & SWEET NATURAL GAS

• Sour Natural Gas


Natural gases containing H S are known as sour natural gases.
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Gases from the reservoir contain H S ranging from barely detectable amount to more than
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0.3% (3000ppm). Most contracts for sale of natural gas require less than 4ppm of H S.
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• Sweet Natural Gas
Natural gases that are free from H2S are known as sweet natural gases. ACID GASES
Natural gases containing CO , H S and COS are termed as acid gases as they form acidic
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solution in presence of water. CO concentration in the natural gas is generally in the range
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of 1 to 4%.
REASONS FOR REMOVAL OF H S
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• 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 SO which is highly toxic and corrosive.
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• H S and other S - compounds can cause catalyst poisoning in the refinery processes.
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REASONS FOR REMOVAL OF CO
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• CO has no heating value and its removal may be required for increasing the energy
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content of the gas per unit volume.


• CO is corrosive in presence of water.
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• For a gas to be sent to the cryogenic plants, the removal of CO may be necessary to
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prevent solidification of the CO


2.

• CO promote hydrate formation.


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PROCESS SELECTION

Each of the acid gas treating processes has advantages relative to the others for certain applications;
therefore, in selection of the appropriate process, the following facts should be considered:

o The type of acid contaminants present in the gas stream


o The concentrations of each contaminant and degree of removal required
o The volume of gas to be treated and temperature and pressure at which the gas is
available
o The feasibility of recovering sulfur
o The desirability of selectively removing one or more of the contaminants without
removing the others
o The presence and amount of heavy hydrocarbons and aromatics in the gas
o The environmental conditions required at the plant site.

Removal of H2S to Meet Pipeline Qualities (4 ppm)

For feeds with small acid gas loadings, one of the batch processes should be considered for removal of
H2S. The most common are: iron sponge, Sulfa-Treat, and Sulfa-Check.

As acid gas loadings increase, the disposal and replacement costs become high, and it becomes necessary
to choose a process that can be regenerated. The amine systems are most often used for these installation
systems. DEA is the most common amine system.

The end product of an amine system is an acid gas stream off the stripper, which must be flared. As acid
gas loadings increase, environmental constraints require that this acid gas stream be converted to sulfur.
One of the processes that converts acid gas to sulfur, such as LO-CAT®, SulFerox®, Claus, or Stretford,
must be added downstream of the amine system. In some cases, it may be feasible to contact the gas
stream to be treated directly with LO-CAT® or SulFerox® solution and eliminate the need to separate the
acid gas components from the gas stream with an amine unit.

When a Claus unit is used, it may be necessary to add tail gas cleanup downstream of the Claus unit if
acid gas loadings are very high.

Removal of CO2

Removal of CO2 to meet pipeline quality specifications can be accomplished with an amine-based
system since the acid gas from the stripper can be vented (assuming levels of H2S in the gas being treated
are very low).

Removal of CO2 with gas permeation may be attractive for low volume gas streams in remote areas where
the loss of methane is not critical. Permeation systems with a second stage recycle may be competitive
with amine systems.
Removal of H2S and CO2

Most commonly, both H2S and CO2 are present and must be removed to meet pipeline quality
requirements. In most cases, essentially all of the H2S will have to be removed, while only a fraction of
the CO2 will have to be removed. Use of a non-selective solvent such as MEA or DEA will require that
the equipment be sized to essentially remove all the CO2 so that the H2S specification can be achieved.
This procedure may be the most economical solution for streams with low CO2 concentrations.

As CO2 concentrations in the feed increase, it becomes more economical to use a selective process such
as MDEA, Sulfinol®, Selexol®, etc., which will remove a higher percentage of H2S than CO2 from a
stream.

Another alternative is to use gas permeation or a carbonate system for bulk removal of CO 2 upstream of
a non-selective amine unit.

Finally, it may be economical to remove both H2S and CO2 to a level where the CO2 content is
acceptable with either a selective or non-selective process, and use a sulfur removal process (iron sponge,
Sulfa-Treat, Sulfa-Check, LO-CAT®, SulFerox®) for final treating of the residue gas.

CLASSIFICATION OF SWEETENING PROCESSES

Sweetening processes are classified as:

 Non-regenerative
 Regenerative Processes with recovery of H S
2
 Regenerative Processes with recovery as elemental Sulfur
SWEETENING PROCESSES

SWEETENING PROCESSES

Solid bed Sweetening Absorption Direct Conversion


Processes Processes Processes
The Iron Sponge Process Stretford process
Molecular Sieves

Physical Absorption Chemical Absorption


Processes Processes
Water Wash (Aquasorption) Process Alkanol-Amine Processes
Selexol Process Hot Potassium Carbonate
Sulfinol Process processes

A: Absorption Process

a. Chemical Absorption
1. Alkanol- Amine Process
2. Hot Potassium Carbonate Process (For bulk removal of CO2 )
b. Physical Absorption
B: Adsorption Process (Solid Bed Sweetening Process)

1. The Iron Sponge Process


2. Molecular Sieve Process
C: Direct Conversion to Elemental Sulfur

1. Stretford Process

D.0 Elemental Sulfur from H2S

H2S gas removed from any of the processes needs to be broken for extraction of Elemental
Sulfur from H2S by Claus Process.
A.a.1: CHEMICAL ABSORPTION BY SOLVENT PROCESSES

Chemical solvent processes use an aqueous solution of a weak base to chemically react with and absorb
the acid gases in the natural gas stream. The absorption driving force is a result of the partial pressure
differential between the gas and the liquid phases. The reactions involved are reversible by changing the
system temperature or pressure, or both. Therefore, the aqueous base solution can be regenerated and
circulated in a continuous cycle. The majorities of chemical solvent processes utilize either an amine or
carbonate solution.

Aqueous Alkanolamine Processes

Originally applied to gas treating in 1930 by Bottoms, alkanolamine have become the most widely used
solvents for the removal of acid gases from natural gas streams.
Triethanolamine (TEA) was the first used commercially for gas treating. It has been displaced for
conventional applications by other alkanolamine such as:
1. Monoetanolamine (MEA),
2. Diethanolamine (DEA),
3. Diisopropanolamine (DIPA),
4. Diglycolamine (DGA) and
5. Methyldiethanolamine (MDEA).
Other formulations such as Formulated solvents, sterically hindered Amines and Caustic Wash Can also
be enumerated for the purpose.
The alkanolamine processes are particularly applicable where acid gas partial pressures are low and/or
low levels of acid gas are desired in the residue gas. Because the water content of the solution minimizes
heavy hydrocarbon absorption, these processes are well suited for gases rich in heavier hydrocarbons.
Some amines can be used to selectively remove H2S in the presence of CO2.
Use of solvents
 Aqueous solutions of weak bases can be used to absorb acid gases from NG.
 Absorption takes place because of partial pressure difference and these bases react with the acid
gases.
 Reactions with ethanol amines are reversible, therefore, recycle and reuse of solvents is possible.

