Natural gas produced in gas fields is a mixture of hydrocarbons, mostly

C₁ through C₆+, inert gases (N₂, He, H₂, Ar, O₂), acidic gases (CO₂ and/or
H₂S), organic sulfur species (RSH, RSR, RSSR) and other impurities. The
H₂S content in soura natural gas spans 0.1 vol%–5 vol%, depending on
the location of fields and the ages of wells, while the concentration of
carbon dioxide (CO₂) ranges from 0.6 vol% to more than 15 vol%.

The acidic gases contained in natural gas must be removed in a

sweetening unit to meet sales gas specifications or to match the
feedstock quality requirements of LNG facilities. H₂S is toxic; it has an
odor similar to that of rotten eggs when its concentration falls to 0.01
ppm–1.5 ppm. At 100 ppm–150 ppm it causes the loss of smell, and at
concentrations higher than 1,000 ppm it causes nearly instantaneous
death with a single breath. Sales gas specifications typically require that
H₂S content be less than 4 ppm in volume.

CO₂ is non-toxic; however, if present at high concentrations it may lower

the natural gas high heating value (HHV). To achieve salable gas, CO₂
content must be kept in the range of 1 vol%–4 vol%. In cryogenic units
CO₂ can freeze out, causing operational problems; therefore, LNG
feedstock cannot contain more than 50 ppm of CO₂.

Mechanism
Chemistry of acid gases. H₂S is a proton donator, according to the
Brønsted acid definition, while CO₂ is an electron acceptor, or a Lewis
acid. Both are weak acids, with CO₂ being slightly stronger than H₂S. The
equilibrium solubility of CO₂ under absorber conditions is, therefore,
higher than that of H₂S. However, when H₂S dissolves in water, it swiftly
protonates water with one or two protons, depending on the pH of the
aqueous solution, as shown in Eqs. 1–2:

H₂S + H₂O ↔ HS– + H₃O+ (1)

HS- + H₂O ↔ S2– + H₃O+ (2)

CO₂ reacts slowly with water to form carbonic acid, which successively
dissociates into bicarbonate/carbonate ions, as shown in Eqs. 3–4:

CO2 + 2H2O ↔ HCO3– + H3O+ (3)

 HCO3– + H2O ↔ CO3²– + H3O+ (4)

The kinetics of CO₂ absorption can be improved by adding an activator to

the aqueous solution. The effect is similar to that of a homogeneous
catalysis. FIG. 1 shows a streamlined mechanism of an activated MDEA
aqueous solution.

This is the most common process used for H2S and C02 removal. Amines
are water-soluble, organic, nitrogen compounds that form a basic
solution in water. They react reversibly with acid-gas components to
form a water-soluble salt. The acid/base reaction is reversed in the
regenerator at low-pressure, high-temperature conditions. The acid gas
is removed at the regenerator overhead while the amine solution is
removed from the bottom and is recirculated to the absorber. Some of
the common amines used are:

a. Monoethanol amine (MEA)

b. Diethanol amine (DEA)
c. Methyl diethanol amine (MDEA)
d. Diglycol amine (DGA)
e. Diisopropanol amine (DIPA)

With the exception of MDEA, amines are generally not selective and will
remove both C02 and H2S from the gas. MDEA will preferentially absorb
H2S over C02 due to faster reaction time. Amines frequently are
"engineered" to increase selectivity and/or absorption capacity. Most
amine solutions are ineffective in removing other sulfur species such as
mercaptans and COS.
Process flow schemes.
The generalized process setup for sweetening operations combines an
absorption unit and a regeneration unit operation, as shown in FIG. 2.
The raw natural gas is contacted by the aqueous solvent (lean solvent) in
the absorption tower, where it picks up the CO₂ and H₂S contained in the
gas. The rich solvent, loaded with acid gases, is extracted from the
bottom of the absorber and regenerated in the stripping tower by
heating, after being flashed in the flash drum. The lean solvent
withdrawn from the regeneration column, generally operated at P < 2
barg and around 125°C, is cooled and recycled in the absorber. The
sweet gas extracted from the top of the absorber is routed to the
dehydration unit, while the acid gas stream exiting the regenerator
overhead KOD is delivered to a sulfur recovery unit.

The presence of a flash drum in the rich solvent circuit depends on the
solubility of hydrocarbons in the solvent. Chemical solvents (MEA, DEA,
MDEA) normally do not require a flash drum, while the physical and
hybrid solvents do require it. As mentioned previously, the process
schemes for physical solvents may feature multiple flash drums between
the absorber and the stripper column.

The technology outlined in FIG. 2 is used in relatively large gas

processing operations for removing at least 20 tpd of sulfur from natural
gas. However, for smaller quantities of H₂S and when deep removal of
acid gases is required, this process may prove uneconomical. In such
cases, adsorption onto solid material (sorbent), chemical conversion and
membrane processes may be considered.