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Natural Gas Sweetening

Sour natural gas compositions can vary over a wide concentration of H2S and CO2 and a wide
concentration of hydrocarbon components. If the H2S content exceeds the sales gas
specification limit, the excess H2S must be separated from the sour gas. The removal of H2S
from sour gas is called “sweetening.”

Sweetening must be done on all sour gas. Sometimes this process is done in field production
facilities, but it is usually delayed until the gas reaches a gasoline plant or refinery. Hydrogen
sulphide and carbon dioxide are called acid gases because, when mixed with water, they form
acidic solutions. Many pipelines required that acid gases be removed from natural gas before
it is transported. Sweetening equipment is often used to remove both hydrogen sulphide and
carbon dioxide.

The process selected for sweetening a sour gas depends on the general conditions:

 H2S and mercaptan concentration in the sour gas, and sales gas H2S and total sulfur
limits
 maximum design flow rate
 raw gas inlet pressure
 requirement for sulfur recovery
 acceptable method of waste products disposal

Typical process equipment for sweetening sour gas with a regenerative solvent:

Figure: Schematic drawing of sweetening process equipment

There are several processes which can be used to strip acid gas from natural gas. For field
processing usually the alkanolamine process is often used. This method uses a chemical of

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the alkanolamine family, such as amine, to strip the acid gases in a process shown in the
simplified flow diagram of an amine sweetening unit. Sour gas enters the absorber tower and
is forced into intimate contact with amine not contaminated with acid gas (lean amine) by a
series of trays and baffles. The acid gas is absorbed by the amine, and sweet natural gas
leaves at the top of the absorber. The foul amine then enters an amine stripping still which
uses steam to heat the amine and distill the acid gas and water vapour from it. Acid gas and
water vapour are cooled, and water vapour is condensed to its liquid state. Water is removed
from the accumulator, while acid gas is vented to a flare where it is burned or is sent to a
sulphur recovery unit which separates the elemental sulphur. Stripped amine is sent to a
reboiler and reclaimer to complete the tasks of removing foreign substances from the amine,
which is then sent back to the absorber as lean amine.

Sweetening solvents

The desirable characteristics of a sweetening solvent are:

 Required removal of H2S and other sulfur compounds must be achieved.

 Pickup of hydrocarbons must be low.
 Solvent vapor pressure must be low to minimize solvent losses.
 Reactions between solvent and acid gases must be reversible to prevent solvent
degradation.
 Solvent must be thermally stable.
 Removal of degradation products must be simple.
 The acid gas pickup per unit of solvent circulated must be high.
 Heat requirement for solvent regeneration or stripping must be low.
 The solvent should be noncorrosive.
 The solvent should not foam in the contactor or still.
 Selective removal of acid gases is desirable.
 The solvent should be cheap and readily available.

There is no one solvent that has all the desirable characteristics. This makes it necessary to
select the solvent that is best suited for treating the particular sour gas mixture from the
various solvents that are available. The sour natural gas mixtures vary in:

 H2S and CO2 content and ratio

 content of heavy or aromatic compounds
 content of COS, CS2, and mercaptans

While most of the sour gas is sweetened with regenerative solvents, for slightly sour gas, it
may be more economical to use scavenger solvents or solid agents. In such processes, the
compound reacts chemically with the H2S and is consumed in the sweetening process,
requiring the sweetening agent to be periodically replaced.

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Regenerative chemical solvents

Table : Solvents used in gas sweetening

Most of the regenerative chemical sweetening solvents are alkanolamines, which are
compounds formed by replacing one, two, or three hydrogen atoms of the ammonia molecule
with radicals of other compounds to form primary, secondary, or tertiary amines respectively.
Amines are weak organic bases that have been used for many years in gas treating to remove
CO2 and H2S from natural gas as well as from synthesis gas. These compounds combine
chemically with the acid gases in the contactor to form unstable salts. The salts break down
under the elevated temperature and low pressure in the still.

