Natural Gas

Natural gas processing is a complex industrial process designed to clean raw natural gas by
separating impurities and various non-methane hydrocarbons and fluids to produce what is
known as 'pipeline quality' dry natural gas.[1]

Background

Natural gas processing begins at the head. The composition of the raw natural gas extracted
from producing wells depends on the type, depth, and location of the underground deposit
and the geology of the area. Oil and natural gas are often found together in the same
reservoir. The natural gas produced from oil wells is generally classified as “associated-
dissolved,” meaning that the natural gas is associated with or dissolved in crude oil. Natural
gas production absent any association with crude oil is classified as “non-associated.” In
2004, 75 percent of U.S. wellhead production of natural gas was non-associated.[citation needed]

Most natural gas production contains, to varying degrees, small (two to eight carbons)
hydrocarbon molecules in addition to methane. Although they exist in a liquid state at
underground pressures, these molecules will become gaseous at normal atmospheric
pressure. Collectively, they are called condensates or natural gas liquids (NGLs). The natural
gas extracted from coal reservoirs and mines (coalbed methane) is the primary exception,
being essentially a mix of mostly methane and carbon dioxide (about 10 percent).

Natural gas processing plants, (or whatever apparatus capable of separating liquid substance
into component parts) are used to purify the raw natural gas produced from underground gas
fields or extracted at the surface from the fluids produced from oil wells. A fully operational
plant will deliver pipeline-quality natural gas that can be used as fuel by residential,
commercial and industrial consumers. Contaminants have been removed and heavier
hydrocarbons (any class of compound containing only hydrogen and carbon; examples are
methane gas (CH4), benzene (C6H6)) have been captured for other commercial uses. For
economic reasons, however, some plants may be designed to yield an intermediate product
typically containing over 90% pure methane and smaller amounts of nitrogen, carbon
dioxide, and sometimes ethane. This can be further processed in downstream plants or used
as feedstock for chemicals manufacturing.

Types of raw natural gas wells

Raw natural gas comes primarily from any one of three types of wells: crude oil wells, gas
wells, and condensate wells.

Natural gas that comes from crude oil wells is typically termed associated gas. This gas can
have existed as a gas cap above the crude oil in the underground formation, or could have
been dissolved in the crude oil.

Natural gas from gas wells and from condensate wells, in which there is little or no crude oil,
is termed non-associated gas. Gas wells typically produce only raw natural gas, while
condensate wells produce raw natural gas along with other low molecular weight
hydrocarbons. Those that are liquid at ambient conditions (i.e., pentane and heavier) are
called natural gas condensate (sometimes also called natural gasoline or simply
condensate).

Natural gas is termed sweet gas when relatively free of hydrogen sulfide; however, some
produced gas does contain this substance and thus is called sour gas.

Raw natural gas can also come from methane deposits in the pores of coal seams, and
especially in a more concentrated state of adsorption onto the surface of the coal itself. Such
gas is referred to as coalbed gas or coalbed methane. Coalbed gas is a from of natural gas
that is has being extracted from coalbed. This coalbed gas has become an important source of
energy in recent decades.

Contaminants in raw natural gas

Raw natural gas typically consists primarily of methane (CH4), the shortest and lightest
hydrocarbon molecule. It also contains varying amounts of:

 Heavier gaseous hydrocarbons: ethane (C2H6), propane (C3H8), normal butane (n-
C4H10), isobutane (i-C4H10), pentanes and even higher molecular weight
hydrocarbons. When processed and purified into finished by-products, all of these are
collectively referred to as NGL (Natural Gas Liquids).
 Acid gases: carbon dioxide (CO2), hydrogen sulfide (H2S) and mercaptans such as
methanethiol (CH3SH) and ethanethiol (C2H5SH).
 Other gases: nitrogen (N2) and helium (He).
 Water: water vapor and liquid water. Also dissolved salts and dissolved gases (acids).
 Liquid hydrocarbons: perhaps some natural gas condensate (also referred to as
casinghead gasoline or natural gasoline) and/or crude oil.
 Mercury: very small amounts of mercury primarily in elemental form, but chlorides
and other species are possibly present.[2]
 Radioactive gas: radon. Also, when radon is present, decay products of radon, such as
polonium, can accumulate in specific locations within processing equipment.

