ChE 4763

Natural gas and Petroleum Engineering

Md. Jahirul Islam

Lecturer
Department of Chemical Engineering
Dhaka University ofEngineering and Technology, Gazipur
Desulfurization/Sweetening
Process

© Md. Jahirul Islam , Lecturer

 Sweet Gas and Acid Gas

Natural gas containing H2S are classified as sour gas Natural gas free
of H2S is called sweet gas.

Removing H2S from Natural gas is called sweetening

© Md. Jahirul Islam

 Reasons for Removal of H2S and CO2

Reasons for removal of H2S:

• H2S is deadly poisonous and corrosive to all metal normally associated with gas transporting, processing
and handling systems; this can lead to premature failure to the system.
• On combustion H2S forms SO2 which is highly toxic and corrosive.
• H2S and other sulfur compounds can cause catalyst poisoning in refinery processes.
• H2S promotes hydrate formation
• It’s a contractual requirement from clients to reduce Sulfur content. Usually the
maximum allowable quantity is 4ppm

Reasons for removal of CO2 :

• CO2 has no heating value
• CO2 forms complex CO2. CO2 which is corrosive in presence of water
• For gas being sent to cryogenic plants, removal of CO2 is necessary to prevent solidification of CO2.
• CO2 promotes hydrate formation

© Md. Jahirul Islam

 Classification of H2S Removal Process

It is primarily of two types.

o Physical/chemical adsorption on a solid
o Physical/chemical absorption into liquid.

• The above two processes can be classified into the followings.

o Non regenerative: Chemsweet process

o Regenerative process with recovery of H2S: Physical absorption process
(water wash, selexol, fluor solvent), amine process, hot carbonate
process, molecular sieve process.
o Regenerative process with recovery of elemental S: Holmes stretford
process.
© Md. Jahirul Islam
 Criteria for Process Selection

 The types and concentrations of impurities in the gas and the degree of removal
desired.
 Temperature and pressure at which the sour gas is available and at which sweet
gas is delivered.
 Volume of gas to be processed and HC composition. CO2 and
H2S ratio in the gas.
 Economics of the process.
 The desirability of the S recovery due to environmental problems.

© Md. Jahirul Islam

 Solid Bed Sweetening Process

It is based upon physical or chemical adsorption of acid gases on the solid surface.
Advantages:
 It offers simplicity, high selectivity and process efficiency which is pressure
independent.
 It is best applied to gases with moderate concentrations of H2S and where CO2 is to be
retained in the gas.
 It is relatively inexpensive.
Disadvantages:
 There is a difficult and expensive regeneration. Excessive pressure loss through the bed.
 Inability to remove large amount of sulfur.
 Sulfur disposal problems since it does not produce saleable sulfur form.

© Md. Jahirul Islam

 Iron Sponge Unit
Reaction Unit: Sour gas is passed through a bed of wood chips that have been
impregnated with a special hydrated form of ferric oxide that has high affinity for H2S.

F e2O 3  3 H 2 S  F e2 S 3  3 H 2O
• Without the water of hydration, the reaction will not proceed. Thus, the operating
temperature should be below 120℉ or a supplemental water spray should be provided.
• The reaction requires the presence of slightly alkaline water and a pH level on the
order of 8–10 should be maintained through the injection of caustic soda with the
water.
• The process operates in a batch type reaction regeneration cycle.
Regeneration unit: Iron oxide is regenerated by passing air over bed. The reaction with
oxygen, is exothermic and air must be introduced slowly so the heat of reaction can be
dissipated.
2 F e 2 S 3  3O 2  F e 2 O 3  6 S
© Md. Jahirul Islam
 Iron Sponge Unit

air serves to regenerate the iron

oxide continuously, which has
reacted with hydrogen sulfide ,
serves to extend the on-stream
life of a given tower but probably
serves to decrease the total
amount of sulfur that a given
weight of bed will remove
If the gas
does not
contain
Sufficient
water

© Md. Jahirul Islam

 Pros/Cons of Iron Sponge Process

• High labor costs for removing packed beds. Operation is simple

• Low capital costs
• The process is usually best applied to gases containing low to medium
• concentrations (300 ppm) of hydrogen sulfide or mercaptans.
• This process tends to be highly selective and does not normally remove significant
quantities of carbon dioxide.
• Some of the elemental sulfur produced in the regeneration step remains in the bed.
• After several cycles this sulfur will cake over the ferric oxide, decreasing the reactivity
of the bed. Typically, after 10 cycles the bed must be removed and a new bed
introduced into the vessel.