Amine Processes

Several processes have been developed using the basic action of various amines. These amines can be
categorized by the number of organic groups bonded to the central nitrogen atom, as primary, secondary
or tertiary. For example:

 Amine or carbonate solutions are normally used.


 All, primary, secondary, and tertiary amines are capable of removing the acid gases.
 Primary amines are more reactive than secondary, which are more reactive than the tertiary
amines.
 DEA is the most commonly used because it is less expensive and design using DEA is
standardized. Installations can be easily done.
Chemistry — the basic reactions applicable for H2S, CO2 and a primary or secondary amine are
shown below with a secondary amine:

For H2S
 RR’NH2 + « H+ + RR’NH
 H2S « H+ + HS-
 HS- « H+ + S=
 H2O « H+ + OH-

For CO2
 RR’NH2 + « H+ + RR’NH
 RR’NCOO- + H2O « RR’NH + HCO3 -
 H2O + CO2 « H+ + HCO3 -
 HCO3 - « H+ + CO3 =
 H2O « H+ + OH-

Solubility of acid gas in amines follows Henry’s Law according to:

 pp(H2S) = H(H2S) [H2S]


 pp(CO2) = H(CO2) [CO2]

The reactions proceed to the right at high pressures and/or low temperatures and to the left at high
temperatures and/or low pressures. Primary amines undergo similar reactions. Tertiary amines can only
react with CO2 following the acid base reaction shown in Eq 21-1. The CO2 reaction is slowed by the
time requirement for solution of CO2 and conversion to bicarbonate, Eq 21 7. This may be the reason that
tertiary amines show a greater selectivity for H2S in the presence of CO2.
Primary amines form stronger bases than secondary amines, which form stronger bases than tertiary
amines. Amines with stronger base properties will be more reactive toward CO2 and H2S gases and will
form stronger chemical bonds. This implies that the acid gas vapor pressure will be lower for a given
loading as amine reactivity increases and a higher equilibrium loading may be achieved.

A typical amine system is shown in Figure (Gas sweetening process flow schematic of amine sweetening).

The sour gas enters the system through an inlet scrubber to remove any entrained water or hydrocarbon
liquids. Then the gas enters the bottom of the amine absorber and flows countercurrent to the amine
solution. The absorber can be either a trayed or packed tower with conventional packing usually used for
500 mm (20 in) or smaller diameter towers, and trays or structured packing for larger towers. The
sweetened gas then leaves the top of the tower. An optional outlet scrubber may be included to recover
entrained amine from the sweet gas. Since the natural gas leaving the top of the tower is saturated with
water, the gas will require dehydration before entering a pipeline.

The amine solution leaves the bottom of the absorber. This solution containing the CO2 and H2S is
referred to as the rich amine. From the absorber, the rich amine flows to the flash tank to remove most of
the dissolved hydrocarbon gases or entrained hydrocarbon condensates. A small amount of the acid gases
will also flash to the vapor phase in this vessel. From the flash tank the rich amine proceeds to the rich
amine/lean amine heat exchanger. This heat exchanger recovers some of the sensible heat from the lean
amine stream to decrease the heat duty on the amine reboiler and the solvent cooler. The preheated rich
amine then enters the amine stripping tower where heat from the reboiler breaks the bonds between the
amine and acid gases. The acid gases are removed overhead and lean amine is removed from the bottom
of the stripper. The hot lean amine flows to the rich amine/lean amine heat exchanger and then to
additional coolers, typically aerial coolers, to lower its temperature to approximately 5.5°C (10°F) above
the inlet gas temperature. This reduces the amount of hydrocarbons condensed in the amine solution when
the amine contacts the sour gas. Typically, a side stream of approximately 3 percent of the amine flow
rate is taken off after the rich/lean amine heat exchanger and is flowed through a charcoal filter to clean
the solution of contaminants. The cooled lean amine is then pumped up to the absorber pressure and
enters the top of the absorber. As the amine solution flows down the absorber it absorbs the acid gases.
The rich amine is then removed at the bottom of the tower and the cycle is repeated.

The most common amine processes are Monoetanolamine (MEA) and diethanolamine (DEA). Both
processes will remove CO2 and H2S to pipeline specifications. Among the newer processes, which have
been developed is Methyldiethanolamine (MDEA). It can be used for selective removal of H2S in the
presence of CO2 and significantly reduces treating costs when CO2 reduction is not necessary.

A.a.1.1 Mono ethanol amine Systems (MEA)

Monoetanolamine (MEA) is a primary amine, which has had widespread use as a gas sweetening agent.
This process is well proven, can meet pipeline specifications, and has more design/operating data
available than any other system. MEA is a stable compound and in the absence of other chemicals suffers
no degradation or decomposition at temperatures up to its normal boiling point.

MEA reacts with CO2 and H2S as follows:

These reactions are reversible by changing the system temperature. The reactions with CO 2 and H2S
shown above are reversed in the stripping column by heating the rich MEA to approximately 118°C at 69
kPa (245°F at 10 psig). The acid gases evolve into the vapor and are removed from the still overhead.
Thus the MEA is regenerated.

A disadvantage of MEA is that it also reacts with carbonyl sulfide (COS) and carbon disulfide (CS 2) to
form heat stable salts, which cannot be regenerated at normal stripping column temperatures. At
temperatures above 118°C (245°F) a side reaction with CO2 exists which produces oxazolidone-2, a heat
stable salt, which consumes MEA from the process.
The normal regeneration temperature in the still will not regenerate heat stable salts or oxazolidone-2.
Therefore, a reclaimer is often included to remove these contaminants. A side stream of from 1 percent to
3 percent of the MEA circulation is drawn from the bottom of the stripping column. This stream is then
heated to boil the water and MEA overhead while the heat stable salts and oxazolidone-2 are retained in
the reclaimer. The reclaimer is periodically shut in and the collected contaminants are cleaned out. When
the contaminants are removed from the system, any MEA bonded to them is also lost.