Because the chemical reactions are reversible by changing the physical conditions of
temperature and pressure between absorber and still, amines are highly suitable for removing
the acid gases from the hydrocarbon gas stream. However, sometimes nonreversible reactions
take place to a minor degree, forming degradation compounds. Such degradation compounds
must be periodically removed by distillation. This occurs in a reclaimer vessel. Primary
amines are more prone to forming degradation compounds than the other solvents.

Primary amines

Monoethanolamine (MEA)

MEA was the earliest amine used for sweetening sour gas. It is a stronger base than
diethanolamine (DEA) and also has a higher vapor pressure than DEA; therefore, vapor
losses are higher than for DEA. MEA forms nonregenerative (degradation) compounds with:

 CO2
 COS
 CS2

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This is a disadvantage, as the degradation compounds must be removed periodically to lessen

the corrosion rate. A reclaimer is usually incorporated in an MEA sweetening train to
periodically remove the degradation products from the solution by distillation.

Diglycolamine (DGA)

The advantage of DGA over MEA appears to be the lower solution circulation rate owing to
the higher solvent concentration, resulting in higher acid gas pickup per volume of solution
circulated.[6] This yields capital savings, as the regeneration equipment is smaller for DGA
than for MEA. Disadvantages appear to be degradation of the chemical with CO2 and greater
solubility of heavier hydrocarbons in the solution, as compared to MEA.

Secondary amines

Diethanolamine (DEA)

It can be used at higher concentrations than MEA. DEA has the advantage of picking up
more acid gas per solution volume circulated, thus effecting some energy saving in
circulation and regeneration. It does not form the nonregenerative products with COS and
CS2 as is the case with MEA, which is another advantage over MEA. DEA is also generally
less corrosive than MEA.

Diisopropanolamine (DIPA)

This secondary amine is not used by itself as a sweetening solvent but is part of the Sulfinol
solvent formulation.

Tertiary amines

Triethanolamine (TEA)

TEA is not in general use for gas sweetening.

Methyldiethanolamine (MDEA)

MDEA reacts more slowly with CO2 than the previously described amines. It forms a
slightly different salt with CO2 from those of the other amines, at a lower rate of reaction.
The difference in the rates of reaction with H2S and CO2 gives MDEA a desirable feature
over other amines, namely selectivity of H2S over CO2. This is an attractive feature in cases
where it is not necessary to remove all the CO2 from the gas stream. By leaving some of the
CO2 in the natural gas, the circulation rate of the solution can be reduced, or the treating
capacity of an existing unit can be increased with MDEA as compared with DEA. As a
tertiary amine, MDEA is naturally a weaker base and is therefore less corrosive than the

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primary and secondary amines. The energy required for regeneration is also less than the
requirement for the other amines.

Types of operating problems

The main problems that can be encountered in the operation of sour gas treating facilities
using chemical solvents are as follows:

 failure to meet H2S specification for sales gas

 solution foaming in the contactor or regenerator
 corrosion in pipes and vessels
 solvent losses

Failure to Meet H2S Sales-Gas Specifications. Treated gas that does not meet the H2S
specifications is not admitted into the sales-gas transmission lines. Potential causes for “going
sour” are:

 a change in the acid gas concentration of feed gas

 a change in the feed gas temperature
 too hot lean amine solution
 too low solvent concentration in solution
 inadequate regeneration of solution
 insufficient contact in absorber
 too low amine circulation rate
 too low absorber pressure
 too high concentration of degradation products
 too high inlet gas rate
 mechanical damage or problems in absorber
 foaming

Solution Foaming

Solution foaming occurs when gas is mechanically entrained in liquid as bubbles. The
tendency to form bubbles increases with decreasing surface tension of the solution owing to
interference of foreign substance at the surface of the solution on the tray. Foaming is thought
to be caused by factors such as:

 liquid hydrocarbons entering the contactor with the sour gas

 acidic amine-degradation products
 treating chemicals from wells or gathering system
 treating chemicals from makeup water
 compressor oil
 fine solid suspensions such as iron sulfide

