Amine gas treating

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Amine gas treating, also known as amine scrubbing, gas sweetening and acid gas removal,
refers to a group of processes that use aqueous solutions of various alkylamines (commonly referred
to simply as amines) to remove hydrogen sulfide (H2S) and carbon dioxide (CO2) from gases.[1][2][3] It is
a common unit process used in refineries, and is also used in petrochemical plants, natural gas
processing plants and other industries.
Processes within oil refineries or chemical processing plants that remove hydrogen sulfide are
referred to as "sweetening" processes because the odor of the processed products is improved by
the absence of hydrogen sulfide. An alternative to the use of amines involves membrane technology.
However, membrane separation is less attractive due to the relatively high capital and operating
costs as well as other technical factors.[4]
Many different amines are used in gas treating:

Diethanolamine (DEA)

Monoethanolamine (MEA)

Methyldiethanolamine (MDEA)

Diisopropanolamine (DIPA)

Aminoethoxyethanol (Diglycolamine) (DGA)

The most commonly used amines in industrial plants are the alkanolamines DEA, MEA, and MDEA.
These amines are also used in many oil refineries to remove sour gases from liquid hydrocarbons
such as liquified petroleum gas (LPG).

Description of a typical amine treater[edit]

Gases containing H2S or both H2S and CO2 are commonly referred to as sour gases or acid gases in
the hydrocarbonprocessing industries.
The chemistry involved in the amine treating of such gases varies somewhat with the particular
amine being used. For one of the more common amines, monoethanolamine (MEA) denoted
as RNH2, the chemistry may be expressed as:
RNH2 + H2S RNH+
3 + SH
A typical amine gas treating process (the Girbotol process, as shown in the flow diagram below)
includes an absorber unit and a regenerator unit as well as accessory equipment. In the
absorber, the downflowing amine solution absorbs H2S and CO2from the upflowing sour gas to
produce a sweetened gas stream (i.e., a gas free of hydrogen sulfide and carbon dioxide) as a
product and an amine solution rich in the absorbed acid gases. The resultant "rich" amine is then
routed into the regenerator (a stripper with a reboiler) to produce regenerated or "lean" amine
that is recycled for reuse in the absorber. The stripped overhead gas from the regenerator is
concentrated H2S and CO2.

Process flow diagram of a typical amine treating process used in petroleum refineries, natural gas
processing plants and other industrial facilities.

Alternative processes[edit]
Alternative stripper configurations include matrix, internal exchange, flashing feed, and
multipressure with split feed. Many of these configurations offer more energy efficiency for
specific solvents or operating conditions. Vacuum operation favors solvents with low heats of
absorption while operation at normal pressure favors solvents with high heats of absorption.
Solvents with high heats of absorption require less energy for stripping from temperature swing
at fixed capacity. The matrix stripper recovers 40% of CO2 at a higher pressure and does not
have inefficiencies associated with multipressure stripper. Energy and costs are reduced since
the reboiler duty cycle is slightly less than normal pressure stripper. An Internal Exchange
stripper has a smaller ratio of water vapor to CO2 in the overheads stream, and therefore less
steam is required. The multipressure configuration with split feed reduces the flow into the
bottom section, which also reduces the equivalent work. Flashing feed requires less heat input
because it uses the latent heat of water vapor to help strip some of the CO 2 in the rich stream
entering the stripper at the bottom of the column. The multipressure configuration is more
attractive for solvents with a higher heats of absorption.[5]

Amines[edit]
The amine concentration in the absorbent aqueous solution is an important parameter in the
design and operation of an amine gas treating process. Depending on which one of the following
four amines the unit was designed to use and what gases it was designed to remove, these are
some typical amine concentrations, expressed as weight percent of pure amine in the aqueous
solution:[1]

Monoethanolamine: About 20 % for removing H2S and CO2, and about 32 % for
removing only CO2.

