Acid Gas Treating

Basic modules of gas processing plant

 Introduction
 Natural gas, while ostensibly being hydrocarbon in nature,
contains large amounts of acid gases, such as hydrogen sulfide
and carbon dioxide.
 Natural gas containing hydrogen sulfide or carbon dioxide is
referred to as sour, and natural gas free from hydrogen sulfide
is referred to as sweet.
 The corrosiveness nature of hydrogen sulfide and carbon
dioxide in the presence of water (giving rise to an acidic
aqueous solution) and because of the toxicity of hydrogen
sulfide and the lack of heating value of carbon dioxide, natural
gas being prepared for sales is required to contain no more
than 5 ppm hydrogen sulfide and to have a heating value of no
less than 920 to 980 Btu/scf.
 However, because natural gas has a wide range of
composition, including the concentration of the two acid
gases, processes for the removal of acid gases vary and are
subject to choice based on the desired end product.
 Introduction Contd….
 There are many variables in treating natural gas. The precise
area of application of a given process is difficult to define.
Several factors must be considered:
1. Types and concentrations of contaminants in the gas.
2. The degree of contaminant removal desired.
3. The selectivity of acid gas removal required.
4. The temperature, pressure, volume, and composition of the
gas to be processed.
5. The carbon dioxide–hydrogen sulfide ratio in the gas.
6. The desirability of sulfur recovery due to process
economics or environmental issues.
 In addition to hydrogen sulfide and carbon dioxide, gas may
contain other contaminants, such as mercaptans and carbonyl
sulfide. The presence of these impurities may eliminate some
of the sweetening processes,
 Introduction Contd….
 As some processes remove large amounts of acid gas but not to a
sufficiently low concentration. However, there are those processes
that are not designed to remove (or are incapable of removing) large
amounts of acid gases.
 These processes are also capable of removing the acid gas impurities
to very low levels when the acid gases are there in low to medium
concentrations in the gas. Process selectivity indicates the preference
with which the process removes one acid gas component relative to
(or in preference to) another.
 For example, some processes remove both hydrogen sulfide and
carbon dioxide; other processes are designed to remove hydrogen
sulfide only.
 It is important to consider the process selectivity for, say, hydrogen
sulfide removal compared to carbon dioxide removal that ensures
minimal concentrations of these components in the product, thus the
need for consideration of the carbon dioxide to hydrogen sulfide in
the gas stream.
 ACID GAS REMOVAL PROCESSES
 The processes that have been developed to accomplish gas purification
vary from a simple once-through wash operation to complex multistep
recycling systems
 There are two general processes used for acid gas removal: adsorption and
absorption
 Adsorption is a physical–chemical phenomenon in which the gas is
concentrated on the surface of a solid to remove impurities. Usually,
carbon is the adsorbing medium, which can be regenerated upon
desorption . The quantity of material adsorbed is proportional to the
surface area of the solid and, consequently, adsorbents are usually granular
solids with a large surface area per unit mass. Subsequently, the captured
gas can be desorbed with hot air or steam to the surface area of the solid.
 There are several limitations to the use of adsorption systems, but it is
generally felt that the major one is the requirement for minimization of
particulate matter and/or condensation of liquids (e.g., water vapor) that
could mask the adsorption surface and reduce its efficiency drastically.
• Absorption differs from adsorption in that it is not a physical–
chemical surface phenomenon, but an approach in which the
absorbed gas is ultimately distributed throughout the absorbent
(liquid). The process depends only on physical solubility and
may include chemical reactions in the liquid phase
(chemisorption). Common absorbing media used are water,
aqueous amine solutions, caustic, sodium carbonate, and
nonvolatile hydrocarbon oils, depending on the type of gas to
be absorbed.
• Usually, the gas–liquid contactor designs that are employed are
plate columns or packed beds.
• Absorption is achieved by dissolution (a physical phenomenon)
or by reaction (a chemical phenomenon). Chemical adsorption
processes adsorb sulfur dioxide onto a carbon surface where it
is oxidized (by oxygen in the flue gas) and absorbs moisture to
give sulfuric acid impregnated into and on the adsorbent.