The raw natural gas must be purified to meet the quality standards specified by the major
pipeline transmission and distribution companies. Those quality standards vary from pipeline
to pipeline and are usually a function of a pipeline system's design and the markets that it
serves. In general, the standards specify that the natural gas:

 Be within a specific range of heating value (caloric value). For example, in the United
States, it should be about 1035 ± 5% BTU per cubic foot of gas at 1 atmosphere and
60 degrees Fahrenheit (41 MJ ± 5% per cubic metre of gas at 1 atmosphere and 0
degrees Celsius).
 Be delivered at or above a specified hydrocarbon dew point temperature (below
which some of the hydrocarbons in the gas might condense at pipeline pressure
forming liquid slugs that could damage the pipeline).
 Dew-point adjustment serves the reduction of the concentration of water and heavy
hydrocarbons in natural gas to such an extent that no condensation occurs during the
ensuing transport in the pipelines
 Be free of particulate solids and liquid water to prevent erosion, corrosion or other
damage to the pipeline.
  Be dehydrated of water vapor sufficiently to prevent the formation of methane
hydrates within the gas processing plant or subsequently within the sales gas
transmission pipeline. A typical water content specification in the U.S. is that gas
must contain no more than seven pounds of water per million cubic feet (MMCFD) of
gas.[3][4]
 Contain no more than trace amounts of components such as hydrogen sulfide, carbon
dioxide, mercaptans, and nitrogen. The most common specification for hydrogen
sulfide content is 0.25 grain H2S per 100 cubic feet of gas, or approximately 4 ppm.
Specifications for CO2 typically limit the content to no more than two or three
percent.
 Maintain mercury at less than detectable limits (approximately 0.001 ppb by volume)
primarily to avoid damaging equipment in the gas processing plant or the pipeline
transmission system from mercury amalgamation and embrittlement of aluminum and
other metals.[2][5][6]

Description of a natural gas processing plant

There are a great many ways in which to configure the various unit processes used in the
processing of raw natural gas. The block flow diagram below is a generalized, typical
configuration for the processing of raw natural gas from non-associated gas wells. It shows
how raw natural gas is processed into sales gas pipelined to the end user markets.[7][8][9][10][11]
It also shows how processing of the raw natural gas yields these byproducts:

 Natural gas condensate

 Sulfur
 Ethane
 Natural gas liquids (NGL): propane, butanes and C5+ (which is the commonly used
term for pentanes plus higher molecular weight hydrocarbons)

Raw natural gas is commonly collected from a group of adjacent wells and is first processed
at that collection point for removal of free liquid water and natural gas condensate. The
condensate is usually then transported to an oil refinery and the water is disposed of as
wastewater.

The raw gas is then pipelined to a gas processing plant where the initial purification is
usually the 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.

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 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 autothermal on tail gasses.

The next step in the gas processing plant is to remove water vapor from the gas using either
the regenerable absorption in liquid triethylene glycol (TEG)[4], commonly referred to as
glycol dehydration, deliquescent chloride desiccants, and or a Pressure Swing Adsorption
(PSA) unit which is regenerable adsorption using a solid adsorbent.[12] Other newer processes
like membranes may also be considered.

Mercury is then removed by using adsorption processes (as shown in the flow diagram) such
as activated carbon or regenerable molecular sieves.[2]

Although not common, nitrogen is sometimes removed and rejected using one of the three
processes indicated on the flow diagram:

 Cryogenic process[13] using low temperature distillation. This process can be modified
to also recover helium, if desired.
 Absorption process[14] using lean oil or a special solvent[15] as the absorbent.
 Adsorption process using activated carbon or molecular sieves as the adsorbent. This
process may have limited applicability because it is said to incur the loss of butanes
and heaver hydrocarbons.

The next step is to recover the natural gas liquids (NGL) for which most large, modern gas
processing plants use another cryogenic low temperature distillation process involving
expansion of the gas through a turbo-expander followed by distillation in a demethanizing
fractionating column.[16][17] Some gas processing plants use lean oil absorption process[14]
rather than the cryogenic turbo-expander process.

