Sweetening of Natural

gas and sulphur recovery

PREPARED BY
ARCHANA
Acid Gas Removal
In addition to water & natural gas liquids removal, one of the most important parts of gas
processing involves the removal of hydrogen sulfide & carbon dioxide.

Natural gas from some wells contains significant amounts of H2S & CO2 & is usually
referred to as sour gas
Sour gas is undesirable because the sulfur compounds it contain can be extremely
harmful, even lethal, to breathe, & the gas can be extremely corrosive
The process for removing H2S from sour gas is commonly referred to as sweetening the
gas
Acid gas removal(i.e. removal of CO2 & H2S from natural gas streams) is achieved by
absorption and/or adsorption
Both the adsorption & absorption processes may be of the physical ( no chemical
reactions involved) or chemical type.
Sweetening Process
Adsorption Process:
Iron Sponge
Sulfa Treat
Zinc Oxide
Molecular sieves
Absorption Process: liquid absorption processes ( which usually employ temperatures
below 50C, 120F) are classified as physical solvent processes or chemical solvent
processes.
Physical solvent processes employ an organic solvent, and absorption is enhanced by low
temperatures, or high pressure, or both
In chemical solvent processes, absorption of the acid gases is achieved mainly by use of
alkaline solutions, such as amines or carbonates
Chemical solvents : Absorption process

Monoethanol amine(MEA)
Diethanol amine(DEA)
Methyldiethanol amine(MDEA)
Diglycol amine(DGA)
Diisopropanol amine(DIPA)
Hot potassium carbonate
Proprietary carbonate systems
Physical solvents : Absorption process

Fluor Flexsorb
Shell Sulfinol
Selexol
Rectisol
Direct conversion of H2S to sulfur

Claus
LOCAT
Stretford
IFP
Sulfa-check
 Solid bed Sweetening processes: The Iron Sponge
Process
Sour gas is passed through a bed of wood chips that have been impregnated with a special hydrated
form of ferric oxide that has a high affinity for H2S.

The process is one of several metal oxide-based processes that scavenge hydrogen sulfide & organic
sulfur compounds (mercaptans) from gas streams through reactions with solid-based chemical
adsorbent
The process is governed by the reaction of a metal oxide with hydrogen sulfide to form the metal
sulfide
The chemical reaction is as follows
+3+3
The temperature must be kept at less than 120F.
for regeneration, the metal oxide is reacted with oxygen to produce elemental sulfur & the
regenerated metal oxide
Iron oxide is regenerated by passing oxygen/air over the bed
2 +3 = 2 + 6S
 The Iron Sponge Process
The process operates in a batch-type reaction-regeneration cycle.
The process is usually best applied to gases containing low to medium concentrations (300 ppm) of H2S or
mercaptans.
This process tends to be highly selective & does not normally remove significant quantities of CO2
The use of iron sponge process for sweetening sour gas is based on adsorption of the acid gases on the
surface of the solid sweetening agent followed by chemical reaction of ferric oxide with H2S.

The reaction requires the presence of slightly alkaline water & a temperature below 43C (110F).
Bed alkalinity (pH +8 to 10) should be checked regularly, usually daily
The pH level is to be maintained through the injection of caustic soda with the water.
if the gas does not contain sufficient water vapor, water may need to be injected into the inlet gas stream
Regeneration of the bed, however, is quite difficult & incus excessive maintenance & operating costs
Also, sulfur eventually covers most of the surface of the ferric oxide particles & further regeneration
becomes impossible.
The Iron Sponge Process
A continuous regeneration process has also been developed, where small amounts of oxygen
or air are added along with the sour gas at the inlet

Some of the elemental sulfur produced in the regeneration step remains in the bed.
After several cycles this sulfur will cake over ferric oxide, decreasing the reactivity of the bed.
Continuous regeneration process gives an improved performance, generating a higher
removal efficiency as well as better regeneration
There are several disadvantage
difficult & expensive regeneration
excessive pressure losses through bed
inability to remove large amount of sulfur, and sulfur disposal problems ( sulfur does not
produce in saleable form)
The Iron Sponge Process:

 Sulfa Treat
This is similar to the iron sponge process

Efficient SulfaTreat process is also iron based using porous form of iron oxide & therefore has much
larger capacity per unit volume of the bed
SulfaTreat beds are much smaller for the same gas capacity when compared to iron sponge beds. Iron
is a very strong oxidizing element & oxidizes sulfur compounds & neutralize them either to other forms
of less harmful sulfur compounds or to the elemental sulfur itself
It uses a patented proprietary mixture of ferric oxide & triferric oxide to react with H2O to sweeten gas
streams.
In sulfa Treat process the iron oxides are supported on the surface of an inert, inorganic substrate
forming a granular material, while in the iron sponge process the ferric oxide is impregnated on wood
chips.
In this process, product can be recycled or disposed in a landfill
Two vessels arranged in series, a lead/lag arrangement, will allow the sulfaTreat material to be used
more efficiently with no interruption in unit service & greater process reliability
Sulfa Treat
The first vessel, the lead unit, acts as the working unit to remove all the H2S at the
beginning of a treatment period with its outlet H2S increasing over time
The exit gas from the first vessel can go to the second vessel, the lag unit, for further
polishing or bypass the second vessel as though the first vessel is operating in a single
vessel arrangement
The second vessel is to be placed in operation as the lag unit to polish the H2S remaining
in the gas when the lead unit outlet H2S starts to approach the specification
Once the lead unit inlet & outlet concentrations are equal, the SulfaTreat material is
considered spent or exhausted .
Then, the gas flow is directed to the second vessel, which becomes the lead unit.
The spent material is removed from the first vessel & the fresh SulfaTreat material
reloaded to be placed into operation as the lag unit without gas flow interruption.
Sulfa Treat