MEA is usually circulated in a solution of 15 percent to 20 percent MEA by weight in water. From
operating experience it has been found that the solution loading should not be greater than 0.3 to 0.4
moles of acid gas per mole of MEA. Both the solution strength and the solution loading are limited to
avoid excessive corrosion. The solution concentration and loading is largely determined by the
H2S/CO2 ratio. Greater the ratio (i.e., the higher the concentration of H2S relative to CO2), the higher the
allowable loading and amine concentration. This is due to the reaction of H2S and iron (Fe) to form iron
sulfide (Fe2S3 and FeS), which forms a protective barrier on the steel surface. This barrier can be stripped
away by high fluid velocities and may lead to increased corrosion on the exposed steel.

The acid gases in the rich amine are corrosive, but the above concentration limits may hold corrosion to
acceptable levels. The corrosion commonly shows up on areas of carbon steel that have been stressed,
such as heat affected zones near welds, in areas of high acid gas concentration, or at a hot gas and liquid
interface. Therefore, stress relieving all equipment after manufacturing is necessary to reduce corrosion,
and special metallurgy is usually used in specific areas such as the still overhead or the reboiler tubes.

MEA systems foam rather easily resulting in excessive amine carryover from the absorber. Foaming can
be caused by a number of foreign materials such as condensed hydrocarbons, degradation products, solids
such as carbon or iron sulfide, excess corrosion inhibitor, valve grease, etc. One of the more effective
methods of foam control is to use a coalescing filter separator at the gas inlet to the MEA contactor. This
removes many of the contaminants before they enter the system. Hydrocarbon liquids are usually
removed in the flash tank. Degradation products are removed in a reclaimer as described above.

MEA storage tanks and surge vessels must have an inert blanket gas system to prevent the oxidation of
MEA. Sweet natural gas or nitrogen can be used as the blanket gas.

MEA has the lowest boiling point and the highest vapor pressure of the amines. This results in MEA
losses of 16 to 48 kg/MMm3 (1 to 3 lbs/MMSCF) of inlet gas.

In summation, MEA systems can effectively treat sour gas to pipeline specifications. However, care in the
design and material selection of MEA systems is required to minimize equipment corrosion.

A.a.1.2 Diethanolamine Systems (DEA)

Diethanolamine (DEA) is a secondary amine also used to treat natural gas to pipeline specifications. As a
secondary amine, DEA is less alkaline than MEA. DEA systems do suffer the same corrosion problems,
but not as severely as those using MEA. Solution strengths are typically from 25 to 35 percent DEA by
weight in water.
DEA reacts with CO2 and H2S as follows:

These reactions are reversible.

DEA has significant advantages over MEA when COS or CS2 are present. DEA reacts with COS and
CS2 to form compounds which can be regenerated in the stripping column. Therefore, COS and CS2 are
removed without a loss of DEA.

High CO2 levels have been observed to cause DEA degradation to oxazolidones. Typically, DEA
systems include a carbon filter but do not include a reclaimer.

The stoichiometry of the reactions of DEA and MEA with CO2 and H2S are the same. The molecular
weight of DEA is 105 compared to 61 for MEA. The combination of molecular weights and reaction
stoichiometry means that approximately 0.77 kg (1.7 lbs) of DEA must be circulated to react with the
same amount of acid gas as 0.45 kg (1.0 lbs) of MEA. The solution strength of DEA ranges up to 35
percent by weight compared to 20 percent for MEA. Loadings for DEA systems range from 0.35 to 0.65
moles of acid gas per mole of DEA without excessive corrosion. The result of this is that the circulation
rate of a DEA solution is slightly less than in a comparable MEA system.

The vapor pressure of DEA is approximately 1/30 of the vapor pressure of MEA. Therefore, amine losses
are much lower than in an MEA system.

A.a.1.3 Di glycol amine® Systems (DGA)

The Fluor Econamine Process uses Diglycolamine® (DGA) to treat natural gas. The active DGA reagent
is 2-(2-aminoethoxy) ethanol, which is a primary amine as follows:

The reactions of DGA with acid gases are the same as those for MEA. Unlike MEA, degradation products
from reactions with COS and CS2can be regenerated.

DGA systems typically circulate a solution of 50 to 70 percent DGA by weight in water. At these solution
strengths and a loading of up to 0.3 moles of acid gas per mole of DGA, corrosion in DGA systems is
slightly less than in MEA systems. The advantages of a DGA system are that the low vapor pressure
decreases amine losses, and the high solution strength permits lower circulation rates.

A.a.1.4 Di iso Propanol Amine Systems (DIPA)


Diisopropanolamine (DIPA) is a secondary amine used in the Shell "ADIP®" process to sweeten natural
gas.

DIPA systems are similar to DEA systems but offer the following advantages:

Carbonyl sulfide (COS) can be removed and the DIPA solution regenerated easily

The system is generally non-corrosive

Lower energy consumption

One feature of this process is that at low pressures DIPA will preferentially remove H 2S. As pressure
increases, the selectivity of the process decreases, and DIPA removes increasing amounts of CO2.
Therefore, this system can be used either to selectively remove H2S or to remove both CO2 and H2S.

A.a.1.5 Methyl di ethanolamine—Methyl di ethanolamine (MDEA) is a tertiary amine


which can be used to selectively remove H2S to pipeline specifications at moderate to high pressure. If
increased concentration of CO2 in the residue gas does cause a problem with contract specifications or
downstream processing, further treatment will be required. The H2S/CO2 ratio in the acid gas can be 10-
15 times as great as the H2S/CO2 ratio in the sour gas. Some of the benefits of selective removal of H2S
include:

 Reduced solution flow rates resulting from a reduction in the amount of acid gas removed.

 Smaller amine regeneration unit.

 Higher H2S concentrations in the acid gas resulting in reduced problems in sulfur recovery.
CO2 hydrolyzes much slower than H2S. This makes possible significant selectivity of
tertiary amines for H2S. This fact is used by several companies who provide process designs
using MDEA for selective removal of H2S from gases containing both H2S and CO2.
Because the reaction between CO2 and tertiary amines forms the acid-base adduct, tertiary
amines are ideally suited for bulk removal of CO2 from natural gas streams. The bulk
removal of CO2 requires only a modest heat input for regeneration. The combination results
in economic bulk removal of CO2 from high CO2 content gas streams.

A.a.1.5.1 Process Description

A.a.1.5.1.1 GENERAL

A.a.1.5.1.2 GAS SWEETENING UNIT


A.1.5.1.3 MDEA PROCESS PRINCIPLES

A.1.5.1.4 DESCRIPTION OF A MDEA TRAIN

A.1.5.1.5 ABSORPTION SECTION

A.1.5.1.6 AMINE REGENERATION SECTION

A.a.1.5.1.1 GENERAL

In the sweetening process, gas is washed with aqueous solutions of Methyl-Di-Ethanol-Amine


(MDEA).