The residue gas from the NGL recovery section is the final, purified sales gas which is
pipelined to the end-user markets.

The recovered NGL stream is sometimes processed through a fractionation train consisting of
three distillation towers in series: a deethanizer, a depropanizer and a debutanizer. The
overhead product from the deethanizer is ethane and the bottoms are fed to the depropanizer.
The overhead product from the depropanizer is propane and the bottoms are fed to the
debutanizer. The overhead product from the debutanizer is a mixture of normal and iso-
butane, and the bottoms product is a C5+ mixture. The recovered streams of propane, butanes
and C5+ may be "sweetened" in a Merox process unit to convert undesirable mercaptans into
disulfides and, along with the recovered ethane, are the final NGL by-products from the gas
processing plant. Currently, most cryogenic plants do not include fractionation for economic
reasons, and the NGL stream is instead transported as a mixed product to standalone
fractionation complexes located near refineries or chemical plants that use the components
for feedstock. In case laying pipeline is not possible for geographical reason,or the distance
between source and consumer exceed 3000km, natural gas is then transported by ship as
LNG (liquefied natural gas) and again converted into its gaseous state in the vicinity of the
consumer.
 Legend:

 Located at gas wells

 Located at gas processing plant
 Red indicates final sales products
 Blue indicates optional unit processes available

Notes:

 Condensate is also called natural gasoline or casinghead gasoline.

 "Pentanes +" refers to pentanes and heavier hydrocarbons, and are also called
natural gasoline.
 "Acid gases" are hydrogen sulfide and carbon dioxide.
 PSA is Pressure Swing Adsorption.
 NGL is Natural Gas Liquids.
 Sweetening processes remove mercaptans from the NGL products.

Consumption

The consumption of natural gas differs widely from country to country. Countries with large
own reserves tend to handle the raw material natural gas more generously, while countries
with scarce or lacking resources are of course more economical. Despite the considerable
findings, the predicted availability of the natural gas reserves has hardly changed.
Applications of Natural Gas

 Fuel for industrial heating and desiccation process

 Fuel for the operation of public and industrial power stations
 Household fuel for cooking, heating and providing hot water
 Fuel for environmentally friendly liquid natural gas vehicles
 Raw material for chemical synthesis
 Raw material for large-scale fuel production using gas-to-liquid (GTL) process (e.g.
to produce sulphur-and aromatic-free diesel with low-emission combustion)

Natural gas, as it is used by consumers, is much different from the natural gas that is brought
from underground up to the wellhead. Although the processing of natural gas is in many
respects less complicated than the processing and refining of crude oil, it is equally as
necessary before its use by end users.

The natural gas used by consumers is composed almost entirely of methane. However,
natural gas found at the wellhead, although still composed primarily of methane, is by no
means as pure. Raw natural gas comes from three types of wells: oil wells, gas wells, and
condensate wells. Natural gas that comes from oil wells is typically termed 'associated gas'.
This gas can exist separate from oil in the formation (free gas), or dissolved in the crude oil
(dissolved gas). Natural gas from gas and condensate wells, in which there is little or no
crude oil, is termed 'nonassociated gas'. Gas wells typically produce raw natural gas by itself,
while condensate wells produce free natural gas along with a semi-liquid hydrocarbon
condensate. Whatever the source of the natural gas, once separated from crude oil (if present)
it commonly exists in mixtures with other hydrocarbons; principally ethane, propane, butane,
and pentanes. In addition, raw natural gas contains water vapor, hydrogen sulfide (H2S),
carbon dioxide, helium, nitrogen, and other compounds. To learn about the basics of natural
gas, including its composition, click here.

Natural gas processing consists of separating all of the various hydrocarbons and fluids from
the pure natural gas, to produce what is known as 'pipeline quality' dry natural gas. Major
transportation pipelines usually impose restrictions on the make-up of the natural gas that is
allowed into the pipeline. That means that before the natural gas can be transported it must be
purified. While the ethane, propane, butane, and pentanes must be removed from natural gas,
this does not mean that they are all 'waste products'.

