Natural Gas Desulfurization

Introduction

Sulfur exists in natural gas as hydrogen sulfide (H2S), and the gas is usually considered sour if
the hydrogen sulfide content exceeds 5.7 milligrams of H2S per cubic meter of natural gas. The
process for removing hydrogen sulfide from sour gas is commonly referred to as sweetening
the gas.

The primary process for sweetening sour natural gas is quite similar to the
processes of glycol dehydration and NGL absorption. In this case, however,
amine solutions are used to remove the hydrogen sulfide. This process is
known simply as the amine process, or alternatively as the Girdler process,
and is used in 95 percent of U.S. gas sweetening operations. The sour gas is
run through a tower, which contains the amine solution. This solution has an
affinity for sulfur, and absorbs it much like glycol absorbing water. There are
two principle amine solutions used, monoethanolamine (MEA) and
diethanolamine (DEA). Either of these compounds, in liquid form, will absorb
sulfur compounds from natural gas as it passes through. The effluent gas is
virtually free of sulfur compounds, and thus loses its sour gas status. Like the
process for NGL extraction and glycol dehydration, the amine solution used
can be regenerated (that is, the absorbed sulfur is removed), allowing it to be
reused to treat more sour gas.
Although most sour gas sweetening involves the amine absorption process, it
is also possible to use solid desiccants like iron sponges to remove the sulfide
and carbon dioxide.
Sulfur can be sold and used if reduced to its elemental form. Elemental sulfur
is a bright yellow powder like material, and can often be seen in large piles
near gas treatment plants, as is shown. In order to recover elemental sulfur
from the gas processing plant, the sulfur containing discharge from a gas
sweetening process must be further treated. The process used to recover
sulfur is known as the Claus process, and involves using thermal and catalytic
reactions to extract the elemental sulfur from the hydrogen sulfide solution.

Natural Gas Desulfurization

In natural gas sulphur exists mainly in the form of H2S. Small amounts of COS and mercaptanes
exists but H2S is the largest contaminant. The gas is called sour if more than approximately 5.7
milligrams of H2S per m3 natural gas is present. The process for the removal of H2S from
natural gas is called the sweetening of the gas. The main process for the removal of H2S from
natural gas is the amine treating unit and a Claus sulphur recovery unit.
specifically, when natural gas is liquefied to LNG, the concentration of carbon dioxide, that of hydrogen
sulfide and that of all the sulfur compounds put together are required to be not higher than 50 ppm (in
volume ratio), not higher than 4 ppm (ditto) and not higher than 30 mg-S/Nm 3, respectively. When natural
gas is used as pipeline gas, the concentration of carbon dioxide need to be held to about 1% (in volume
ratio) and sulfur compounds such as hydrogen sulfide and mercaptan have to be removed to a content
level same as that of LNG.

measurement
Introduction
Hydrogen sulfide and other sulfur bearing compounds exist naturally in many natural gas fields
throughout the world. It is generally necessary to remove these sulfur bearing compounds from
the gas in order to preserve public safety, reduce corrosion in pipelines, meet contractual
agreements and to control odor in the gas. Thus the determination of hydrogen sulfide and total
sulfur in natural gas is critical to the natural gas industry. Hydrogen Sulfide Measurement
Requirements Hydrogen sulfide (H2S) is a clear, colorless, extremely toxic gas that has a rotten
egg smell at low concentrations. The human nose can detect H2S at concentrations below 100
parts per billion. Caution must be used when relying on the sense of smell to detect H2S because
fatal concentrations of H2S anesthetize the sense of smell. H2S is generally present in raw
natural gas reserves in varying concentrations ranging from parts per million to percentage
levels. There are several processes in gas refining facilities designed to remove the H2S from the
gas. The measurement of H2S is critical in ensuring that processed natural gas meets contractual
specifications for their customer. Typical allowable limits of H2S range from 4 to 16 ppm by
volume. Total Sulfur Measurement Requirements In most natural gas reserves, the majority of
sulfur is present as H2S. However, in some reserves there may be significant concentrations of
other sulfur generally be divided into four main groups: 1) mercaptans or thiols, 2) sulfides, 3)
disulfides and 4) thiophenes. There are also processes in gas refining facilities designed to
remove these other sulfur compounds. Total sulfur measurement is also critical in ensuring that
processed gas meets contractual pipeline specifications. Typical allowable limits for total sulfur
range from 16 to 80 ppm by volume. Total sulfur measurement is further complicated by the
issue of gas odorization. Odor is imparted to natural gas in populated areas for safety reasons by
the addition of sulfur compounds. Typical odorant compounds are iso-propyl mercaptan, normalpropyl mercaptan, tertiary-butyl mercaptan and thiophene. Total sulfur measurement and/or

