Raw natural gases contain variable amounts of carbon dioxide, hydrogen
sulfide, and water vapor. The presence of hydrogen sulfide in natural
gas for domestic consumption cannot be tolerated because it is poisonous.
It also corrodes metallic equipment. Carbon dioxide is undesirable,
because it reduces the heating value of the gas and solidifies under the
high pressure and low temperatures used for transporting natural gas. For
obtaining a sweet, dry natural gas, acid gases must be removed and water
vapor reduced. In addition, natural gas with appreciable amounts of heavy
hydrocarbons should be treated for their recovery as natural gas liquids.
Acid Gas Treatment
Acid gases can be reduced or removed by one or more of the following
methods:
1. Physical absorption using a selective absorption solvent.
2. Physical adsorption using a solid adsorbent.
3. Chemical absorption where a solvent (a chemical) capable of reacting
reversibly with the acid gases is used.
Physical Absorption
Important processes commercially used are the Selexol, the Sulfinol,
and the Rectisol processes. In these processes, no chemical reaction
occurs between the acid gas and the solvent. The solvent, or absorbent, is
a liquid that selectively absorbs the acid gases and leaves out the hydrocarbons.
In the Selexol process for example, the solvent is dimethyl ether
of polyethylene glycol. Raw natural gas passes countercurrently to the
descending solvent. When the solvent becomes saturated with the acid
gases, the pressure is reduced, and hydrogen sulfide and carbon dioxide
are desorbed. The solvent is then recycled to the absorption tower.
Physical Adsorption
In these processes, a solid with a high surface area is used. Molecular
sieves (zeolites) are widely used and are capable of adsorbing large
amounts of gases. In practice, more than one adsorption bed is used for
continuous operation. One bed is in use while the other is being regenerated Regeneration is accomplished by passing hot dry fuel gas through the
bed. Molecular sieves are competitive only when the quantities of hydrogen
sulfide and carbon disulfide are low.
Molecular sieves are also capable of adsorbing water in addition to the
acid gases.
Chemical Absorption (Chemisorption)
These processes are characterized by a high capability of absorbing
large amounts of acid gases. They use a solution of a relatively weak
base, such as monoethanolamine. The acid gas forms a weak bond with
the base which can be regenerated easily. Mono- and diethanolamines are
frequently used for this purpose. The amine concentration normally
ranges between 15 and 30%. Natural gas is passed through the amine
solution where sulfides, carbonates, and bicarbonates are formed.
Diethanolamine is a favored absorbent due to its lower corrosion rate,
smaller amine loss potential, fewer utility requirements, and minimal
reclaiming needs.3 Diethanolamine also reacts reversibly with 75% of
carbonyl sulfides (COS), while the mono- reacts irreversibly with 95% of
the COS and forms a degradation product that must be disposed of.
Diglycolamine (DGA), is another amine solvent used in the
Econamine process (Fig 1-2).4 Absorption of acid gases occurs in an
absorber containing an aqueous solution of DGA, and the heated rich solution (saturated with acid gases) is pumped to the regenerator.
Diglycolamine solutions are characterized by low freezing points, which
make them suitable for use in cold climates.
Strong basic solutions are effective solvents for acid gases. However,
these solutions are not normally used for treating large volumes of natural
gas because the acid gases form stable salts, which are not easily
regenerated. For example, carbon dioxide and hydrogen sulfide react
with aqueous sodium hydroxide to yield sodium carbonate and sodium
sulfide, respectively.
CO2 + 2NaOH (aq) r Na2 CO3 + H2O
H2S + 2 NaOH (aq) r Na2S + 2 H2O
However, a strong caustic solution is used to remove mercaptans from
gas and liquid streams. In the Merox Process, for example, a caustic solvent
containing a catalyst such as cobalt, which is capable of converting
mercaptans (RSH) to caustic insoluble disulfides (RSSR), is used for
streams rich in mercaptans after removal of H2S. Air is used to oxidize
the mercaptans to disulfides. The caustic solution is then recycled for
regeneration. The Merox process (Fig. 1-3) is mainly used for treatment
of refinery gas streams .