In fact, associated hydrocarbons, known as 'natural gas liquids' (NGLs) can be very valuable
by-products of natural gas processing. NGLs include ethane, propane, butane, iso-butane, and
natural gasoline. These NGLs are sold separately and have a variety of different uses;
including enhancing oil recovery in oil wells, providing raw materials for oil refineries or
petrochemical plants, and as sources of energy.

While some of the needed processing can be accomplished at or near the wellhead (field
processing), the complete processing of natural gas takes place at a processing plant, usually
located in a natural gas producing region. The extracted natural gas is transported to these
processing plants through a network of gathering pipelines, which are small-diameter, low
pressure pipes. A complex gathering system can consist of thousands of miles of pipes,
interconnecting the processing plant to upwards of 100 wells in the area. According to the
American Gas Association's Gas Facts 2000, there was an estimated 36,100 miles of
gathering system pipelines in the U.S. in 1999.
In addition to processing done at the wellhead and at centralized processing plants, some
final processing is also sometimes accomplished at 'straddle extraction plants'. These plants
are located on major pipeline systems. Although the natural gas that arrives at these straddle
extraction plants is already of pipeline quality, in certain instances there still exist small
quantities of NGLs, which are extracted at the straddle plants.

The actual practice of processing natural gas to pipeline dry gas quality levels can be quite
complex, but usually involves four main processes to remove the various impurities:

 Oil and Condensate Removal

 Water Removal
 Separation of Natural Gas Liquids
 Sulfur and Carbon Dioxide Removal

In addition to the four processes above, heaters and scrubbers are installed, usually at or near
the wellhead. The scrubbers serve primarily to remove sand and other large-particle
impurities. The heaters ensure that the temperature of the gas does not drop too low. With
natural gas that contains even low quantities of water, natural gas hydrates have a tendency to
form when temperatures drop. These hydrates are solid or semi-solid compounds, resembling
ice like crystals. Should these hydrates accumulate, they can impede the passage of natural
gas through valves and gathering systems. To reduce the occurrence of hydrates, small
natural gas-fired heating units are typically installed along the gathering pipe wherever it is
likely that hydrates may form.

Oil and Condensate Removal

In order to process and transport associated dissolved natural gas, it must be separated from
the oil in which it is dissolved. This separation of natural gas from oil is most often done
using equipment installed at or near the wellhead.

The actual process used to separate oil from natural gas, as well as the equipment that is
used, can vary widely. Although dry pipeline quality natural gas is virtually identical across
different geographic areas, raw natural gas from different regions may have different
compositions and separation requirements. In many instances, natural gas is dissolved in oil
underground primarily due to the pressure that the formation is under. When this natural gas
and oil is produced, it is possible that it will separate on its own, simply due to decreased
pressure; much like opening a can of soda pop allows the release of dissolved carbon dioxide.
In these cases, separation of oil and gas is relatively easy, and the two hydrocarbons are sent
separate ways for further processing. The most basic type of separator is known as a
conventional separator. It consists of a simple closed tank, where the force of gravity serves
to separate the heavier liquids like oil, and the lighter gases, like natural gas.

In certain instances, however, specialized equipment is necessary to separate oil and natural
gas. An example of this type of equipment is the Low-Temperature Separator (LTX). This is
most often used for wells producing high pressure gas along with light crude oil or
condensate. These separators use pressure differentials to cool the wet natural gas and
separate the oil and condensate. Wet gas enters the separator, being cooled slightly by a heat
exchanger. The gas then travels through a high pressure liquid 'knockout', which serves to
remove any liquids into a low-temperature separator. The gas then flows into this low-
temperature separator through a choke mechanism, which expands the gas as it enters the
separator. This rapid expansion of the gas allows for the lowering of the temperature in the
separator. After liquid removal, the dry gas then travels back through the heat exchanger and
is warmed by the incoming wet gas. By varying the pressure of the gas in various sections of
the separator, it is possible to vary the temperature, which causes the oil and some water to
be condensed out of the wet gas stream. This basic pressure-temperature relationship can
work in reverse as well, to extract gas from a liquid oil stream.

Water Removal

In addition to separating oil and some condensate from the wet gas stream, it is necessary to
remove most of the associated water. Most of the liquid, free water associated with extracted
natural gas is removed by simple separation methods at or near the wellhead. However, the
removal of the water vapor that exists in solution in natural gas requires a more complex
treatment. This treatment consists of 'dehydrating' the natural gas, which usually involves one
of two processes: either absorption, or adsorption.