Natural Gas Desulfurization

individual sulfur compound analysis may be required to balance odor injection levels. Overview
of Sulfur Measurement Technology Listed below are some of the commonly used sulfur
measurement techniques with their key features and limitations.
Lead Acetate Tape.
Methodology. This method relies on the chemical reaction of H2S with lead acetate impregnated
paper tape to form lead sulfide. The lead sulfide appears as a brown stain on the paper tape. A
light source is used to illuminate the tape where the reaction is to occur and light detector is used
to monitor the reflection of the source from the tape. A concentration of H2S can be determined
by the rate of staining on the tape. Lead acetate tape can be used to measure total sulfur by
mixing the sample stream with hydrogen and passing it through a quartz tube heated to 1000 o C.
This process quantitatively converts sulfur bearing compounds to H2S which can then be
measured at the tape. Key Features and Limitations. The lead acetate tape method is H2S
specific, very sensitive, and has an equimolar response to sulfur when used in the total sulfur
mode. Tape is typically linear up to 50 ppm. Higher ranges can be achieved with dilution
systems.
Sulfur Chemiluminescence. Methodology
. This is a two step measurement process in which a small amount of sample is
injected into a hydrogen rich flame or an enclosed combustion assembly. The
hydrogen to air ratio combined with the presence of a vacuum allow for the
formation of sulfur monoxide (SO) in the combustion assembly. The combustion
gases from the flame or combustion assembly are then drawn under vacuum to a
reaction cell where ozone from an ozone generator is continuously added. SO reacts
with ozone to form an electronically excited state of sulfur dioxide (SO2) which
releases ultraviolet (UV) radiation upon relaxation. The released UV radiation is
detected with a photomultiplier tube and is linearly proportional to the amount of
sulfur present in the sample. Sample can be injected directly to the analyzer to
arrive at a total sulfur concentration. The addition of a chromatograph column prior
to the detector allows for the measurement of individual sulfur compounds. Key
Features and Limitations. The sulfur chemiluminescence detector is linear over a
large range, very sensitive and has an equimolar response to sulfur compounds.
This allows for the use of a single component, single point calibration which greatly
simplifies the calibration process.
Flame Photometric Detector (FPD)
. Methodology. FPDs are generally employed as chromatograph detectors. The
effluent from a chromatograph column is passed through a hydrogen rich, low

Natural Gas Desulfurization

temperature flame. Sulfur species are converted to S2 which becomes excited and
emits radiation upon relaxation. The emitted radiation is monitored by a
photomultiplier tube. Key Features and Limitations. The FPD is very sensitive and
selective to sulfur. Its response to sulfur is, however, non linear and non equimolar
which makes it difficult to calibrate because several multi-component standards of
varying concentration are required.
Ultraviolet (UV) Absorption. Methodology.
This method relies on the ultraviolet absorption characteristics of H2S. The optical
system consists of a UV lamp as a source, a transparent sample cell through which
the sample gas flows, and a single photomultiplier tube detector. In front of the
detector is a motor driven beam splitter which alternately directs the source beam
to a reference filter and a measurement filter. The measurement filter is selected to
correspond to an absorbency peak of H2S while the reference filter is selected to
correspond to some non-absorbing region of the spectrum for H2S. In this way the
absorption of the sample can be measured and is proportional to the amount of H2S
present in the sample. Key Features and Limitations. The UV absorption method is
typically used at percentage levels of H2S, however, by lengthening the cell and
pressurizing the sample in the cell, measurement at ppm levels is possible. This
method is subject to strong positive interference from olefins and aromatic
compounds. Chromatographic techniques are sometimes employed to separate the
H2S from interfering species.
Wet Electrochemical Detectors. Methodology.
The wet electrochemical detector relies on the reduction/oxidation reaction
between reduced sulfur compounds and a solution of chromic acid. This method is
used as a chromatograph detector for the measurement of individual sulfur
compounds and has widespread use in odorant analysis. The sulfur compounds are
eluted from a column and passed through a measurement electrode assembly. The
electrode assembly consists of two platinum mesh electrodes, one of which is
immersed in the chromic acid solution while the other is suspended above the
solution. The two electrodes are held in contact by a layer of the solution which is
suspended between the two electrodes by capillary action. The column effluent is
passed over the upper electrode. The chromic acid near the surface of the electrode
is reduced, creating an excess of electrons at the upper electrode. The strength of
the resulting current between the two electrodes is proportional to the amount of
sulfur compound present.
Key Features and Limitations. This method offers linear response to sulfur
compounds in the low ppm range, however the response is not equimolar. It only