A.a.1.5.1.2 GAS SWEETENING UNIT


The main purpose of this gas treatment step is to remove the H2S from the sour gas with a high
severity, and at same time, to limit the CO2 co-absorption to the minimum required and in any case, to
be not more than 32%.

A.a.1.5.1.3 MDEA PROCESS PRINCIPLES

The selective removal of H2S is made by washing the sour gas with an aqueous solution of Methyl-Di-
Ethanol-Amine (MDEA).

Methyl-di ethanol amine (MDEA) is a tertiary amine, which does not react easily with CO2. The
selectivity is so promoted by using the differences in reaction rates between both H2S and CO2 and the
tertiary amine.

First the case of a primary or secondary amine (mono ethanolamine or di ethanolamine) whose
reactions with the acid components H2S and CO2 are similar is investigated.

H2S reacts to give amine hydrosulfide:

H2S + R2NH HS - , R2NH2+ (I)

CO2 can react directly with amine to form an amine carbonate:

CO2 + 2R2NH R2NCOO- , R2NH2+ (2)

But CO2 can also react with water or hydroxyl ions to form carbonic acid or bicarbonate ions:

CO2 + H2O H2CO3 (3)

CO2 + HO- HCO3- (4)


-
These acids then react with the amine to form amine bicarbonate (HCO3, RNH2+) and amine
carbonate (CO2, (R2NH2+) 2).

As regards kinetics, 3 types of reaction can be distinguished

- Reaction (1) whose rate is infinite,


- Reaction (2) whose rate is moderate, depending on amine

- Reaction (3) and (4), known to be slow

As a matter of fact, the molecular structure of the tertiary amine prevents the direct reaction of CO2
with carbonate formation (reaction (2)).

Reaction rate difference between H2S and CO2 is thus clearly marked since there only remains
reaction (1) whose rate is infinite and reaction (3) and (4) whose rates are slow.

To perform a selective de-sulfurization using a MDEA solution, it is necessary to provide in the


absorber a gas-liquid contact time large enough to remove H2S but short enough to retain CO2
partially.

o H2S and CO2 absorption performance control is therefore mainly controlled by the gas-liquid
contact time in the absorber. Contact time depends on:
o The gas flow rate
o A liquid height above active plate area - the number of plates in absorber

The first 2 parameters cannot be acted upon. The 3rd parameter (plate quantity) allows adjusting
contact time according to the feeding conditions and required performance.

A.a.1.5.1.4 DESCRIPTION OF A MDEA TRAIN

Inlet pressure of raw gas varies from 57 - 65 kg/cm2a and temperature ranges from 20 C to 33 C.

The working pressure in the gas washing unit (inlet separator, absorption column, outlet separator) is
the range of 57 - 61 kg/cm2a.

A.a.1.5.1.5 ABSORPTION SECTION


Raw gas is first heated in steam heater. Then it is passed through the pressure regulating control valve.
Its temperature is maintained above 25C by controlling the heater steam flow.

This raw gas is then mixed with the condensate treating unit-derived raw gas, which is made up of the
light hydrocarbon fraction contained in the raw condensates.

This raw gas mixture passes through a knock out drum where liquid carry over (water, hydrocarbon)
are retained to be pumped to the condensate treating unit.

Upon leaving separator, raw gas enters an amine absorber column where it comes into contact counter
currently with the aqueous solution of MDEA.

The lean MDEA solution at 45C enters into the upper part of the column. Different liquid feed
possibility to the column allows selecting the adequate number of the trays to obtain the required
results taking into account feed gas quality and operating conditions. The selected feed position could
be to trays 1, 3, 5, 7 or 9 and the switching over from one to another is manual. The MDEA feed
nozzles are arranged such that the liquid feed is fed to the downcomers of trays (1, 3, 5, 7 and 9 and
not on to the trays themselves.
The upper tray is dry and retains the major part of carryovers. The total lean MDEA solution flows to
the column under flow control.

At absorber top, treated gas contains less than 4 ppm vol. H2S. Temperature ranges from 40 C to 44
C. The gas is cooled to 38 C by passing through a water cooler.

Liquid phase resulting from cooling (condensed water + amine carryover) is separated in the treated
gas KO- Drum and returned to rich amine circuit at a lower pressure.

Treated gas is piped to TEG drying unit.

A.a.1.5.1.6 AMINE REGENERATION SECTION


The stream of the rich amine solution is recovered under level control valve from the bottom of the
absorber and piped to the rich amine flash drum. The sour flashed gas from this drum contains about
200 ppm (vol.) H2S. In order to meet the fuel gas specifications (less than 4 ppm vol. of H2S) this sour
fuel-gas is brought into contact with a small lean MDEA flow in a 6 valve tray absorption tower
placed on the top of the rich amine flash drum.

The rich amine solution flows from the flash drum to the rich/lean amine exchanger. The rich amine
flash drum level control valve is located downstream of the exchanger in order to minimize the
solution degassing by the exchanger plates. MDEA solution stripping is accomplished in the
regenerator by the vapor generated from the reboiler.

The lean amine collected at the bottom of the regenerator is routed through amine/amine exchanger
and cooled to 45 C in a lean amine cooler and sent to a large lean amine storage tank.

The hot acid-gas/steam mixture from the overhead of the regenerator is cooled to 50 C in a condenser
where water vapor condenses. This condensed vapor is separated in the reflux drum and pumped back
to the top section of the regenerator.

The trays are provided for washing the acid gas with reflux water in order to minimize amine
carryover.

Acid gas is sent to an acid gas header through a pressure control valve, which maintains a 2.0 kg/cm2a
minimum pressure on top of the reflux drum.

From the storage tank, lean amine is pumped back to the absorbers by the main amine charge pump.

The discharged amine stream is split into two parts through flow rate control valves: a main stream
flows to the high pressure Absorber and a smaller one to the fuel-gas absorber.

A.a.1.6 Tri ethanolamine — Tri ethanolamine (TEA) is a tertiary amine and has exhibited
selectivity for H2S over CO2 at low pressures. TEA was the first amine commercially used for
gas sweetening. It was replaced by MEA and DEA because of its inability to remove H2S and
CO2 to low outlet specifications. TEA has potential for the bulk removal of CO2 from gas
streams. It has been used in many ammonia plants for CO2 removal.
A.a.2 (Hot Carbonate Process)
The basic process employs an aqueous solution of potassium carbonate (K2CO3). The contactor and
stripper both operate at temperatures in the range of 110–116°C. The process is not suitable for gas
streams containing only H2S. If H2S is to be removed to pipeline specification or there are low CO2
outlet specifications, special designs or a two-stage system is to be used.