Absorption occurs when the water vapor is taken out by a dehydrating agent. Adsorption
occurs when the water vapor is condensed and collected on the surface.

Glycol Dehydration

An example of absorption dehydration is known as Glycol Dehydration. In this process, a

liquid desiccant dehydrator serves to absorb water vapor from the gas stream. Glycol, the
principal agent in this process, has a chemical affinity for water. This means that, when in
contact with a stream of natural gas that contains water, glycol will serve to 'steal' the water
out of the gas stream. Essentially, glycol dehydration involves using a glycol solution,
usually either diethylene glycol (DEG) or triethylene glycol (TEG), which is brought into
contact with the wet gas stream in what is called the 'contactor'. The glycol solution will
absorb water from the wet gas. Once absorbed, the glycol particles become heavier and sink
to the bottom of the contactor where they are removed. The natural gas, having been stripped
of most of its water content, is then transported out of the dehydrator. The glycol solution,
bearing all of the water stripped from the natural gas, is put through a specialized boiler
designed to vaporize only the water out of the solution. While water has a boiling point of
212 degrees Fahrenheit, glycol does not boil until 400 degrees Fahrenheit. This boiling point
differential makes it relatively easy to remove water from the glycol solution, allowing it be
reused in the dehydration process.

A new innovation in this process has been the addition of flash tank separator-condensers. As
well as absorbing water from the wet gas stream, the glycol solution occasionally carries with
it small amounts of methane and other compounds found in the wet gas. In the past, this
methane was simply vented out of the boiler. In addition to losing a portion of the natural gas
that was extracted, this venting contributes to air pollution and the greenhouse effect. In order
to decrease the amount of methane and other compounds that are lost, flash tank separator-
condensers work to remove these compounds before the glycol solution reaches the boiler.
Essentially, a flash tank separator consists of a device that reduces the pressure of the glycol
solution stream, allowing the methane and other hydrocarbons to vaporize ('flash'). The
glycol solution then travels to the boiler, which may also be fitted with air or water cooled
condensers, which serve to capture any remaining organic compounds that may remain in the
glycol solution. In practice, according to the Department of Energy's Office of Fossil Energy,
these systems have been shown to recover 90 to 99 percent of methane that would otherwise
be flared into the atmosphere.
Solid-Desiccant Dehydration

Solid-desiccant dehydration is the primary form of dehydrating natural gas using adsorption,
and usually consists of two or more adsorption towers, which are filled with a solid
desiccant. Typical desiccants include activated alumina or a granular silica gel material. Wet
natural gas is passed through these towers, from top to bottom. As the wet gas passes around
the particles of desiccant material, water is retained on the surface of these desiccant
particles. Passing through the entire desiccant bed, almost all of the water is adsorbed onto
the desiccant material, leaving the dry gas to exit the bottom of the tower.

Solid-desiccant dehydrators are typically more effective than glycol dehydrators, and are
usually installed as a type of straddle system along natural gas pipelines. These types of
dehydration systems are best suited for large volumes of gas under very high pressure, and
are thus usually located on a pipeline downstream of a compressor station. Two or more
towers are required due to the fact that after a certain period of use, the desiccant in a
particular tower becomes saturated with water. To 'regenerate' the desiccant, a high-
temperature heater is used to heat gas to a very high temperature. Passing this heated gas
through a saturated desiccant bed vaporizes the water in the desiccant tower, leaving it dry
and allowing for further natural gas dehydration.

Separation of Natural Gas Liquids

Natural gas coming directly from a well contains many natural gas liquids that are commonly
removed. In most instances, natural gas liquids (NGLs) have a higher value as separate
products, and it is thus economical to remove them from the gas stream. The removal of
natural gas liquids usually takes place in a relatively centralized processing plant, and uses
techniques similar to those used to dehydrate natural gas.

There are two basic steps to the treatment of natural gas liquids in the natural gas stream.
First, the liquids must be extracted from the natural gas. Second, these natural gas liquids
must be separated themselves, down to their base components.