© Md. Jahirul Islam

 Molecular Sieve Process

• Synthetic crystalline sodium-calcium Alumino Silicate sieve bed

• It is porous in structure and has very large surface area.
• Remove components through a combination of a "sieving" and physical adsorption
process.
• It adsorbs the molecules on the basis of their size.
• The sieve posses highly localized charge on the surface area that acts as the
adsorption site for the polar material.
• It offers high H2S adsorption efficiency.
• It offers a mean of simultaneous dehydration and desulfurization.

© Md. Jahirul Islam

 Molecular Sieve Process

Factors affecting Molecular Sieve Process

• H2S adsorption capacity increases with increasing H2S/CO2 ratio and decreases with
increasing temperature.
• Increasing contact time H2S adsorption is favorable up to a point, beyond that there is
no effect.
• Optimum operating pressure is about 450 psia.

© Md. Jahirul Islam

 Molecular Sieve Process

• The bed is regenerated by passing a portion of the sweetened gas, preheated to about
400-600°F or more, for about 1.5 hours to heat the bed.
• As the temperature of the bed increases, it releases the adsorbed H2S into the
regeneration gas stream.
• The sour effluent regeneration gas is flared off.
• About 1-2% of the gas treated is lost in this regeneration process.

© Md. Jahirul Islam

Molecular Sieve Process

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 Pros and Cons of Molecular Sieve Process

• Besides regeneration losses. gas is also lost by the adsorption of hydrocarbon components
by the sieve.
• Unsaturated hydrocarbon components such as olefins and aromatics tend to be strongly
adsorbed.
• Molecular sieves are also prone to poisoning by several chemicals such as glycols and
require thorough gas cleaning methods prior to the adsorption step.
• The process requires a cyclic operation, since it is batch-type, with a cycle time on the order
of 2 hours.
• Initial capital investments are high, and regeneration requires a lot of heat. For gas streams
containing CO2, carbonyl sulfide may form as shown in the following reversible reaction:
H2S + CO2 = COS + H2O
Molecular sieves tend to catalyze this reaction.
© Md. Jahirul Islam
 Physical Absorption Process

Water Wash (Aquasorption) Process

• This process is effective for high pressure gas, with high acid gas content and high H2S
to CO2 ratio.

• According to Maddox (1982), a water wash operation followed by an amine process is

12 to 15% lower in capital investment, and about 50% lower in operating expenses as
compared to a single amine unit for an equivalent sweetening job. For gases with a
high H2S to CO2, ratio, the savings can be as much as 40% in investment, and 60 to 70%
in operating costs.

© Md. Jahirul Islam

 Physical Absorption Process

Water Wash (Aquasorption) Process

• In the water wash sweetening process, sour gas is sent upward through a contactor,
countercurrent to the water.
• The partially sweetened gas from the top of the tower is sent to further treatment
units (typically, an amine unit).
• The rich water solution from the bottom of the tower is sent to an intermediate
pressure flash tank for recovery of dissolved hydrocarbons.
• A power recovery turbine is provided for repressurizing the water before sending it to a
low pressure flash tank where all of the acid gas is removed, and the lean water
obtained is recycled.

© Md. Jahirul Islam

Physical Absorption Process

Figure: A typical water wash process.

