Amine gas treating

From Wikipedia, the free encyclopedia

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 liquefied petroleum gas (LPG).

Description of a typical amine treater

Gases containing H2S or both H2S and CO2 are commonly referred to as sour gases or acid gases
in the hydrocarbon processing 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 CO2 from 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

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 CO2 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
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 CO2 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 H2S 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

MEA and DEA are primary and secondary amines. They are very reactive and can effectively
remove a high volume of gas 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
In oil refineries, that stripped gas is mostly H2S, much of which often comes from a sulfur-
removing 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 CO2. (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

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 CO2 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 CO2, thus, increasing the capital cost.[12]