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While solids suspended in the solution by themselves might not cause foaming, it is thought
that they tend to stabilize the foam. The results from foaming can be:

 severe upsets in the process tower

 leading to carryover and loss of chemical
 possible damage to downstream process equipment or material

The best way to reduce the propensity for foaming is to ensure that the sour gas entering the
contactor is clean, free of condensed liquids, and that the solution is cleaned up by
mechanical and carbon filtration. The addition to the solution of antifoam agents is
sometimes effective in controlling the foaming tendency of the solution. However, this does
not solve the basic problem. Too much antifoam in the solution can actually add to the
foaming problem.

Corrosion

Corrosion is common in most amine plants. It is necessary to control the corrosion rate by the
addition of corrosion inhibitor and by use of stainless steel in certain pieces of process
equipment. In the case of MEA solutions, corrosion rates tend to increase with increasing
solution strengths beyond about 22% MEA, as well as with high levels of amine degradation
products in the solution. Most of the process piping and vessels in amine plants are built with
carbon steel.

It is not possible to predict with certainty where corrosive attack will take place. Experience
has shown that the most likely areas for corrosive attack are those where the temperatures are
high, such as in:

 the top part of the still

 the reboiler tubes
 the heat exchangers
 some connecting piping

Hydrogen blisters are sometimes evident after many years of service in the shell of the
contactor or still. Hydrogen-induced cracking can also occur in welds in the vessels or piping
after many years of service. Corrosion/erosion can occur in areas where fluid velocities are
high, such as:

 in the return line from the reboiler

 at the point of entry of the reboiler vapors into the still
 downstream of pressure letdown valves

As compared with CO2 and H2S mixtures, corrosion rates in amine systems, especially MEA
systems, generally increase with:

 increasing temperature
 increasing amine concentration

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 increasing mole loadings

 pure acid gas

MEA is generally much more corrosive than DEA, and MDEA is only slightly corrosive. Use
of Corrosion Inhibitors. The use of corrosion inhibitors is a common practice to reduce the
attack on steel by H2S and CO2 in aqueous environments. In most sour gas sweetening
installations, a corrosion inhibitor is continuously injected into the sweetening solution.

Solvent Loss

In all regenerative solvent systems, it is necessary to periodically add pure solvent to the
solution because of the loss of solvent during operation. Solvent losses in gas treating
systems can occur because of:

 vaporization
 entrainment
 degradation and removal of degradation products
 mechanical losses

Solvents used in gas treating, like any other liquids, have a vapor pressure that increases with
temperature. In a gas sweetening system, there are three vessels where gas and liquid streams
separate:

 contactor
 flash tank
 reflux drum

By far the largest gas stream is the one leaving the contactor. To reduce the solvent losses
from this source, a water wash process is usually applied to the treated gas downstream of the
contactor. Solvent losses from the flash tank are usually quite small, as the amount of gas
leaving this vessel is usually small when compared to the total plant stream. When the
solution is regenerated in the still, some solvent leaves the still overhead with the acid gas
stream and the water vapor. Upon cooling the still overhead stream and condensing most of
the water and amine, the liquid is returned to the top of the still as reflux, which also recovers
most of the solvent. Nevertheless, some solvent vapor leaves the top of the reflux drum with
the acid gas stream. Lower reflux drum temperatures reduce solvent losses at this point.

Entrainment of solvent occurs during foaming or under high gas velocity situations. By
preventing foaming and by staying within design throughput, entrainment losses can be
avoided.

In amine systems, some degradation of the solvent occurs. Primary amines are most
susceptible to this problem, and such systems require special separation equipment to
periodically remove the degradation products that contribute to corrosion. The degradation
products are mainly caused by irreversible reactions between the solvent and CO2.

