PMRE 413: Natural Gas Engineering

Desulfurization/Sweetening Process
Sweet Gas and Acid Gas

• Natural gas containing H2S are classified as sour gas

• Natural gas free of H2S is called sweet gas.
 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 CO 2 is necessary to prevent
solidification of CO2.
• CO2 promotes hydrate formation
Classification of H2S Removal Process

• It is primarily two types.

– Physical/chemical adsorption on a solid

– Physical/chemical absorption into liquid.

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

• Non regenerative: Chemsweet process

• Regenerative process with recovery of H2S: Physical absorption process (water
wash, selexol, fluor solvent), amine process, hot carbonate process, molecular
sieve process.
• Regenerative process with recovery of elemental S: Holmes stretford process.
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.
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 H 2S 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.
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.

Fe2O3  3H 2 S  Fe2 S3  3H 2O

a. Temperature should be at less than 120 oF.

b. 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.
c. 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 Fe2 S3  3O2  Fe2 O3  6 S
 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
 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.
 Problem: Iron sponge unit
Given:
Qg=2MMscfd
S.G=0.6
H2S=19ppm
P=1200psig
T=100oF
Design an iron sponge unit
1.
2. Maximum diameter to prevent channeling
3.

=19ppm
4.

d in inch
H in ft
Molecular Sieve Process
• Synthetic crystalline Sodium Alumino Silicate sieve bed
• It is porous in structure and has very large surface area.
• It is a 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.
• 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.
• Sieve bed is regenerated by flowing pre-heated (400-600oF) sweetend gas
• Sour effluent is flared, 1-2% of gas treated is lost for regeneration
Molecular sieve process
Physical Absorption Process

• This process rely upon physical absorption of acid components as the gas
sweetening mechanism
• Solubility of acid gases depend upon the partial pressure of acid gas and
temperature. Higher acid gas partial pressure and low temperature increases the
acid gas removal
• Corrosion and fouling problem are minimal
• Solvent used is recovered by flashing rich solvent in the flash tank at lower P
• No heat required for regeneration
• Offers good to fair selectivity
• Requires sulfur recovery unit since this processes do not alter the acid components
chemically in any manner
• Most solvents have relatively high solubility for heavier HC particularly aromatics
and unsaturated components. Hence danger of HC being lost with Sulphur
• Suitable process for Inlet gas with low concentration of C3+
Selexol Process Uses DMPEG
(Dimethyl Ether of Poly-Ethyline Glycol)

H2S and CO2

CO2

Removes entrained gas

Methane and CO2

 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.
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.
Outlet Condenser
Scrubber Reflux Drum

Reboiler

Inlet Flash
Booster
Scrubber Tank
 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
Solvent
1 ft3= 7.48 Gallons
 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

Carbonate Process

• This process converts H2S to S of 99.9% purity

• CO2 content remain unaltered
• 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
 T=230oF T=245oF
P=1atmp

Acid rich K2CO3

 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.
 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