 Zinc Oxide
The zinc oxide process is similar to the iron sponge process

It uses a solid bed of granular zinc oxide to react with the H2S to form water & Zinc sulfide
ZnO + H2S -> ZnS + H2O
The rate of reaction is controlled by the diffusion process, as the sulfide ion must first diffuse to the
surface of the zinc oxide to react
High temperature (> 250F) increases the diffusion rate & is normally used to promote the reaction rate
Zinc oxide is usually contained in long, thin beds to lessen the chances of channeling
Pressure drop through the beds is low
Bed life is a function of gas H2S content & can vary from 6 months to in excess of 10 Years
The spent catalyst is discharged by gravity flow & contains up to 20 weight percent of sulfur
The process has seen decreasing use due to increasing disposal problems with the spent catalyst,
which is classified as a heavy metal salt
Solid bed Sweetening processes: Molecular Sieves Process
 Solid bed Sweetening processes: Molecular Sieves Process
The molecular sieve process uses synthetically manufactured solid crystalline zeolite in a dry bed to
remove gas impurities
Molecular sieves are porous in structure with all the pores exactly the same size & have a very large
surface area
Molecular sieves remove components through a combination of a sieving & physical adsorption process
They are highly selective in the removal of H2S & other sulfur compounds from natural gas
Within the pores the crystal structures creates a large number of localized polar charges called active
sites.
Polar gas molecules, such as H2S & water, that enter the pores form weak ionic bonds at the active sites.
Nonpolar molecules such as paraffin hydrocarbons will not bond to the active sites.
Thus, molecular sieves units will dehydrate the gas ( remove water vapor) as well as sweeten it.
They remove water also ( a polar compound) & thus offer a means of simultaneously dehydration &
desulfurization
Molecular sieve should be selected with a pore size that will admit H2S & water while preventing heavy
HCs & aromatic compounds from entering the pores
 Molecular Sieves Process
CO2 molecules are about the same size as H2S molecules & present problems.
CO2 is non-polar & will not bond to the active sites, the CO2 will enter the pores.

Small quantities of CO2 will become trapped in the pores & this way small portion of CO2 are removed
This way CO2 will obstruct the access of H2S & water to active sites & decrease the effectiveness of the pores
The process flow scheme is similar to the iron sponge process.
The bed is regenerated by passing a portion of the sweetened gas, preheated to about 400-600F 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
According to Rushton & Hays(1961), about 1-2% of the gas treated is lost in the regeneration process
Besides regeneration losses, gas is also lost by the adsorption of hydrocarbon components by sieve
Unsaturated hydrocarbon components such as olefins & aromatics tend to be strongly adsorbed (Conviser, 1965)
Molecular sieves are also prone to poisoning by several chemicals such as glycols & 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
Absorption Process: Physical solvent Processes
These processes are based on the solubility of H2S &/or CO2 within the solvent
Instead of on chemical reactions between the acid gas & the solvent
Solubility depends first & foremost on the partial pressure & secondarily on temperature
Higher pressure & temperature increase the solubility of H2S & CO2 in the solvent &
thus decrease the acid-gas components
Various organic solvents are used to absorb the acid gases
Regeneration of the solvent is accomplished by flashing to lower pressures &/or stripping with
solvent vapour or inert gas
Some solvents can be regenerated by flashing only & require no heat
Other solvents require stripping & some heat for regeneration of the solvents
Solvent regeneration heat requirement is less in physical solvent process as compared to
chemical solvent process
Physical solvents processes have a high affinity for heavy hydrocarbons
Under following circumstances physical solvent
processes should be considered for gas sweetening

The partial pressure of the acid gases in the feed is 50psi or higher
The concentration of heavy HCs in the feed is low. That is, the gas stream is lean in
propane-plus
Only bulk removal of acid gases is required
Selective H2S removal is required
Physical Solvent Process
Physical Solvent Process
The sour gas contacts the solvent using counter-current flow in the absorber