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responds to reduced sulfur species and thus cannot measure carbonyl sulfide,
making a true total sulfur analysis impossible.

Solid State Electrochemical Sensors.

Methodology. Solid state sensors are constructed using a semi-conductor material
that is applied to a non-conducting substrate between two electrodes. The substrate
is heated to a temperature such that the gas being monitored can cause a
reversible change in the conductivity of the semi-conductor material. Under zero
gas conditions, oxygen molecules tie up free electrons in the semiconductor
material by absorbing to its surface, thus inhibiting electrical flow. As H2S molecules
are introduced, they replace the oxygen molecules releasing the free electrons thus
decreasing the resistance between the two electrodes. This change in resistance is
measured directly and is proportional to the concentration of H2S in the gas. Key
Features and Limitations. Solid state sensors are typically used for ambient air
monitoring for protection of personnel and equipment. They generally have high
zero drift and are susceptible to poisoning, making them ineffective as process
analyzers.
Sulfur Titrators
. Methodology. Sulfur titrators operate on the principle of the reduction-oxidation
reaction between sulfur bearing compounds and bromine (Br2) and are typically
used in chromatographic applications. Bromine gas (Br2) is generated
electrochemically from a solution containing hydrobromic acid (HBr). The titrametric
cell is basically a three electrode coulometric titration. Three electrodes are used:
the first serves as a common, the second is used to generate the Br2, and the third
is a hydrogen generating electrode. The titration proceeds by flowing the
chromatograph column effluent through the titrametric cell at a fixed flow rate. The
Br2 that is generated in the cell reacts with the sulfur compound as it elutes from
the column, and both are consumed. The electrical current necessary to generate
just enough Br2 to react with all of the sulfur compound is measured and is
proportional to the amount of sulfur compound present. Key Features and
Limitations. Sulfur titrators are typically used as chromatograph detectors which
provides measurement of individual sulfurcompounds. They do not respond to
carbonyl sulfide (COS) or carbon disulfide (CS2), thus making a true total sulfur
measurement impossible.
Tunable Laser Diode (TDL).
Methodology. The tunable laser diode relies on the absorption characterizes of H2S
in the near infrared. A laser is used as the light source instead of traditional infrared

Natural Gas Desulfurization

sources. The gas sample flows through a cell where is it irradiated by the laser and
any H2S in the sample will absorb energy from the laser. The amount of light
absorbed is proportional to the concentration of H2S in the sample. Features and
Limitations. Tunable laser diode is a direct spectroscopic method and thus requires
no consumable components. Sensitivity into the ppm range can be achieved by the
use of multipath cells. The TDL is subject to interferences from the hydrocarbon
matrix and thus it is required to know the concentration of the specific
hydrocarbons in the sample. The analyzer results are subject to change if the
hydrocarbon matrix changes. The TDL is also subject to positive interferences from
other sulfur compounds in the gas, such as mercaptans. A scrubber is required to
remove H2S from the sample and then compare the spectra of the sample against
the sample with H2S removed. Length of Stain Tubes. Methodology. These are glass
tubes filled with lead acetate impregnated onto an inert substrate. A fixed volume of
sample gas is drawn into the tube by means of a hand held pump. Any H2S present
in the sample will react with the lead acetate to form lead sulfide, which can be
seen as a brown stain inside the tube. The length of the stain inside the tube is
proportional to the amount of H2S in the sample. Features and Limitations. Accuracy
of stain tubes is +/- 25% and are only useful as a rough estimate of H2S
concentration. Stain tubes are also available which respond specifically to
mercaptans or thiophene. Stain tubes do not provide complete total sulfur
measurement because they do not respond to carbonyl sulfide or sulfides and
disulfides.
Calibration of Sulfur Analyzers
All sulfur analyzers rely on known reference standards for their calibration. Proper
calibration is essential for good analyzer accuracy. There are several methods
available for generating H2S and total sulfur calibration standards, which are listed
below. Permeation Devices. A small amount of the pure compound of interest is
encapsulated in a reservoir. One end of the reservoir is sealed against a
semipermeable membrane. The surface area and chemical characteristics of the
membrane allow a small amount of the compound to permeate through the
membrane at a known rate. A carrier gas flowing at a known rate picks up the
permeated sample and thus generates a gas stream of known concentration.
Permeation devices are generally temperature and flow dependent, so care must be
exercised to ensure that proper temperature control and flow rates are used for a
specific device. Dilution Techniques. Dilution techniques can be used to generate
calibration standards of a desired concentration on site. Typically, a small amount of
pure H2S is injected via a syringe into a large cylindrical container and then diluted
with air. By varying the amount of H2S injected and the amount of air used for
dilution, virtually any desired concentration can be generated. Standards generated
in this manner should be used immediately because they tend to degrade over