NGL Extraction

There are two principle techniques for removing NGLs from the natural gas stream: the
absorption method and the cryogenic expander process. According to the Gas Processors
Association, these two processes account for around 90 percent of total natural gas liquids
production.

The Absorption Method

The absorption method of NGL extraction is very similar to using absorption for dehydration.
The main difference is that, in NGL absorption, an absorbing oil is used as opposed to glycol.
This absorbing oil has an 'affinity' for NGLs in much the same manner as glycol has an
affinity for water. Before the oil has picked up any NGLs, it is termed 'lean' absorption oil.
As the natural gas is passed through an absorption tower, it is brought into contact with the
absorption oil which soaks up a high proportion of the NGLs. The 'rich' absorption oil, now
containing NGLs, exits the absorption tower through the bottom. It is now a mixture of
absorption oil, propane, butanes, pentanes, and other heavier hydrocarbons. The rich oil is
fed into lean oil stills, where the mixture is heated to a temperature above the boiling point of
the NGLs, but below that of the oil. This process allows for the recovery of around 75
percent of butanes, and 85 - 90 percent of pentanes and heavier molecules from the natural
gas stream.

The basic absorption process above can be modified to improve its effectiveness, or to target
the extraction of specific NGLs. In the refrigerated oil absorption method, where the lean oil
is cooled through refrigeration, propane recovery can be upwards of 90 percent, and around
40 percent of ethane can be extracted from the natural gas stream. Extraction of the other,
heavier NGLs can be close to 100 percent using this process.

The Cryogenic Expansion Process

Cryogenic processes are also used to extract NGLs from natural gas. While absorption
methods can extract almost all of the heavier NGLs, the lighter hydrocarbons, such as ethane,
are often more difficult to recover from the natural gas stream. In certain instances, it is
economic to simply leave the lighter NGLs in the natural gas stream. However, if it is
economic to extract ethane and other lighter hydrocarbons, cryogenic processes are required
for high recovery rates. Essentially, cryogenic processes consist of dropping the temperature
of the gas stream to around -120 degrees Fahrenheit.

There are a number of different ways of chilling the gas to these temperatures, but one of the
most effective is known as the turbo expander process. In this process, external refrigerants
are used to cool the natural gas stream. Then, an expansion turbine is used to rapidly expand
the chilled gases, which causes the temperature to drop significantly. This rapid temperature
drop condenses ethane and other hydrocarbons in the gas stream, while maintaining methane
in gaseous form. This process allows for the recovery of about 90 to 95 percent of the ethane
originally in the gas stream. In addition, the expansion turbine is able to convert some of the
energy released when the natural gas stream is expanded into recompressing the gaseous
methane effluent, thus saving energy costs associated with extracting ethane.

The extraction of NGLs from the natural gas stream produces both cleaner, purer natural gas,
as well as the valuable hydrocarbons that are the NGLs themselves.

Natural Gas Liquid Fractionation

Once NGLs have been removed from the natural gas stream, they must be broken down into
their base components to be useful. That is, the mixed stream of different NGLs must be
separated out. The process used to accomplish this task is called fractionation. Fractionation
works based on the different boiling points of the different hydrocarbons in the NGL stream.
Essentially, fractionation occurs in stages consisting of the boiling off of hydrocarbons one
by one. The name of a particular fractionator gives an idea as to its purpose, as it is
conventionally named for the hydrocarbon that is boiled off. The entire fractionation process
is broken down into steps, starting with the removal of the lighter NGLs from the stream. The
particular fractionators are used in the following order:

 Deethanizer - this step separates the ethane from the NGL stream.
 Depropanizer - the next step separates the propane.
 Debutanizer - this step boils off the butanes, leaving the pentanes and heavier
hydrocarbons in the NGL stream.
 Butane Splitter or Deisobutanizer - this step separates the iso and normal butanes.
By proceeding from the lightest hydrocarbons to the heaviest, it is possible to separate the
different NGLs reasonably easily.

To learn more about the fractionation of NGLs, click here.