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The most serious losses of solvent usually result from mechanical actions or problems. These
include:

 filter changeouts
 drips from pumps or flanges
 vessel cleaning and draining

Sulfur Recovery
 25% of the natural gas being brought into production from new sources requires H2S
removal and disposal.
 Currently only two methods are available for dealing with large quantities of H2S:

 Disposal of the gas by injection into underground formations

 Conversion of the H2S into a usable product, elemental sulfur

Where environmental regulations permit and production of elemental sulphur is not

economically attractive, injection wells provide a safe means for H2S disposal. However,
more commonly, H2S is converted into elemental sulfur, much of which goes into sulfuric
acid production. The most common method of converting H2S into elemental sulfur, is the
Claus process or one of its modifications. Two modified Claus configurations: straight
through and split flow

The straight-through process is the preferred and simplest, and it can process feed streams
that contain more than 55 mol% H2S; with air or acid gas preheat, it can process 30 to 55
mol% H2S in the feed. The split-flow configuration can process feeds that contain 5 to 30
mol% H2S. Lower concentration feeds require other variations. The straight-through process
provides the highest sulfur-recovery efficiency.

The exit stream from Claus plants usually cannot meet environmental emission requirements,
and, consequently, a tail gas cleanup unit (TGCU) is often employed to eliminate the last of
the sulfur compounds. The most commonly used processes are Shell Claus Offgas Treating
(SCOT), SUPERCLAUS, and cold-bed adsorption (CBA).

PROPERTIES OF SULFUR

The thermophysical properties of sulfur are unusual.

Sulfur vapor exists as Sx, where x can have values from 1 through 8 (allotropes of sulphur;
Sulfur has a large number of allotropes, second only to carbon).

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Figure1: Sulfur-vapor species as a function of temperature.

Figure1 shows the distribution of sulfur-vapor species as a function of temperature. Note that
at lower temperatures, S8 dominates, but as the temperature rises S8 converts to S6, and
finally to S2. The sequence is not unexpected, because increased temperature means
increased energy for the molecules, which leads to the breakup of the clusters. The formation
of sulfur clusters has a very pronounced effect on the physical properties that have a
significant effect on processing operations, notably viscosity (fluid flow) and heat capacity
(heat transfer).

SULFUR RECOVERY PROCESSES

CLAUS PROCESS

All Claus units involve an initial combustion step in a furnace. The combustion products then
pass through a series of catalytic converters, each of which produces elemental sulfur.

The Claus process consists of the vapor-phase oxidation of hydrogen sulfide to form water
and elemental sulfur, according to the overall reaction:

3 H2S + 3/2 O2 → 3 H2O + (3/x) Sx .........................(i)

The above overall reaction does not represent the reaction mechanism or show intermediate
steps. In practice, the reaction is carried out in two steps:

H2S + 3/2 O2 ↔ H2O + SO2 .....................................(ii)

2 H2S + SO2 ↔ 2 H2O + (3/x) Sx.............................(iii)

The first reaction is a highly exothermic combustion reaction, whereas the second is a more
weakly exothermic reaction promoted by a catalyst to reach equilibrium.

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Figure2: Equilibrium conversion of hydrogen sulfide to sulfur.

Figure2 shows the equilibrium conversion obtained for H2S into elemental sulfur by the
Claus reaction. Kohl and Nielsen (1997) state that the unusual shape of the equilibrium curve
is caused by the existence of different sulfur species at different reaction temperatures. They
point out that at a sulphur partial pressure of 0.7 psia (0.05 bar) and temperatures below
700°F (370°C), the vapor is mostly S6 and S8, but at the same partial pressure and
temperatures over approximately 1,000°F (540°C), S2 predominates. This shift in species
causes the equilibrium constant in the reaction to shift from a downward slope to an upward
slope, as shown in Figure. This behavior has a significant effect on the operation of the Claus
process.