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time. Also, great caution must be exercised when using pure H2S, due to its high
toxicity. Prepared Cylinders. Many gas supply companies offer prepared pressurized
cylinders of H2S and total sulfur standards of any desired concentration. Bottled
gases are the most convenient and easy to use standards. There are, however,
several points to consider when choosing and using bottled sulfur standards.
Prepared H2S and sulfur standards have a shelf life. Most manufacturers will
guarantee an H2S standard
for 6 months at a concentration below 10 ppm and for one year at concentrations
above 10 ppm. Standards should be replaced according to the manufacturers
specified shelf life. Bottled standards are available in many sizes, so the amount of
calibration gas can be purchased according to your specific requirements. H2S
standards should be packed in a background of nitrogen, as opposed to methane or
any other hydrocarbon background. H2S in nitrogen standards are more stable
because nitrogen is generally available in purer and drier grades than most
hydrocarbons. It is the trace amounts of moisture in the background gas that
contribute the most to the standars degradation.
Where possible, mixing several different sulfur compounds in the same gas mixture
should be avoided. Sulfur compounds are very reactive and will tend to react with
each other, the cylinder walls and trace levels of impurities in the background gas.
One example of this occurs in mixtures containing hydrogen sulfide and carbonyl
sulfide (COS). The COS tends to hydrolyze at high pressure in the presence of trace
amounts of moisture to form H2S. Therefore, over time, the COS concentration in
the bottle will fall while the H2S concentration will increase. Avoid the use of any
brass components in your calibration system. This includes the valve stem on the
bottle, pressure regulators, associated tubing and flow devices. Brass will absorb
significant amounts of sulfur, leading to erroneous calibration. 316 stainless steel
should be used for all sample wetted parts. One should constantly be aware of the
reactive nature of H2S and sulfur compounds in general. Even 316 stainless steel
will absorb sulfur. It is a good idea to thoroughly purge regulators and tubing with
the calibration gas before performing a calibration routine. Sample Conditioning
Systems The purpose of the sample conditioning system is to deliver a clean,
particulate free, dry sample to the analyzer that is representative of the gas in the
pipeline. Once again, due to the reactive nature of sulfur compounds, there are
some special considerations when designing a sample system for sulfur
measurement. Sample gas will typically be extracted from the pipeline by means of
a probe regulator. The probe will typically extend into the middle 1/3 of the pipeline
to avoid extracting any contaminants from the inside of the pipeline wall. The probe
regulator will also reduce the pressure of the sample from pipeline pressure down to
10 50 psig. Making the pressure drop right at the pipeline is desirable for two
reasons: 1) the pressure drop occurs right at the probe tip where the gas
temperature is likely to be higher thus minimizing the Joules-Thompson effect and 2)