Diethanolamine: About 20 to 25 % for removing H2S and CO2

Methyldiethanolamine: About 30 to 55% % for removing H2S and CO2

Diglycolamine: About 50 % for removing H2S and CO2

The choice of amine concentration in the circulating aqueous solution depends upon a
number of factors and may be quite arbitrary. It is usually made simply on the basis of
experience. The factors involved include whether the amine unit is treating raw natural
gas or petroleum refinery by-product gases that contain relatively low concentrations of both
H2S and CO2 or whether the unit is treating gases with a high percentage of CO 2 such as the
offgas from the steam reforming process used in ammonia production or the flue
gases from power plants.[1]
Both H2S and CO2 are acid gases and hence corrosive to carbon steel. However, in an
amine treating unit, CO2 is the stronger acid of the two. H2S forms a film of iron sulfide on the
surface of the steel that acts to protect the steel. When treating gases with a high
percentage of CO2, corrosion inhibitors are often used and that permits the use of higher
concentrations of amine in the circulating solution.
Another factor involved in choosing an amine concentration is the relative solubility of H 2S
and CO2 in the selected amine.[1]The choice of the type of amine will affect the required
circulation rate of amine solution, the energy consumption for the regeneration and the
ability to selectively remove either H2S alone or CO2 alone if desired. For more information
about selecting the amine concentration, the reader is referred to Kohl and Nielsen's book.

MEA and DEA[edit]

MEA and DEA are primary and secondary amines. They are very reactive and can
effectively remove a high volume of gas removal due to a high reaction rate. However, due
to stoichiometry, the loading capacity is limited to 0.5 mol CO2 per mole of amine.[6] MEA and
DEA also require a large amount of energy to strip the CO2 to during regeneration, which
can be up to 70% of total operating costs. They are also more corrosive and chemically
unstable compared to other amines.[6]

Uses[edit]
In oil refineries, that stripped gas is mostly H2S, much of which often comes from a sulfurremoving process called hydrodesulfurization. This H2S-rich stripped gas stream is then
usually routed into a Claus process to convert it into elemental sulfur. In fact, the vast
majority of the 64,000,000 metric tons of sulfur produced worldwide in 2005 was byproduct
sulfur from refineries and other hydrocarbon processing plants.[7][8] Another sulfur-removing
process is the WSA Process which recovers sulfur in any form as concentrated sulfuric acid.
In some plants, more than one amine absorber unit may share a common regenerator unit.
The current emphasis on removing CO2 from the flue gases emitted by fossil fuel power
plants has led to much interest in using amines for removing CO 2. (See also: Carbon capture
and storage and Conventional coal-fired power plant.)
In the specific case of the industrial synthesis of ammonia, for the steam reforming process
of hydrocarbons to produce gaseous hydrogen, amine treating is one of the commonly used
processes for removing excess carbon dioxide in the final purification of the gaseous
hydrogen.
In the biogas production it is sometimes necessary to remove carbon dioxide from the
biogas to make it comparable with the natural. The removal of the sometimes high content
of hydrogen sulfide is necessary to prevent corrosion of metallic parts after burning the bio
gas.[9][10]

Carbon capture and storage[edit]

Amines are used to remove CO2 in various areas ranging from natural gas production to the
food and beverage industry, and have been for over sixty years. [11]
There are multiple classifications of amines, each of which has different characteristics
relevant to CO2 capture. For example, Monoethanolamine (MEA) reacts strongly with acid
gases like CO2 and has a fast reaction time and an ability to remove high percentages of
CO2, even at the low CO2 concentrations. Typically, Monoethanolamine (MEA) can capture
85% to 90% of the CO2 from the flue gas of a coal-fired plant, which is one of the most
effective solvent to capture CO2.[12]
Challenges of carbon capture using amine include:

Low pressure gas increases difficulty of transferring CO2 from the gas into amine

Oxygen content of the gas can cause amine degradation and acid formation

CO2 degradation of primary (and secondary) amines

High energy consumption

Very large facilities

Finding suitable location for the removed CO2[13]

The partial pressure is the driving force to transfer CO2 into the liquid phase. Under the low
pressure, this transfer is hard to achieve without increasing the reboilers heat duty, which
will result in higher cost.[13]
Primary and secondary amines, for example, MEA and DEA, will react with CO 2 and form
degradation products. O2 from the inlet gas will cause degradation as well. The degraded
amine is no longer able to capture CO2, which decreases the overall carbon capture
efficiency.[13]
Currently, variety of amine mixtures are being synthesized and tested to achieve a more
desirable set of overall properties for use in CO2 capture systems. One major focus is on
lowering the energy required for solvent regeneration, which has a major impact on process
costs. However, there are tradeoffs to consider. For example, the energy required for
regeneration is typically related to the driving forces for achieving high capture capacities.
Thus, reducing the regeneration energy can lower the driving force and thereby increase the
amount of solvent and size of absorber needed to capture a given amount of CO 2, thus,
increasing the capital cost.[12]