Potassium carbonate processes are somewhat effective in removing carbonyl sulfide (COS) and carbon
disulfide (CS2).

These reactions are reversible based on the partial pressures of the acid gases. Note that potassium
bicarbonate (KHCO3) solutions are not readily regenerable in the absence of CO2 so that these processes
are only employed for H2S removal when quantities of CO2 are present. Potassium carbonate also reacts
reversibly with COS and CS2.

The overall reactions for CO2 and H2S with potassium carbonate can be represented by:

K2CO3 + CO2 + H2O « 2 KHCO3


K2CO3 + H2S « KHS + KHCO3

A highly concentrated aqueous solution of potassium carbonate 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 (Hot K2CO3 system)


CO2 partial pressures in the range of 30-90 psi are necessary for efficient operation.

The reactions takes place in the carbonate process are:


K CO + CO + H O 2KHCO 1
2 3 2 2 3

K CO + H S KHS + KHCO 2
2 3 2 3

Reactions (1) (K CO + CO + H O 2KHCO ) proceed in two steps:


2 3 2 2 3

• The first step is hydrolysis of the potassium carbonate:


K CO + H O KOH + KHCO ----------------------------- 3
2 3 2 3

• Potassium hydroxide thus formed, reacts with CO to form potassium bicarbonate:


2
KOH + CO KHCO ------------------------------------- 4
2 3

Reactions (2) (K CO + H S KHS + KHCO ) proceed in two steps:


2 3 2 3

K CO + H O KOH + KHCO ------------------- 5


2 3 2 3

Potassium hydroxide formed also reacts with H S to form potassium bisulfide


2

KOH + H S KHS (Potassium Bisulfide) + H O ---------------- 6


2 2

Thus KOH formed during reactions, reacts with CO2 and H2S to form KHCO3 and KHS.

KHS hydrolyzes to form H2S and KOH

KHS + H O H S + KOH ---------------------------------------------------7


2 2

In brief,

KOH is produced during reaction of K2CO3 and H2O.

KOH reacts with CO2 and H2S to produce KHCO and KHS
3

KHS Hydrolyzes to form H S and KOH


2

The above cycle goes on to react with CO and H S


2 2

COS carbonyl sulfide


It can be removed without significant solution degradation

Carbonate process has the advantage that both Potassium Bisulfide (KHS) and carbonyl sulfide (COS) can
be removed without significant solution degradation.

Carbonyl sulfide will hydrolyze as follows:


COS + H O CO + H S -----------------------------------------------------8
2 2 2

K CO + H S KHS + KHCO ------------------------------------- 9


2 3 2 3

KHS + H O H S + KOH ---------------------------------------------------10


2 2
KOH reacts with CO2 and H2S to produce KHCO and KHS
3

KHS Hydrolyzes to form H S and KOH


2

The above cycle goes on to react with CO and H S


2 2
• Carbon disulfide
Carbon disulfide hydrolyzes to form COS and H S
2

CS + H O COS + H S -------------------------------------------------------- 11
2 2 2

H S reacts as per reaction 2.


2

COS hydrolyzes as per reaction 8.

• Mercaptans reacts with potassium carbonate solution to form mercaptides


K CO + RSH RSK + KHCO
2 3 3 + ------------------------------------ 12
(Gas sweetening flow schematic of a hot carbonate process) shows a typical hot carbonate system for
gas treating.

Process Diagram (K2CO3 SYSTEM)

Process Description (K2CO3 SYSTEM)


• The sour gas enters the bottom of the absorber and flows counter-current to the potassium
carbonate. The sweet gas then exits the top of the absorber. The absorber is typically operated at
230°F; therefore, a sour/ sweet gas exchanger may be included to recover sensible heat and
decrease the system heat requirements.

• The acid-rich potassium carbonate solution from the bottom of the absorber is flashed to a flash
drum, where much of the acid gas is removed.

• The solution then proceeds to the stripping column, which operates at approximately 245°F and
near-atmospheric pressure. The low pressure, combined with a small amount of heat input, drives
off the remaining acid gases.

• The lean potassium carbonate from the stripper is pumped back to the absorber. The lean solution
may or may not be cooled slightly before entering the absorber. The heat of reaction from the
absorption of the acid gases causes a slight temperature rise in the absorber.
• The solution concentration for a potassium carbonate system is limited by the solubility of the
potassium bicarbonate (KHCO3) in the rich stream. The high temperature of the system increases
the solubility of KHCO3, but the reaction with CO2 produces two moles of KHCO3 per mole of
K2CO3 reacted. For this reason the KHCO3 in the rich stream limits the lean solution K2CO3
concentration to 20-35% by weight.

• The entire system is operated at high temperatures to increase the solubility of potassium
carbonate. Therefore, the designer must be careful to avoid dead spots in the system where the
solution could cool and precipitate solids.

• If solids do precipitate, the system may suffer from plugging, erosion, or foaming.

• The hot potassium carbonate solutions are extremely corrosive. All carbon steel must be stress-
relieved to limit corrosion. A variety of corrosion inhibitors are available to decrease corrosion.

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 CO
2

and steam were released by pressure reduction.


• Remedy – Corrosion inhibitors includes arsenic and vanadium salts as well as
dichromate.
• 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.
• The absorber and stripper can be made of carbon steel.
• When CO is the only acid gas constituents, potassium dichromate will serve as an
2
effective corrosion inhibitors (but from 1000 to 3000 ppm).
• If sufficient quantity of H S is present, formation of the potassium bisulfide inhibits
2

corrosion to a significant extent.


• In cases where corrosion is a problem with H S present, the commercially available film-
2

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 cavitations 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 CO removal, arsenic trioxide most commonly used;
2
selenous acid and tellurous acid are also used. For H S removal, alkaline arsenites and
2
arsenates (usually KH AsO3 and KH AsO4) are used.
2 2

A. b: Physical Absorption Processes


These processes rely upon physical absorption of acid components as the gas sweetening
mechanism. 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.
 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 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 like
H2S and CO2 chemically in any manner. So after recovery of the gases, a process Claus will be
required to extract elemental Sulfur.