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packing the sample transport lines with a lower pressure greatly reduces sample
transport times. Once the sample is transported to the analyzer, any particulate or
entrained liquids can be removed with a coalescing filter. Typically this filter is
equipped with a sweep valve which sweeps away any removed liquids and also acts
as a speed loop, ensuring that the sample in the transport line is representative of
the sample in the pipeline. In cases where there are large amounts of entrained
liquids, a gas permeable membrane filter can be used which will allow only the gas
portion of the sample to pass to the analyzer. As with the calibration system, all
sample wetted parts should be of 316 stainless steel construction. Getting Good
Sulfur Numbers: Verification and Troubleshooting of Sulfur Analyzers Due to the
reactive nature of sulfur compounds it can be difficult to obtain reliable H2S and/or
total sulfur analysis results. Verification of sulfur analyzers can be equally as
difficult. The discussion below addresses some of the issues that may arisewhen
attempting to interpret the results of a sulfur analyzer. Keep the calibration standard
current. The calibration standard is the most important trouble shooting tool
available to ensure that the sulfur analyzer is operating within its specifications. It is
very important when doing sulfur measurement to keep the sample transport lines
free of contaminants such as water, glycol, amine and condensed hydrocarbon
liquids. Keep the sample transport lines as direct and as short as possible from the
sample point to the analyzer. Also, avoid low spots or cold spots in the sample
transport lines where liquids are likely to collect. If liquids do collect in the sample
system, H2S is likely to be absorbed by the liquids, possibly causing false low
readings. A liquid pool may also absorb a certain amount of H2S and then release it
upon a change in temperature or pressure, causing temporary false high readings.
Choosing an appropriate sample point will also help in minimizing sample line
contamination. Putting the sample point slightly farther away from the process may
compromise theimprove analyzer reliability. At certain times it may be necessary or
desirable to verify the reading of an on line instrument. Two common ways of doing
this are by length of stain tubes or by sending a sample to a laboratory. When using
length of stain tubes, be sure to take the sample from the same point that the
analyzer does.
actual sample system to eliminate any problems that may be associated with the
sample system itself. Bear in mind that length of stain tubes are accurate to +/25% of reading and only provide an estimate of theH2S concentration. When taking
a sample to send to a laboratory, also use the same sample point that the analyzer
uses and where possible take Some consideration must also be given to the sample
container itself. Due to their reactive nature the sulfur compounds of interest may
be absorbed by the container, leading to false low or even zero readings from the
laboratory analysis. If using a sample bomb, it should be of 316 stainless steel
construction and must be clean. It should also be sufficiently purged to allow for
absorption of the sulfur compounds in the walls of the bomb. Teflon lined sample
bombs are available that will minimize sample absorption, however, Teflon is still

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susceptible to absorption. A sample container deactivation process is now available

that will virtually eliminate sulfur absorption. The container is deactivated by
appdeactivated by applying a microthin layer of silica to the container wall, thus
eliminating contact between the sample and the container. Sample transport tubing
treated with this process is also available. An alternative to sample bombs where
the sample is available at low pressure (less than 2 psig) is the sample bag. These
bags are typically made of an inert polymer (usually Tedlar) and are fitted with a
valve for sample introduction
Summary
Determination of hydrogen sulfide (H2S) and/or total sulfur content in natural gas
pipelines is necessary to preserve public safety, reduce corrosion in pipelines and
related equipment, meet contractual agreements and to control odor of the gas.
There are several different methods for the measurement of sulfur in pipelines, each
with its own inherent advantages and disadvantages. Calibration and sample
handling systems are an integral part of the sulfur measurement system. Due
consideration must be given to the reactive nature of sulfur compounds when
designing sulfur measurement systems and when verifying and troubleshooting
these systems.

REMOVAL OF SULPHUR
Removal of acid gases (hydrogen sulfide and carbon dioxide). There are many processes that are
available for that purpose as shown in the flow diagram, but amine treating is the process that was
historically used. However, due to a range of performance and environmental constraints of the
amine process, a newer technology based on the use of polymeric membranes to separate the
carbon dioxide and hydrogen sulfide from the natural gas stream has gained increasing acceptance.
Membranes are attractive since no reagents are consumed.[13]
The acid gases, if present, are removed by membrane or amine treating can then be routed into a
sulfur recovery unit which converts the hydrogen sulfide in the acid gas into either elemental sulfur or
sulfuric acid. Of the processes available for these conversions, the Claus process is by far the most
well known for recovering elemental sulfur, whereas the conventional Contact process and the WSA
(Wet sulfuric acid process) are the most used technologies for recovering sulfuric acid.
The residual gas from the Claus process is commonly called tail gas and that gas is then processed
in a tail gas treating unit (TGTU) to recover and recycle residual sulfur-containing compounds back
into the Claus unit. Again, as shown in the flow diagram, there are a number of processes available
for treating the Claus unit tail gas and for that purpose a WSA process is also very suitable since it
can work autothermally on tail gases.