 As currently practiced, acid gas removal processes
involve the chemical reaction of the acid gases with a
solid oxide (such as iron oxide) or selective absorption
of the contaminants into a liquid (such as ethanolamine)
that is passed countercurrent to the gas.
 Then the absorbent is stripped of the gas components
(regeneration) and recycled to the absorber. The process
design will vary and, in practice, may employ multiple
absorption columns and multiple regeneration columns.
 Liquid absorption processes [which usually employ
temperatures below50◦C (120◦F)] are classified either
as physical solvent processes or as chemical solvent
processes. The former processes employ an organic
solvent, low temperatures, or high pressure.
 In chemical solvent processes, absorption of the acid
gases is achieved mainly by use of alkaline solutions
such as amines or carbonates.
 Regeneration (desorption) can be brought about by the
use of reduced pressures and/or high temperatures,
where by the acid gases are stripped from the solvent.
Amine washing of natural gas involves chemical
reaction of the amine with any acid gases with the
liberation of an appreciable amount of heat and it is
necessary to compensate for the absorption of heat.
Amine derivatives such as ethanolamine
(monoethanol-amine), diethanol-amine,triethanol-
amine, methyldiethanol-amine, diisopropanol-amine,
and diglycol-amine have been used in commercial
applications
 Batch Type Processes
 The most common type of process for acid gas removal is the
batch type process and may involve a chemical process in which
the acid gas reacts chemically with the cleaning agent, usually a
metal oxide.
 These processes are not merely physical separation processes in
which the acid gas is removed by a physical phenomenon, such as
adsorption. Thus, the batch-type processes have the common
requirement that the process be operated as a batch system where,
at the end of the cycle, the chemical agent must be changed or
regenerated in order to continue treating.
 Batch processes are limited to removing small amounts of sulfur,
i.e., low gas flow rates and/or small concentrations of hydrogen
sulfide.
 Batch Type Processes
• Metal Oxide Processes
• Iron Sponge Process
• Zinc Oxide Process
 Slurry Processes
 Slurry processes were developed as alternatives to iron sponge.
 Slurries of iron oxide have been used to selectively absorb
hydrogen . The results have been inconsistent; problems include
obtaining stoichiometric use, premature hydrogen sulfide
breakthrough, and foaming. Also, high corrosion rates have been
reported.
 This has been circumvented by coating the contact vessels with
phenolic or epoxy resins .
 The chemical cost for these processes is higher than that for iron
sponge process, but this is partially offset by the ease and lower
cost with which the contact tower can be cleaned out and
recharged. Also, because liquids freeze and foam, antifreeze must
be added in winter, and an anti foamant agent should be available.
Finally, obtaining approval to dispose of the spent chemicals, even
if they are non-hazardous, is time-consuming.
 Slurry process

• Chemsweet Process
• Sulfa-Check Process
 Amine Processes
• Chemical absorption processes with aqueous alkanolamine solutions are used for
treating gas streams containing hydrogen sulfide and carbon dioxide. However,
depending on the composition and operating conditions of the feed gas, different
amines can be selected to meet the product gas specification. Amines are
categorized as being primary, secondary, and tertiary depending on the degree of
substitution of the central nitrogen by organic groups.
• Primary amines react directly with H2S, CO2, and carbonyl sulfide (COS).
Examples of primary amines include monoethanolamine(MEA) and the
proprietary diglycolamine agent (DGA).
• Secondary amines react directly with H2S and CO2and react indirectly with some
COS. The most common secondry amine is diethanolamine (DEA), while
diisopropanolamine (DIPA) is another example of a secondary amine, which is
not as common anymore in amine-treating systems.
• Tertiary amines react directly with H2S, react indirectly with CO2, and react
indirectly with little COS. The most common examples of tertiary amines are
methyldiethanolamine (MDEA) and activated methyldiethanolamine.