The melting point of amorphous sulfur is 248°F (120°C), and its normal boiling point is
832°F (445°C). Figure 2 shows that the maximum conversion to sulfur by reaction (i) is
obtained at temperatures near the melting point of sulfur, but to maintain sulfur in the vapor
state, relatively high temperatures are required. Consequently, if the catalytic converters are
to operate under conditions in which the sulfur does not condense on the catalyst, they cannot
operate at optimum equilibrium conversion. This is the reason for having a series of
converters, with the sulfur product withdrawn from the reacting mixture between converters.
Withdrawing the sulfur product causes the reaction (iii) to shift to the right, which results in
more sulfur product.

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Process

Figure: Straight-through Claus unit.

Figure presents a simplified flow diagram for the Straight-through Claus unit. In the straight-
through configuration, the first reaction takes place in a combustion furnace operating near
ambient pressure (3 to 8 psig). The air flow rate is adjusted to react with one third of the H2S,
along with any other combustibles, such as hydrocarbons and mercaptans. The H2S reaction
is exothermic (637 Btu/scf, or 24,000 kJ/m3, at 25°C at 1 atm) and is used to produce steam
in a waste-heat boiler. Both reactions take place in the furnace−boiler combination, and the
gases exit the waste-heat boiler in the range of 500 to 650°F (260 to 343°C), which is above
the sulfur dew point, so no sulfur condenses in the boiler.

The combustion furnace−boiler is followed by several catalytic reactors in which only the
second reaction takes place because all the O2 has been consumed in the furnace. Each
catalytic reactor is followed by a condenser to remove the sulfur formed. The gas is cooled to
300 to 400°F (149 to 204°C) in the condenser to remove elemental sulfur. The condenser
generally achieves cooling by heat exchange with water to produce low-pressure steam.
Vapor that leaves the condenser is at the sulfur dew point, so the gas is reheated before
passing to the next converter to prevent sulfur deposition on the catalyst.

A combustion-furnace flame temperature of 1700°F (927°C) should be maintained because

the flame is not stable below this value. The straight-through configuration cannot be used at
H2S concentrations below 55%, because the feed gas heating value is too low.
Concentrations as low as 40% are acceptable, if the air or acid gas is preheated.

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Figure: Split-flow Claus unit. Typically two thirds of feed bypasses the reaction

furnace.

For H2S concentrations in the range 25 to 40%, the split flow configuration can be utilized. In
this scheme, the feed is split, and one third or more of the feed goes to the furnace and the
remainder joins the furnace exit gas before entering the first catalytic converter. When two
thirds of the feed is bypassed, the combustion air is adjusted to oxidize all the H2S to SO2,
and, consequently, the necessary flame temperature can be maintained. The split-flow process
has two constraints:

1. Sufficient gas must be bypassed so that the flame temperature is greater than approximately
1,700°F (927°C).

2. Maximum bypass is two thirds because one third of the H2S must be reacted to form SO2.

If air preheating is used with the split-flow configuration, gases with as little as 7% H2S can
be processed. Generally, the sulfur recovery in the conventional plants discussed above varies
from 90 to 96% for two catalytic converters. It increases to 95 to 98% for three catalytic
converters.

CLAUS TAIL GAS CLEANUP

Before sulfur emissions restrictions were imposed, the offgas from the Claus unit was flared
to convert the remaining H2S to SO2. Now, environmental agencies demand higher sulfur
recovery and additional treating of the Claus tail gas is needed. The tail gas cleanup entails
either an add-on at the end of the Claus unit or a modification of the Claus unit itself. The
processes for this final sulfur removal are generally divided into three categories:

 Direct oxidation of H2S to sulfur

 Sub-dew point Claus processes
 SO2 reduction and recovery of H2S

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Direct Oxidation of H2S to Sulfur

Figure: SUPERCLAUS unit.