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Amine gas treating

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.

Natural Gas Desulfurization

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.

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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

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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]

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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

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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]

Membrane technology
Membrane technology covers all engineering approaches for the transport of substances between
two fractions with the help of permeable membranes. In general, mechanical separation processes
for separating gaseous or liquid streams use membrane technology.

Applications

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Ultrafiltration for a swimming pool

Venous-arterial extracorporeal membrane oxygenation scheme

Membrane separation processes operate without heating and therefore use less energy than
conventional thermal separation processes such as distillation, sublimation or crystallization. The
separation process is purely physical and both fractions (permeate and retentate) can be used. Cold
separation using membrane technology is widely used in the food
technology, biotechnology and pharmaceuticalindustries. Furthermore, using membranes enables
separations to take place that would be impossible using thermal separation methods. For example,
it is impossible to separate the constituents of azeotropic liquids or solutes which
form isomorphiccrystals by distillation or recrystallization but such separations can be achieved
using membrane technology. Depending on the type of membrane, the selective separation of
certain individual substances or substance mixtures is possible. Important technical applications
include the production of drinking water by reverse osmosis (worldwide approximately 7 million cubic
metres annually), filtrations in the food industry, the recovery of organic vapours such as petrochemical vapour recovery and the electrolysis for chlorine production.
In waste water treatment, membrane technology is becoming increasingly important. With the help
of ultra/microfiltration it is possible to remove particles, colloids and macromolecules, so that wastewater can be disinfected in this way. This is needed if waste-water is discharged into sensitive
waters especially those designated for contact water-sports and recreation.
About half of the market is in medical applications such as use in artificial kidneys to remove toxic
substances by hemodialysisand as artificial lung for bubble-free supply of oxygen in the blood.
The importance of membrane technology is growing in the field of environmental protection
(NanoMemPro IPPC Database). Even in modern energy recovery techniques membranes are
increasingly used, for example in fuel cells and in osmotic power plants.

Mass transfer[edit]
Two basic models can be distinguished for mass transfer through the membrane:

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the solution-diffusion model and

the hydrodynamic model.

In real membranes, these two transport mechanisms certainly occur side by side, especially during
ultra-filtration.

Solution-diffusion model[edit]
In the solution-diffusion model, transport occurs only by diffusion. The component that needs to be
transported must first be dissolved in the membrane. The general approach of the solution-diffusion
model is to assume that the chemical potential of the feed and permeate fluids are in equilibrium with
the adjacent membrane surfaces such that appropriate expressions for the chemical potential in the
fluid and membrane phases can be equated at the solution-membrane interface. This principle is
more important for dense membranes without natural pores such as those used for reverse osmosis
and in fuel cells. During the filtration process a boundary layer forms on the membrane.
This concentration gradient is created by molecules which cannot pass through the membrane. The
effect is referred as concentration polarization and, occurring during the filtration, leads to a reduced
trans-membrane flow (flux). Concentration polarization is, in principle, reversible by cleaning the
membrane which results in the initial flux being almost totally restored. Using a tangential flow to the
membrane (cross-flow filtration) can also minimize concentration polarization.

Hydrodynamic model[edit]
Transport through pores in the simplest case is done convectively. This requires the size of the
pores to be smaller than the diameter of the two separate components. Membranes which function
according to this principle are used mainly in micro- and ultrafiltration. They are used to
separate macromolecules from solutions, colloids from a dispersion or remove bacteria. During this
process the retained particles or molecules form a pulpy mass (filter cake) on the membrane, and
this blockage of the membrane hampers the filtration. This blockage can be reduced by the use of
the cross-flow method (cross-flow filtration). Here, the liquid to be filtered flows along the front of the
membrane and is separated by the pressure difference between the front and back of the membrane
into retentate (the flowing concentrate) on the front and permeate (filtrate) on the back. The
tangential flow on the front creates a shear stress that cracks the filter cake and reduces the fouling.