 Processes using ethanolamine and potassium phosphate are now
widely used. The ethanolamine process, known as the Girbotol
process, removes acid gases (hydrogen sulfide and carbon
dioxide) from liquid hydrocarbons as well as from natural and
from refinery gases.
 The Girbotol treatment solution is an aqueous solution of
ethanolamine, which is an organic alkali that has the reversible
property of reacting with hydrogen sulfide under cool conditions
and releasing hydrogen sulfide at high temperatures.
 The ethanolamine solution fills a tower called an absorber
through which the sour gas is bubbled. Purified gas leaves the top
of the tower, and the ethanolamine solution leaves the bottom of
the tower with the absorbed acid gases.
 The ethanolamine solution enters a reactivator tower where heat
drives the acid gases from the solution. Ethanolamine solution,
restored to its original condition, leaves the bottom of the
reactivator tower to go to the top of the absorber tower, and acid
gases are released from the top of the reactivator.
 Depending on the application, special solutions such as mixtures of amines
with physical solvents, such as sulfolane and piperazine;and amines that
have been partially neutralized with an acid such as phosphoric acid may
also be used.

 The proper selection of the amine can have a major impact on the
performance and cost of a sweetening unit. However, many factors must be
considered when selecting an amine for a sweetening application
Considerations for evaluating an amine type in gas treating systems are
numerous. It is important to consider all aspects of the amine chemistry and
type, While studying each issue, it is important to understand the
fundamentals of each amine solution.

 MEA and DEA have found the most general application in the sweetening
of natural gas streams. Even though a DEA system may not be as efficient
as some of the other chemical solvents are, it may be less expensive to
install because standard packaged systems are readily available. In
addition, it may be less expensive to operate and maintain. DEA is a
weaker base than MEA and therefore the DEA system does not typically
suffer the same corrosion problems but does react with hydrogen.
 DEA also removes carbonyl sulfide and carbon dislduflide
partially as its regenerable compound with COS and CS2
without much solution losses. One key difference among the
various specialty amines is selectivity toward hydrogen
sulfide. Instead of removing both hydrogen sulfide and carbon
dioxide, as generic amines such as MEA and DEA do, some
products readily remove hydrogen sulfide to specifications,
but allow controlled amounts of carbon dioxide to slip
through.
 The selectivity of MDEA-based products can lead to more
energy savings. For example, allowing carbon dioxide to
remain in the treated gas reduces the amount of acid gas in the
amine that needs to be regenerated, thus reducing the amount
of energy required. The use of MDEA for selective H2S
removal is based on the fact that unlike DEA, MDEA does not
react directly with CO2.
 Some advantages of the activated MDEA are as follows.
 Chemical solvent processes generally have a higher
energy requirement than physical solvent processes, but
are very selective toward hydrocarbons. However,
among these processes, the activated methyl
diethanolamine process, which removes hydrogen
sulfide completely and carbon dioxide as required, has a
low energy requirement.
 With the exception of acid gas dryness and pressure, the
activated methyl diethanolamine process meets all of
the necessary quality characteristics for a reinjection
scheme; most remarkably the liberation of acid gases
without hydrocarbons, where the presence of
hydrocarbons reduces the density and water solubility
of the pressurized acid gas fluids
 The only disadvantage of the activated methyl diethanolamine
process is liberation of acid gases at low pressure.
 A series of chemical activators used with methyl
diethanolamine offers the most cost-effective answer to
complete or controlled acid gas removal from sour to very
sour natural gases.
 However, there are limitations of even the most advanced
activated methyl diethanolamine-only based gas treatment
technologies in handling very highly acid gas-loaded natural
or associated oil field gases, especially for bulk acid gas
removal when the acid gases are destined for cycling and/or
disposal by reinjection.
 The Elf-activated MDEA process from Total FinaElf is
probably the most cost-effective solution today to meet the
widest range of applications from complete CO2 removal to
bulk H2S and/or CO2 removal even for acid gas reinjection
projects.