Sulfur and Carbon Dioxide Removal

In addition to water, oil, and NGL removal, one of the most important parts of gas processing
involves the removal of sulfur and carbon dioxide. Natural gas from some wells contains
significant amounts of sulfur and carbon dioxide. This natural gas, because of the rotten
smell provided by its sulfur content, is commonly called 'sour gas'. Sour gas is undesirable
because the sulfur compounds it contains can be extremely harmful, even lethal, to breathe.
Sour gas can also be extremely corrosive. In addition, the sulfur that exists in the natural gas
stream can be extracted and marketed on its own. In fact, according to the USGS, U.S. sulfur
production from gas processing plants accounts for about 15 percent of the total U.S.
production of sulfur.

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.

In all, the Claus process is usually able to recover 97 percent of the sulfur that has been
removed from the natural gas stream. Since it is such a polluting and harmful substance,
further filtering, incineration, and 'tail gas' clean up efforts ensure that well over 98 percent of
the sulfur is recovered.
Gas processing is an instrumental piece of the natural gas value chain. It is instrumental in
ensuring that the natural gas intended for use is as clean and pure as possible, making it the
clean burning and environmentally sound energy choice. Once the natural gas has been fully
processed, and is ready to be consumed, it must be transported from those areas that produce
natural gas, to those areas that require it.

Sour gas

Sour gas is natural gas or any other gas containing significant amounts of hydrogen sulfide
(H2S). Natural gas is usually considered sour if there are more than 5.7 milligrams of H2S per
cubic meter of natural gas, which is equivalent to approximately 4 ppm by volume[1]. (On the
other hand, natural gas that does not contain significant amounts of hydrogen sulfide is called
"sweet gas.")

Although the terms acid gas and sour gas are used interchangeably, strictly speaking, a sour
gas is any gas that contains hydrogen sulfide in significant amounts, whereas an acid gas is
any gas that contains significant amounts of acidic gases such as carbon dioxide (CO2) or
hydrogen sulfide. Thus, carbon dioxide by itself is an acid gas but it is not a sour gas.

Before a raw natural gas containing hydrogen sulfide and/or carbon dioxide can be used, the
raw gas must be treated to remove those impurities to acceptable levels, commonly by an
amine gas treating process.[1][2] The removed H2S is most often subsequently converted to by-
product elemental sulfur in a Claus process or it can be treated in a WSA Process unit where
the by-product is sulfuric acid. Alternatively, the highly H2S concentrated gas, the by-product
of the amine treatment plant, can be recompressed by compressor units specifically designed
to handle highly toxic gas and injected in the reservoir. Such a solution was installed in the
Sultanate of Oman and was successfully put in operation in about 1998.

Processes within oil refineries or natural gas processing plants that remove mercaptans and/or
hydrogen sulfide are commonly referred to as sweetening processes because they result in
products which no longer have the sour, foul odors of mercaptans and hydrogen sulfide.

Hydrogen sulfide is a toxic gas. It also places restrictions on the materials that can be used
for piping and other equipment handling sour gas, as many metals are sensitive to sulfide
stress cracking. The presence of hydrogen sulfide in gas causes lower quality burning and the
production of sulfur dioxide, and so is regulated in commercially sold gas.