Membrane operations[edit]
According to the driving force of the operation it is possible to distinguish:

Pressure driven operations

microfiltration

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ultrafiltration

nanofiltration

reverse osmosis

Concentration driven operations

dialysis

pervaporation

forward osmosis

artificial lung

gas separation

Operations in an electric potential gradient

electrodialysis

membrane electrolysis e.g. chloralkali process

electrodeionization

electrofiltration

fuel cell

Operations in a temperature gradient

membrane distillation

Membrane shapes and flow geometries[edit]

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Cross-flow geometry

Dead-end geometry

There are two main flow configurations of membrane processes: cross-flow (or) tangential flow and
dead-end filtrations. In cross-flow filtration the feed flow is tangential to the surface of membrane,
retentate is removed from the same side further downstream, whereas the permeate flow is tracked
on the other side. In dead-end filtration the direction of the fluid flow is normal to the membrane
surface. Both flow geometries offer some advantages and disadvantages. Generally, dead-end
filtration is used for feasibility studies on a laboratory scale. The dead-end membranes are relatively
easy to fabricate which reduces the cost of the separation process. The dead-end membrane
separation process is easy to implement and the process is usually cheaper than cross-flow
membrane filtration. The dead-end filtration process is usually a batch-type process, where the
filtering solution is loaded (or slowly fed) into the membrane device, which then allows passage of
some particles subject to the driving force. The main disadvantage of a dead end filtration is the
extensive membrane fouling and concentration polarization. The fouling is usually induced faster at
higher driving forces. Membrane fouling and particle retention in a feed solution also builds up a
concentration gradients and particle back flow (concentration polarization). The tangential flow
devices are more cost and labor-intensive, but they are less susceptible to fouling due to the
sweeping effects and high shear rates of the passing flow. The most commonly used synthetic
membrane devices (modules) are flat sheets/plates, spiral wounds, and hollow fibers.
Flat plates are usually constructed as circular thin flat membrane surfaces to be used in dead-end
geometry modules. Spiral wounds are constructed from similar flat membranes but in the form of a
pocket containing two membrane sheets separated by a highly porous support plate. [1] Several
such pockets are then wound around a tube to create a tangential flow geometry and to reduce
membrane fouling. hollow fiber modules consist of an assembly of self-supporting fibers with dense
skin separation layers, and a more open matrix helping to withstand pressure gradients and maintain
structural integrity.[1] The hollow fiber modules can contain up to 10,000 fibers ranging from 200 to

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2500 m in diameter; The main advantage of hollow fiber modules is very large surface area within
an enclosed volume, increasing the efficiency of the separation process.

Spiral wound membrane module

Hollow fiber membrane module

Separation of air into oxygen and nitrogen through a membrane

Disc tube module is using a cross-flow geometry, and consists of a pressure tube and hydraulic
discs, which are held by a central tension rod, and membrane cushions that lie between two discs. [2]

Membrane performance and governing equations[edit]

The selection of synthetic membranes for a targeted separation process is usually based on few
requirements. Membranes have to provide enough mass transfer area to process large amounts of
feed stream. The selected membrane has to have high selectivity (rejection) properties for certain
particles; it has to resist fouling and to have high mechanical stability. It also needs to be

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reproducible and to have low manufacturing costs. The main modeling equation for the dead-end
filtration at constant pressure drop is represented by Darcys law:[1]
where Vp and Q are the volume of the permeate and its volumetric flow rate respectively
(proportional to same characteristics of the feed flow), is dynamic viscosity of permeating fluid, A is
membrane area, Rm and R are the respective resistances of membrane and growing deposit of the
foulants. Rm can be interpreted as a membrane resistance to the solvent (water) permeation. This
resistance is a membrane intrinsic property and is expected to be fairly constant and independent of
the driving force, p. R is related to the type of membrane foulant, its concentration in the filtering
solution, and the nature of foulant-membrane interactions. Darcys law allows for calculation of the
membrane area for a targeted separation at given conditions. The solute sieving coefficient is
defined by the equation:[1]
where Cf and Cp are the solute concentrations in feed and permeate respectively. Hydraulic
permeability is defined as the inverse of resistance and is represented by the equation: [1]
where J is the permeate flux which is the volumetric flow rate per unit of membrane area. The solute
sieving coefficient and hydraulic permeability allow the quick assessment of the synthetic membrane
performance.