In general, a physical solvent process should be considered when:

· The partial pressure of the acid gas in the feed is greater than 345 kPa.
· The heavy hydrocarbon concentration in the feed gas is low.
· Bulk removal of the acid gas is desired.
· Selective removal of H2S is desired.
These processes are economically attractive because little or no 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 vapors.

In general, physical solvents are capable of removing COS, CS2, and mercaptans. The processes operate
at ambient or sub-ambient temperature to enhance the solubility of the acid gases. The solvents are
relatively noncorrosive so carbon steel can be used. Chemical losses are low due to low solvent vapor
pressure. Physical solvents will absorb heavy hydrocarbons from the gas stream resulting in high
hydrocarbon content in the acid gas stream as well as possibly significant hydrocarbon losses.

A physical solvent process is shown below (Typical flow schematic of a physical solvent process).
Some of the physical absorption processes are summarized below.

The sour gas contacts the solvent using countercurrent flow in the absorber. Rich solvent from the
absorber bottom is flashed in stages to near atmospheric pressure. This causes the acid gas partial
pressures to decrease and the acid gases evolve to the vapor phase and are removed. The regenerated
solvent is then pumped back to the absorber.

The example in Figure (Typical flow schematic of a physical solvent process) is a simple one where
flashing is sufficient to regenerate the solvent. Some solvents require a stripping column just prior to the
circulation pump. Some systems require temperatures below ambient, thus refrigeration using power
turbines replaces the pressure reducing valves.
B.0 Adsorption Process
B.1 Iron Sponge Process
(Direct sulfur removal process): The iron sponge process selectively removes H2S from
gas or liquid streams. The process is limited to treating streams containing low concentrations of H2S at
pressures ranging from 170 to 8300 kPa. The process employs hydrated iron oxide, impregnated on wood
chips. Care must be taken with the iron sponge bed to maintain pH, gas temperature, and moisture content
to prevent loss of bed activity. Consequently, injections of water and sodium carbonate are sometimes
needed. H2S reacts with iron oxide to form iron sulfide and water. When the iron oxide is consumed, the
bed must be changed out or regenerated. The bed can be regenerated with air; however, only about 60%
of the previous bed life can be expected. The bed life of the batch process is dependent upon the quantity
of H2S, the amount of iron oxide in the bed, residence time, pH, moisture content, and temperature.

The change-out of the spent sponge beds is hazardous. Iron sulfide exposed to air will rapidly oxidize and
can result in spontaneous combustion of the spent bed. To prevent this, the entire bed should be wetted
before beginning the change-out operation.

 The iron sponge process utilizes the chemical reaction of ferric oxide with H S to sweeten gas
2
streams. This process is economically applied to gases containing small amounts of H S. This
2
process does not remove carbon dioxide.

• The reaction of hydrated colloidal iron oxide and H S produces iron sulfide and water as follows:
2

2 Fe2 O 3 + 6 H2S = 2 Fe2 S3 + 6 H2O


Fe O + H2S = Fe S + H2O
The reaction requires the presence of water and a temperature below 49°C (120°F). When temperatures
exceed 49°C (120°F), careful control of pH must be maintained. If the gas does not contain sufficient
water vapor, water may need to be injected into the inlet gas stream. A pH level of 8 to 10 can be
maintained through the injection of caustic soda, soda ash, lime, or ammonia with the water.
Although the presence of free alkalies enhances H S removal, it creates potential safety hazards, promotes
2
formation of undesirable salts and adds to capital costs.
Summary:
 The iron sponge process uses the chemical reaction of ferric oxide with H2S to sweeten gas
streams. This process is applied to gases with low H2S concentrations (300 ppm) operating at low
to moderate pressures (50-500 psig). Carbon dioxide is not removed by this process. The reaction
of H2S and ferric oxide produces water and ferric sulfide as follows:

2Fe2O3 + 6H2S -> 2Fe2S3 + 6H20

 The reaction requires the presence of slightly alkaline water and a temperature below 110°F. If
the gas does not contain sufficient water vapor, water may need to be injected into the inlet gas
stream.
 Additionally, bed alkalinity should be checked daily. A pH level of 8-10 should be maintained
through the injection of caustic soda with the water.

 The ferric oxide is impregnated on wood chips, which produces a solid bed with a large ferric
oxide surface area. Several grades of treated wood chips are available, based on iron oxide
content. The most common grades are 6.5-, 9.0-, 15.0-, and 20-lb iron oxide. The chips are
contained in a vessel, and sour gas flows through the bed and reacts with the ferric oxide. Figure
shows a typical vessel for the iron sponge process.

 Sour gas passes through a bed of wood chips that have been impregnated with hydrated
form of ferric oxide that has a high affinity for H S.
2

 The chemical reaction is as follows:

Fe2O3 + 3 H2S Fe2S3 + 3 H2O

o
 The temperature must be less than 120 F

The Ferric Sulfide can be oxidized with air to produce sulfur and regenerate the ferric
oxide.

 Iron oxide is regenerated by passing oxygen/air over the bed according to the reaction:

2Fe S + 3 O2 Fe2O3 + 6 S
2 3

S + 2 O2 2 S O2
2

The regenerated step must be performed with great care as the reaction with oxygen is
exothermic (that is gives off heat). Air must be introduced slowly so that heat of reaction can be
dissipated. If the air is introduced quickly, the heat of reaction may ignite the bed.

Some of the elemental sulfur produced in regeneration step remains in the bed. After several
cycles this sulfur will make a cake over the ferric oxide, decreasing the reactivity of the bed.
Typically after 10 cycles the bed must be removed from the vessel and replaced with the new
bed.
The advantages of the Iron Sponge Process are:
1. Simplicity.
2. Absolute selectivity (H S).
2
3. 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)
B.2 Molecular Sieves (Indirect sulfur removal process)
Molecular Sieve Process

Molecular sieve processes use synthetically manufactured crystalline solids in a dry bed to remove gas
impurities. The crystalline structure of the solids provides a very porous material having uniform pore
size. Within the pores the crystalline structure creates a large number of localized polar charges called
active sites. Polar gas molecules such as H2S and water vapor, which enter the pores, form weak ionic
bonds at the active sites. Non-polar molecules such as paraffin hydrocarbons will not bond to the active
sites.

Molecular sieves are available with a variety of pore sizes. A molecular sieve should be selected with a
pore size that will admit H2S and water while preventing heavy hydrocarbons and aromatic compounds
from entering the pores. Carbon dioxide molecules are about the same size as H2S molecules, but are non-
polar. Thus, CO2 will enter the pores but will not bond to the active sites. Small quantities of CO 2 will
be removed by becoming trapped in the pores by bonded H2S or H2O molecules blocking the pores. More
importantly, CO2 will obstruct the access of H2S and H2O to the active sites, decreasing the overall
effectiveness of the molecular sieve. Beds must be sized to remove all H2O and provide for interference
from other molecules in order to remove all H2S.