 Process Description
 The general process flow diagram for an amine-sweetening plant varies
little, regardless of the aqueous amine solution used as the sweetening
agent (Figure ). The sour gas containing H2S and/or CO2will nearly
always enter the plant through an inlet separator (scrubber) to remove
any free liquids and/or entrained solids.
 The sour gas then enters the bottom of the absorber column and flows
upward through the absorber in intimate countercurrent contact with the
aqueous amine solution, where the amine absorbs acid gas constituents
from the gas stream. Sweetened gas leaving the top of the absorber
passes through an outlet separator and then flows to a dehydration unit
(and compression unit, if necessary) before being considered ready for
sale.
 In many units the rich amine solution is sent from the bottom of the
absorber to a flash tank to recover hydrocarbons that may have dissolved
or condensed in the amine solution in the absorber. The rich solvent is
then preheated before entering the top of the stripper column. The
amine–amine heat exchanger serves as a heat conservation device and
lowers total heat requirements for the process
Schematic of amine gas-sweetening
process flow diagram
 A part of the absorbed acid gases will be flashed from the heated
rich solution on the top tray of the stripper. The remainder of the
rich solution flows downward through the stripper in
countercurrent contact with vapor generated in the reboiler. The
reboiler vapor (primarily steam) strips the acid gases from the rich
solution. The acid gases and the steam leave the top of the stripper
and pass overhead through a condenser, where the major portion
of the steam is condensed and cooled. The acid gases are
separated in the separator and sent to the flare or to processing.
The condensed steam is returned to the top of the stripper as
reflux.
 The lean amine solution from the bottom of the stripper column is
pumped through an amine–amine heat exchanger and then
through a cooler before being introduced to the top of the
absorber column. The amine cooler serves to lower the lean amine
temperature to the 100◦F range. Higher temperatures of the lean
amine solution will result in excessive amine losses through
vaporization and also lower acid gas-carrying capacity in the
solution because of temperature effects.
 Experience has shown that amine gas treatment is a
fouling service. Particulates formed in the plant as
well as those transported into the plant can be very
bothersome. A filtration scheme of mechanical and
activated carbon filters is therefore important in
maintaining good solution control.
 Mechanical filters such as cartridge filters or precoat
filters remove particulate material while carbon
filters remove chemical contaminants such as
entrained hydrocarbons and surface-active
compounds.
 Process selection
 Each of the previous treating processes has advantages
relative to the others for certain applications; therefore, in
selection of the appropriate process, the following facts
should be
 Air pollution regulations regarding sulfur compound disposal
and/or Tail Gas Clean Up (TGCU) requirements
 Type and concentration of impurities in the sour gas
 Specifications for the residue gas
 Specifications for the acid gas
 Temperature and pressure at which the sour gas is available
and at which the sweet gas must be delivered
 Process selection
Volume of gas to be processed
Hydrocarbon composition of the gas
Selectivity required for acid gas removal
Capital cost and operating cost
Royalty cost for process
Liquid product specifications
Disposal of by-products considered hazardous
chemicals
 Process selection
 Decisions in selecting a gas treating process can often be
simplified by gas composition and operating conditions. High
partial pressures (50 psia) of acid gases enhance the
probability of using a physical solvent.
 The presence of significant quantities of heavy hydrocarbons
in the feed discourages using physical solvents.
 Low partial pressures of acid gases and low outlet
specifications generally require the use of amines for adequate
treating. Process selection is not easy and a number of
variables must be weighed prior to making a process selection.
After preliminary assessment, a study of relevant alternatives
is usually required.
 In general, batch and amine processes are used for over 90%
of all onshore wellhead applications.
 Process selection
 Amine processes are preferred, because of the lower
operating cost, when the chemical cost for this
process is prohibitive, and justifies the higher
equipment cost.
 The key determinant is the sulfur content of the feed
gas. When the sulfur content is below 20-pound
sulfur per day, batch processes are more economical,
and when the sulfur content is over 100-pound sulfur
per day amine solutions are preferred
END