Membrane separation processes[edit]

Membrane separation processes have a very important role in the separation industry. Nevertheless,
they were not considered technically important until the mid-1970s. Membrane separation processes
differ based on separation mechanisms and size of the separated particles. The widely used
membrane processes include microfiltration, ultrafiltration, nanofiltration, reverse
osmosis, electrolysis, dialysis, electrodialysis, gas separation, vapor permeation, pervaporation,
membrane distillation, and membrane contactors.[3] All processes except for pervaporation involve no
phase change. All processes except (electro)dialysis are pressure driven. Microfltration and
ultrafiltration is widely used in food and beverage processing (beer microfiltration, apple juice
ultrafiltration), biotechnological applications and pharmaceutical industry (antibiotic production,
protein purification), water purification and wastewater treatment, the microelectronics industry, and
others. Nanofiltration and reverse osmosis membranes are mainly used for water purification
purposes. Dense membranes are utilized for gas separations (removal of CO 2 from natural gas,
separating N2 from air, organic vapor removal from air or a nitrogen stream) and sometimes in
membrane distillation. The later process helps in the separation of azeotropic compositions reducing
the costs of distillation processes.

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Ranges of membrane based separations

Pore size and selectivity[edit]

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The pore distribution of a fictitious ultrafiltration membrane with the nominal pore size and the D 90

The pore sizes of technical membranes are specified differently depending on the manufacturer.
One common distinction is by nominal pore size. It describes the maximum pore size
distribution[4] and gives only vague information about the retention capacity of a membrane. The
exclusion limit or "cut-off" of the membrane is usually specified in the form of NMWC (nominal
molecular weight cut-off, or MWCO, molecular weight cut off, with units in Dalton). It is defined as the
minimum molecular weight of a globular molecule that is retained to 90% by the membrane. The cutoff, depending on the method, can by converted to so-called D90, which is then expressed in a metric
unit. In practice the MWCO of the membrane should be at least 20% lower than the molecular
weight of the molecule that is to be separated.
Filter membranes are divided into four classes according to pore size:

Pore
size

Molecular
mass

> 10

Process

Filtratio
n

Removal of

"Classic" filter

> 0.1 m

> 5000 kDa

microfiltration

< 2 bar

larger bacteria, yeast, particles

100-2 n
m

5-5000 kDa

ultrafiltration

1-10 bar

bacteria, macromolecules, proteins,

larger viruses

2-1 nm

0.1-5 kDa

nanofiltration

3-20 bar

viruses, 2- valent ions[5]

< 1 nm

< 100 Da

reverse
osmosis

10-80 ba
r

salts, small organic molecules

The form and shape of the membrane pores are highly dependent on the manufacturing process
and are often difficult to specify. Therefore, for characterization, test filtrations are carried out and the
pore diameter refers to the diameter of the smallest particles which could not pass through the
membrane.
The rejection can be determined in various ways and provides an indirect measurement of the pore
size. One possibility is the filtration of macromolecules (often dextran, polyethylene
glycol or albumin), another is measurement of the cut-off by gel permeation chromatography. These

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methods are used mainly to measure membranes for ultrafiltration applications. Another testing
method is the filtration of particles with defined size and their measurement with a particle sizer or
by laser induced breakdown spectroscopy (LIBS). A vivid characterization is to measure the rejection
of dextran blue or other colored molecules. The retention of bacteriophage and bacteria, the socalled "bacteriachallenge test", can also provide information about the pore size.

Nominal pore size

micro-organism

ATCC root number

0.1 m

Acholeplasma laidlawii

23206

0.3 m

Bacillus subtilis spores

82

0.5 m

Pseudomonas diminuta

19146

0.45 m

Serratia marcescens

14756

0.65 m

Lactobacillus brevis

To determine the pore diameter, physical methods such as porosimetry (mercury, liquid-liquid
porosimetry and Bubble Point Test) are also used, but a certain form of the pores (such
as cylindrical or concatenated spherical holes) is assumed. Such methods are used for membranes
whose pore geometry does not match the ideal, and we get "nominal" pore diameter, which
characterizes the membrane, but does not necessarily reflect its actual filtration behavior and
selectivity.
The selectivity is highly dependent on the separation process, the composition of the membrane and
its electrochemical properties in addition to the pore size. With high selectivity, isotopes can be
enriched (uranium enrichment) in nuclear engineering or industrial gases like nitrogen can be
recovered (gas separation). Ideally, even racemics can be enriched with a suitable membrane.
When choosing membranes selectivity has priority over a high permeability, as low flows can easily
be offset by increasing the filter surface with a modular structure. In gas phase filtration different
deposition mechanisms are operative, so that particles having sizes below the pore size of the
membrane can be retained as well.