SUPERCLAUS is an example of selective oxidation for final sulfur removal. This process
involves a slightly modified two-stage Claus unit followed by a third-stage catalytic reactor to
oxidize the remaining H2S to elemental sulfur. Figure shows the overall process.

Reactors 1 and 2 use the standard Claus catalyst, whereas the third reactor contains the
selective oxidation catalyst. The Claus unit itself is operated with a deficiency of air so that
the gas that exits the second reactor contains 0.8 to 3 vol% H2S. Sufficient air is added to this
exit gas to keep the oxygen level in the 0.5 to 2 vol% range. The mixture then goes to the
third reactor, where the following catalytic reaction occurs:

2H2S + O2 → 2S + 2H2O

The selective oxidation catalyst in the third reactor does not promote the reaction

2H2S + 3O2 ↔ 2SO2 + 2H2O

or the reverse reaction of sulfur with H2O

3S + 2H2O ↔ 2H2S + SO2

and, consequently, a total recovery rate of 99% or higher can be reached.

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Sub-Dew Point Claus Processes

This category has several processes, the cold-bed adsorption (CBA) process is the most
widely used sub-dew point process.

Figure: Cold-bed adsorption unit. Dashed line denotes regeneration stream.

Figure shows one of its many possible variations. The front end of the unit is a Claus reactor,
and the sub-dew point process takes place in the final two catalytic converters, CBA #1 and
CBA #2. One converter is in service while the other is being regenerated. After the gas leaves
the final condenser, it is not reheated but is sent to the third converter (CBA #2), which is
operated at a temperature well below the sulfur dew point. This flow results in a better
equilibrium conversion but deposits sulfur on the catalyst and causes a gradual loss of
activity. During the period that CBA #2 is in service, CBA #1 is being heated and regenerated
with a slip stream from Claus #1. After regeneration is complete, the reactor can be cooled
with a slip stream from the final condenser. When the catalyst in CBA #2 is exhausted, valves
are switched, and CBA #1 becomes the adsorbing reactor while CBA #2 undergoes
regeneration. Total sulfur recoveries greater than 99% can be obtained with CBA processes.

Reduction of SO2 and Recovery of H2S

Figure: Shell Claus Offgas Treating (SCOT) unit.

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The SCOT process is an example of the process that reduces the SO2 in the Claus plant
offgas back to H2S. It then uses amine treating to remove the H2S, which is recycled back to
the Claus plant for conversion to elemental sulfur. The process can produce an exit gas that
contains 10 to 400 ppmv of total sulfur, while increasing total sulfur recovery to 99.7% or
higher. Figure shows a simplified process flow diagram of the SCOT process.

The feed, offgas from the Claus unit, is heated to 575°F (302°C) in an inline burner, along
with a reducing gas, H2 or a CO and H2 mixture. The reducing gas is supplied either from an
outside source or generated by partial oxidation in an inline burner. The mixture then flows to
the SCOT catalytic reactor (cobalt−molybdenum on alumina), where the sulfur compounds,
including SO2, CS2, and COS are reduced to H2S and water. The gas that leaves the reactor
goes to a waste-heat exchanger, where it is cooled to about 320°F (160°C) and produces low-
pressure steam. The gas from the waste-heat exchanger then flows through a quench tower,
where it is cooled to approximately 100°F (38°C) by externally cooled recycle water in
countercurrent flow. The water from the tower is condensed, and the excess water is sent to a
sour water stripper. Gas from the quench tower then contacts an aqueous amine solution in
the absorption column. The amine is generally methyldiethanolamine (MDEA) or
diisopropylamine (DIPA) to absorb H2S while slipping CO2. The gas that exits the top of the
absorber contains very little H2S (10 to 400 ppm) and is sent to an incinerator. The rich
amine that leaves the bottom of the absorber flows to the regenerator, where heat is applied to
strip the H2S from the amine solution. The overhead from the regenerator is cooled to
condense the water, and the H2S is recycled to the Claus unit. Lean amine is cooled and
returned to the absorber.

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