The adsorption process usually occurs at moderate pressure. Ionic bonds tend to achieve an optimum
performance near 3100 KPa (450 psig), but the system can be used for a wide range of pressures.

The molecular sieve bed is regenerated by flowing hot sweet gas through the bed. The hot stripping gas
breaks the ionic bonds and removes the H2S and H2O from the sieve. Typical regeneration temperatures
are in the range of 150°C to 200°C (300°F to 400°F).

Molecular sieve beds can suffer chemical and mechanical degradation. Care should be taken to minimize
mechanical damage to the solid crystals as this may decrease the bed's effectiveness. The main causes of
mechanical damage are the sudden pressure and/or temperature changes that may occur when switching
from adsorption to regeneration cycles. Proper instrumentation can significantly extend bed life.

Molecular sieves are generally limited to small gas streams operating at moderate pressures. Due to these
operating limitations, molecular sieve units have seen limited use for gas sweetening operations. They are
generally used for polishing applications following one of the other processes.

 Can handle large or small streams.


 Reduces total sulfur content by removing hydrogen sulfide, Mercaptan, and partially removing
organic sulfur in the same adsorber vessel.
 Will produce copper-strip, doctor-sweet product.
 Will dry in the same step with additional equipment.
 Requires that the regeneration gas be made slightly sour by use of this stream to strip sulfur
compounds from the molecular sieve.
Molecular sieve processes can be used for removal of sulfur compounds from gas streams. Hydrogen
sulfide can be selectively removed to meet 5.7 mg/m3 specification. The sieve bed can be designed to
dehydrate and sweeten simultaneously. In addition, molecular sieve processes can be used for CO2
removal. In general, the concentrations of acid gas are such that cycle times are in the order of 6-8 hours.
To operate properly the sieves must be regenerated at a temperature close to 315°C for a long enough
period of time to remove all adsorbed materials, usually one hour or more. Regeneration of a molecular
sieve bed concentrates the H2S into a small regeneration stream which must be treated or disposed of.
During the regeneration cycle, the H2S will exhibit a peak concentration in the regeneration gas. The peak
is approximately 30 times the concentration of the H2S in the inlet stream. Knowing the concentration of
this stream is essential for the design of a gas treater for the regeneration gas.

Parameters Affecting the Adsorptive Capacity


• The adsorptive capacity of molecular sieves for H S decreases with increasing temperature.
2

• The adsorptive capacity of molecular sieves for H S increases with increasing H S/CO ratio.
2 2 2

• Increasing contact time is favorable to H S removal up to a point, beyond which there is no


2

effect.
• The effect of pressure was found to be quite small; however, about 450 psia was identified as
optimum pressure.

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, H S and other sulfur compounds from natural
2
gas. Hence, they offer a means of simultaneous dehydration and desulfurization.
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 CO , carbonyl sulfide may form as shown in the following reversible
2
reaction:
H S + CO = COS + H O
2 2 2

Molecular sieves tend to catalyze this reaction.


C. (Process for Direct Conversion to elemental Sulfur)
The processes are based on the use of chemical reactions to oxidize H S and produce elemental
2
sulfur. These processes are generally based either on the reaction of H S and O or H S and SO . Both
2 2 2 2
reactions yield water and elemental sulfur. These processes are licensed and involve specialized catalysts
and/or solvents.
An example of a process using O to oxidize H S is the Stretford process, which is licensed by the British
2 2
Gas Corporation. In this process the gas stream is washed with an aqueous solution of sodium carbonate,
sodium vanadate and anthraquinone disulfonic acid.

The Holmes-Stretford Process


1. Outlines:
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).

• This process converts H S to elemental sulfur of almost 99.9% purity.


2
• The process is selective for H S, and can reduce the H S content to as low as 1 ppm.
2 2
• CO content remains almost unaltered by this process.
2
• Operating costs are lower and the process has better flexibility in application, that is, it
can be designed for larger pressure and temperature ranges.

2. Steps of the reaction process:

• H2S is converted to S. H2S is reduced to 1 ppm and CO2 is unaffected.

• Operating cost is less and adaptable to a wide range of P and T.

• Uses aqueous solutions of Na2CO3 and NaHCO3 in ratio 1:3, and sodium salt of Anthraquinone
disulfonic acid (ADA).

• PH is 8.5 to 9.5.

• Alkali vanadate is the best additives in reducing H2S TO S. In the presence of ADA, they are
regenerated.

3. Stretford Solution
The Stretford solution consists of following chemicals in a dilute water solution:
CHEMICAL ADDITIVE PURPOSE

Na salt of ADA dissolution in the solution

Na Meta vanadate to provide active vanadium

Na-K tartarate to prevent formation of a complex V-O precipitate

Sequestering agent to prevent precipitation of metallic ions from solution

Na2CO3 to maintain alkalinity

NaHCO3 to reduce absorption of CO2

4. The postulated reaction mechanism involves five steps:


I. Absorption of H S in alkali
2
II. Reduction of ADA by addition of hydrosulfide to a carbonyl group
III. Liberation of elemental sulfur from reduced ADA by interaction with oxygen
dissolved in the solution
IV. Reoxidation of the reduced ADA by air
V. Reoxygenation of the alkaline solution, providing dissolved oxygen for step
(3).
5. Chemical Reactions
5.1 The overall reaction of the Holmes-Stretford process is the atmospheric
oxidation of H S to elemental sulfur:
2

2H S + O 2H O + 2S
2 2 2

The reaction occurs in the following steps:


Na CO + H S NaHS + NaHCO
2 3 2 3

4NaVO + 2NaHS + H O Na V O + 4NaOH + 2S


3 2 2 4 9

2Na V O + 2NaOH + H O + 2ADA 4NaVO + 2ADA (reduced)


2 4 9 2 3

2ADA (reduced) + O 2ADA + H O


2 2

5.2 The description of the chemical reactions involved is:

H2S+ Na2CO3=NaHS + NaHCO3


Sodium carbonate provides the alkaline solution for initial adsorption of H2S and the formation of
¾
hydrosulfide (HS ). The hydrosulfide is reduced in a reaction with sodium Meta vandate to precipitate
sulfur.
- +5 +4
HS + V = S + V

Anthraquinone disulfonic acid (ADA) reacts with 4-valent vanadium and converts it back to 5-valent.
+4 +5
V + ADA = V + ADA (reduced)

Oxygen from the air converts the reduced ADA back to the oxidized state.