© Md. Jahirul Islam
 Physical Absorption Process

Selexol Process
• This process uses dimethyl ether of polyethylene glycol (DMPEG) as a solvent.
Solubilities in Selexol solvent of H2S and CO2 and other acid gas components are
directly proportional to the partial pressures of these components.
• The solubility of H2S is about 10 times greater than CO2 and hydrocarbon solubility is
quite small. Heavier hydrocarbons. however, have greater solubility. and intermediate
flashes are generally required for hydrocarbon removal

© Md. Jahirul Islam

 Physical Absorption Process

Selexol Process
• Figure 6-3 shows a flow scheme for a low H2S to CO2 ratio gas. Sour gas, pretreated to
remove any solids and free liquids, is dehydrated, cooled to 40°F. and sent to the
absorber for a countercurrent contact with Selexol solvent.
• Rich selexol from the bottom of the absorber is sent, via a surge tank to remove
entrained gas that is recycled back into the absorber. and a power recovery turbine for
pressurizing the solvent, to a high pressure flash. Most of the absorbed methane and
some of the CO2 is released in this flash and is recycled to the absorber.
• In the second flash stage, most of the vapor released is CO2 and it is vented after power
recovery. Finally, the Selexol is sent to the low pressure flash, which is operated at 16
psia, Here, H2S and the remaining CO2 are flashed off as the vapor stream, which is
vented to the atmosphere.

© Md. Jahirul Islam

Physical Absorption Process

H2S and CO2

CO2

Removes entrained gas

Methane and CO2

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 Chemical Absorption Process

• Chemical solvent process uses an aqueous solution of a weak base to chemically

react with and absorb the acid gases in the natural gas stream.
• The absorption occurs as a result of the driving force of the partial pressure from the
gas to the liquid.
• The reactions involved are reversible by changing the system temperature or
pressure or both.
• The aqueous base solution can be regenerated and thus circulated in a continuous
cycle.

© Md. Jahirul Islam

 Alkaline Amine Process
• Most prominent and widely used process for H2S and CO2 recovery.
• It offers good selectivity at low cost, good flexibility in design and operation.
• Solvents like MEA,DEA, TEA are normally used in this process.

© Md. Jahirul Islam

Alkaline Amine Process

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 Comparison of MEA & DEA as solvent

• MEA has greater cleaning efficiency (H2S)

• DEA has lower vapor pressure, hence DEA loss is very insignificant compared to MEA

• DEA is less corrosive

• Low circulation rate is required for removing same amount of Sour gas

• Less heat per volume is required to regenerate DEA

© Md. Jahirul Islam

 Problem: Amine process

Given:
Qg=100MMscfd
S.G=0.67
H2S inlet =19ppm
H2S outlet =4ppm
CO2 inlet= 4.03%
CO2 outlet=2%
CD(contactor)=0.689
P=1000psig
T=100oF

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

Problem: Amine process

© Md. Jahirul Islam

 Carbonate Process

• The basic hot carbonate process uses an aqueous solution of potasium carbonate
• A highly concentrated solution is used to improve process performance.
• 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
• Uses an aqueous solution of K2CO3 or a solution of sodium carbonate and bicarbonate
with a ratio of 1:3 resulting a pH of about 8.5 to 9.5.
• Hot K2CO3 solution is extremely corrosive. Hence corrosion inhibitors like Fatty amines or
Potassium dichromate are used to decrease corrosion
• Not efficient to achieve low H2S content HC

© Md. Jahirul Islam

Carbonate Process

© Md. Jahirul Islam

 Elemental Sulfur Recovery
There are two common methods of sulfur recovery:
1.Liquid redox and
2.Claus sulfur recovery processes.

•Liquid redox sulfur recovery processes are liquid-phase oxidation processes that use a
dilute aqueous solution of Iron or Vanadium to remove H2S selectively by chemical
absorption from sour gas streams.
•The mildly alkaline lean liquid scrubs the H2S from the inlet gas stream, and the catalyst
oxidizes the H2S to elemental sulfur.
•The Claus process is used to recover sulfur from the amine regenerator vent gas stream
in plants where large quantities of sulfur are present
•The reduced catalyst is regenerated by contact with air in the oxidizer(s).
•Sulfur is removed from the solution by flotation or settling, depending on the process.

© Md. Jahirul Islam

 Sulfur Recovery Process (Claus Process)

The chemistry of the units involves:

1. Partial oxidation of hydrogen sulfide to sulfur dioxide and
2. The catalytically promoted reaction of H2S and SO2 to produce elemental sulfur.

The reactions are staged and are as follows.

H2S + 3/2O2 → SO2 + H2O; thermal stage
SO2 + 2H2S → 3S + 2H2O; thermal and catalytic stage

© Md. Jahirul Islam