Rich solvent from the absorber bottom is flashed in stages to a pressure near atmospheric
This causes the acid-gas partial pressures to decrease
The acid gases evolve to the vapor phase & are removed
The regenerated solvent is then pumped back to the absorber
In the above process, flashing is sufficient to regenerate the solvent
Some solvents require a stripping column just prior to the circulation pump
Most physical solvent processes are proprietary & are licensed by the company that
developed the process
 Fluor Flexsorb Solvent Process
This process uses propylene carbonate as a physical solvent to remove CO2 & H2S

Propylene carbonate also remove C2+ HCs, COS, SO2, CS2, & H2O from the NG stream
This process is used for bulk removal of CO2 & is not used to treat to less than 3 % CO2
The system requires special design features, large absorbers, & higher circulation rates to obtain pipeline quality
propylene carbonate has the following characteristics, which make it suitable as a solvent for acid gad treating:
High degree of solubility for CO2 & other gases
Low heat of solution for CO2
Low vapour pressure at operating temperature
Low solubility for light hydrocarbons ( C1, C2)
Chemically nonreactive toward all natural gas components
Low viscosity
Noncorrosive toward common metals
 Fluor Flexsorb Solvent Process
These characteristics combine to yield a system that has low heat & pumping requirements, is
relatively noncorrosive, & suffers only minimal solvent losses ( less than 1 lb/ MMscf)
Solvent temperature below ambient are usually used to increase the solubility of acid gas
components & therefore decrease circulation rates

Sulfinol Process:
It is licensed by Shell
Sulfinol process combines the properties of a physical & chemical solvent
Sufinol solution consists of a mixture of sulfolane ( tetrahydrothiophene 1-1 dioxide), which is a
physical solvent, diisoproponalamine(DIPA)( a chemical solvent), & water.
The physical solvent sulfolane provides the system with bulk removal capacity
Sulfolane is an excellent solvent of sulfur compounds such as H2S, COS, & CS2.
Aromatic & heavy hydrocarbons & CO2 are soluble in sulfolane to a lesser degree.
Sulfinol Process:
Sulfinol is usually used for streams with an H2S to CO2 ratio greater than 1:1 or where it
is not necessary to remove the CO2 to the same levels as is required for H2S removal
The physical solvent allows much greater solution loadings of acid gas than for pure
amine-based systems
Typically, a sulfinol solution of 40 % sulfolane, 40% DIPA & 20% water can remove 1.5
moles of acid gas per mole of Sulfinol solution
The chemical solvent DIPA acts as secondary treatment to remove H2S & CO2.
The DIPA allows pipeline quality residual levels of acid gas to be achieved easily
A stripper is required to reverse the reaction of the DIPA with CO2 & H2S. This add
additional cost to the system
Selexol Process

Selexol Process
This process uses dimethyl ether of polyethylene glycol (DMPEG) as a solvent

Solubilities in Selexol solvent of H2S& CO2 & 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 & hydrocarbon solubility is quite
small
Heavier hydrocarbons, however, have greater solubility, & intermediate flashes are
generally required for HCs removal
Hegwer & Harris (1970) describe three plants installed for a wide range of H2S to CO2
ratios
1. One plant for a high H2S to CO2 ratio
2. Low H2S to CO2 ratio
3. Gas containing large amounts of both H2S & CO2
Previous flow diagram for a low H2S to CO2 ratio gas
Selexol Process
Sour gas preheated to remove any solids & free liquids, is dehydrated, cooled to 40F

It is sent to the absorber for a countersurrent 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, & a power recovery turbine for pressurizing the
solvent, to a high pressure flash
Most of the absorbed methane & some of the CO2 is released in this flash, & is recycled to
the absorber
In the second flash stage, most of the vapor released is CO2 & it is vented after power
recovery
Finally, the Selexol is sent to the low pressure flash, which is operated at 16 psia.
In the low pressure flash, the H2S & the remaining CO2 are flashed off as the vapor
stream, which is vented to the atmosphere
Chemical Absorption
The Alkanol-Amine Processes : Most prominent & widely Used processes for H2S & CO2
removal

The Carbonate Processes

Alkanol-Amine Processes
Some commonly used alkanol-amines for absorption desulfurization are

Monoethanolamine (MEA)
Diethanolamine (DEA)
Triethanolamine (TEA)
Diglycolamine (DGA)
Di-isopropanolamine(DIPA)
Methyldiethanolamine(MDEA)
They are selected according to their relative ability to interact with & remove CO2 &/or
H2S
Among all above, MEA &DEA processes are most widely used
The chemistry can be represented by simple equations

For low partial pressures of the acid gases

At high acid-gas partial pressure, the reactions will lead to the formation of other products

The Carbonate Processes
Carbonate washing is a chemical conversion process in which contaminants in natural gas
are converted to compounds that not objectional
Basic hot carbonate process uses an aqueous solution of potassium carbonate

Both the absorber & the regenerator are operated at high temp of about 230-240 F
The process requires relatively high partial pressures of CO2
And this process can not be used for gas stream that contain only H2S
Difficult to treat gas to pipeline specification with this process
Direct conversion of H2S to sulfur

Claus
LOCAT
Stretford
IFP
Sulfa-check
Thank You