Reduced ADA + ADA = ADA + H O


2

The overall reaction is: 2H2S+ O2 = 2H2O + S

6. Stretford Process
Oxidized solution is delivered from the pumping tank to the top of the absorber tower where it contacts
the gas stream in a countercurrent flow. The bottom of the absorber tower consists of a reaction tank from
which the reduced solution passes to the solution flash drum, which is situated above the oxidizer. The
reduced solution passes from here into the base of the oxidizer vessel.

Hydrocarbon gases, which have been dissolved in the solution at the plant pressure, are released from the
top of the flash drum. Air is blown into the oxidizer and the main body of the solution, now re-oxidized,
passes into the pumping tank.

The sulfur is carried to the top of the oxidizer by froth created by the aeration of the solution and passes
into the thickener. The function of the thickener is to increase the weight percent of sulfur which is
pumped to one of the alternate sulfur recovery methods of filtration, filtration and autoclaves,
centrifugation or centrifugation with heating.

7. Fig. (Stretford Process) shows a simplified diagram of the process.


D.0 Elemental Sulfur from H2S

Converting Hydrogen Sulfide to Sulfur by Claus Process

Introduction:
Hydrogen sulfide (H2S) is a smelly, corrosive, highly toxic gas. Besides its other bad habits, it also
deactivates industrial catalysts. H2S is commonly found in natural gas and is also made at oil refineries,
especially if the crude oil contains a lot of sulfur compounds.

Because H2S is such an obnoxious substance, it is converted to non-toxic and useful elemental sulfur at
most locations that produce it. The process of choice is the Claus Sulfur Recovery process.

The Claus process is used to treat gas streams containing high concentrations of H 2S. The chemistry of
the units involves partial oxidation of hydrogen sulfide to sulfur dioxide, and the catalytically promoted
reaction of H2S and SO2 to produce elemental sulfur. The reactions are staged and are as follows:

(Typical flow diagram of a two-stage Claus process plant) shows a simplified process flow diagram
of the Claus process).
The first stage of the process converts H2S to sulfur dioxide and to sulfur by burning the acid gas stream
with air in the reaction furnace. This provides SO2 for the next phase of the reaction. Multiple reactors
are provided to achieve a more complete conversion of the H2S. Condensers are provided after each
reactor to condense the sulfur vapor and separate it from the main stream. Conversion efficiencies of 94 to
95 percent can be attained with two catalytic stages while up to 97 percent conversion can be attained
with three catalytic stages. As dictated by environmental concerns the effluent gas is vented, incinerated
or sent to a "tail gas treating unit."

Description of the Claus Process

First the H2S is separated from the host gas stream using amine extraction. Then it is fed to the Claus unit,
where it is converted in two steps:

1. Thermal Step. The H2S is partially oxidized with air. This is done in a reaction furnace at high
temperatures (1000-1400 deg C). Sulfur is formed, but some H2S remains unreacted, and some
SO2 is made.
2. Catalytic Step. The remaining H2S is reacted with the SO2 at lower temperatures (about 200-350
deg C) over a catalyst to make more sulfur.

A catalyst is needed in the second step to help the components react with reasonable speed. Unfortunately
the reaction does not go to completion even with the best catalyst. For this reason two or three stages are
used, with sulfur being removed between the stages. Engineers know how different factors like
concentration, contact time and reaction temperature influence the reaction, and these are set to give the
best conversions.

The reaction is as follows: 2H2S + SO2 ==> 3S + 2H2O

Inevitably a small amount of H2S remains in the tail gas. This residual quantity, together with other trace
sulfur compounds, is usually dealt with in a tail gas unit. The latter can give overall sulfur recoveries of
about 99.8%, which is very impressive indeed.

Sulfur Production by the Claus Process


Process Improvements
Over the years many improvements have been made to the Claus process. Recent developments include:

 SUPERCLAUS (TM). A special catalyst in the last reactor oxidizes the H2S selectively to sulfur,
avoiding formation of SO2. Significantly higher conversions are obtained at modest cost.
 Oxygen Claus. The combustion air is mixed with pure oxygen. This reduces the amount of
nitrogen passing through the unit, making it possible to increase throughput.
 Better Catalysts. Higher activities have been achieved with catalysts that provide higher surface
areas and macro-porosity.

CS2 destruction: Carbon disulfide (CS2) is a side product made in the furnace. Laboratory work has
shown that special catalysts operating in the furnace can destroy the CS2 before it gets into the catalytic
section. A commercially available catalyst like this might be developed for use in a Claus plant.

Catalyst Temperature Policy: The conversion of H2S goes faster at higher temperatures, but a more
favorable equilibrium is obtained at lower temperatures. It isn't obvious whether higher or lower
temperatures are needed in the third converter. Kinetic modeling may supply the answer, thereby
improving conversion or reducing catalyst replacement cost.

The residual gas from the Claus process is commonly called tail gas and that gas is then processed in a
tail gas treating unit (TGTU) to recover and recycle residual sulfur-containing compounds back into the
Claus unit. However, there are a number of processes available for treating the Claus unit tail gas. The
final residual gas from the TGTU is incinerated. Thus, the carbon dioxide in the raw natural gas ends up
in the incinerator flue gas stack.

Tail Gas Treating

There are many different processes used in tail gas treating today. These processes can be grouped into
two categories: the first category is an extension of the Claus reaction in a dry or a liquid system. Leading
among these processes are the Sulfreen and the Cold Bed Absorption (CBA) processes. These are similar
processes, using two parallel Claus reactors in a cycle, where one reactor operates below the sulfur dew
point to absorb the sulfur, while the second is regenerated with heat to recover the absorbed sulfur. Even
though recoveries are normally 99 to 99.5 percent of the inlet sulfur stream, incineration of the outlet gas
is required to meet environmental air quality.

The second category of tail gas processes involves the conversion of the sulfur compounds to H2S and
then the absorbing of the H2S from the stream. The SCOT process appears to be the leading choice among
this type of process. The SCOT process uses an amine to remove the H2S, which is usually recycled back
to the Claus plant. Other types of processes oxidize the sulfur compounds to SO2 and then convert the
SO2 to a secondary product such as ammonium thiosulfate, a fertilizer. These plants can remove more
than 99.5 percent of the sulfur and may eliminate the need for incineration. Costs of achieving tail gas
cleanup are high; typically double the cost of a Claus unit.