5.3 Natural Gas Processing

5.3.1 General1
Natural gas from high-pressure wells is usually passed through field separators at the well to
remove
hydrocarbon condensate and water. Natural gasoline, butane, and propane are usually present
in the gas, and
gas processing plants are required for the recovery of these liquefiable constituents (see
Figure 5.3-1).
Natural gas is considered "sour" if hydrogen sulfide (H2 S) is present in amounts greater than
5.7 milligrams
per normal cubic meters (mg/Nm3) (0.25 grains per 100 standard cubic feet [gr/100 scf]).
The H S must be
2
removed (called "sweetening" the gas) before the gas can be utilized. If H2 S is present, the
gas is usually
sweetened by absorption of the H2S in an amine solution. Amine processes are used for over
95 percent of
all gas sweetening in the United States. Other methods, such as carbonate processes, solid
bed absorbents,
and physical absorption, are employed in the other sweetening plants. Emission data for
sweetening
processes other than amine types are very meager, but a material balance on sulfur will give
accurate
estimates for sulfur dioxide (SO2).
The major emission sources in the natural gas processing industry are compressor engines,
acid gas
wastes, fugitive emissions from leaking process equipment and if present, glycol dehydrator
vent streams.
Compressor engine emissions are discussed in Section 3.3.2. Fugitive leak emissions are
detailed in Protocol
For Equipment Leak Emission Estimates, EPA-453/R-95-017, November 1995. Regeneration
of the glycol
solutions used for dehydrating natural gas can release significant quantities of benzene,
toluene, ethylbenzene,
and xylene, as well as a wide range of less toxic organics. These emissions can be estimated
by a
thermodynamic software model (GRI-GLYCalcTM) available from the Gas Research
Institute. Only the SO
2
emissions from gas sweetening operations are discussed here.
5.3.2 Process Description2-3
Many chemical processes are available for sweetening natural gas. At present, the amine
process
(also known as the Girdler process), is the most widely used method for H2 S removal. The
process is
summarized in reaction 1 and illustrated in Figure 5.3-2.
where:
R = mono, di, or tri-ethanol
N = nitrogen
H = hydrogen
S = sulfur
The recovered hydrogen sulfide gas stream may be: (1) vented, (2) flared in waste gas flares
or
modern smokeless flares, (3) incinerated, or (4) utilized for the production of elemental
sulfur or sulfuric acid.
If the recovered H2S gas stream is not to be utilized as a feedstock for commercial
applications, the gas is
usually passed to a tail gas incinerator in which the H2 S is oxidized to SO2 and is then
passed to the
atmosphere out a stack. For more details, the reader should consult Reference 8.

5.3.3 Emissions4-5
Emissions will result from gas sweetening plants only if the acid waste gas from the amine
process is
flared or incinerated. Most often, the acid waste gas is used as a feedstock in nearby sulfur
recovery or sulfuric acid plants. See Sections 8.13 "Sulfur Recovery", or 8.10, "Sulfuric
Acid", respectively,
for these associated processes.
When flaring or incineration is practiced, the major pollutant of concern is SO2 . Most plants
employ
elevated smokeless flares or tail gas incinerators for complete combustion of all waste gas
constituents,
including virtually 100 percent conversion of H2 S to SO2 . Little particulate, smoke, or
hydrocarbons result
from these devices, and because gas temperatures do not usually exceed 650EC (1200EF),
significant
quantities of nitrogen oxides are not formed. Emission factors for gas sweetening plants with
smokeless
flares or incinerators are presented in Table 5.3-1. Factors are expressed in units of kilograms
per 1000 cubic
meters (kg/103 m3) and pounds per million standard cubic feet (lb/106 scf).
Some plants still use older, less-efficient waste gas flares. Because these flares usually burn
at
temperatures lower than necessary for complete combustion, larger emissions of
hydrocarbons and
particulate, as well as H2S, can occur. No data are available to estimate the magnitude of
these emissions
from waste gas flares.

GAS PROCESSING
Black & Veatch is a world leader in all aspects of natural gas processing – from gas treating
and sulfur recovery to NGL recovery and fractionation to LNG. Black & Veatch provides
process design, engineering, procurement and construction (EPC) services, delivering to our
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From feasibility studies to plant startup, the value you gain with Black & Veatch is significant.
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that is focused on excellence in execution in every phase of your project.
If you are looking for complete performance that delivers price and schedule certainty, as well
as long-term value for your project, one company brings it all together, Black & Veatch.
FULL-SCOPE SOLUTIONS
Wherever you operate along the gas value chain, Black & Veatch has you covered.
ACID GAS REMOVAL
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• Solvent flows to 12,000 gpm
DEHYDRATION
• Glycols, solid bed and hybrid systems
• 100+ units
• Size range: to 2,200 MMSCFD
SULFUR RECOVERY
• Claus, CBA, SCOT, ARCO Tail Gas and oxygen enrichment technology
• 300+ projects worldwide (more than 40,000 ltpd) • Single-facility capacities over 4,000 ltpd
• Acid gas conditions:
Ammonia – up to 45%
Hydrogen Sulfide – 12 to 100%
Hydrogen Cyanide – up to 2%
NGL RECOVERY
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• 75+ units
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• Innovative execution capabilities

In order to understand the chemistry of natural gas, it is important to be familiar with some
basic concepts of general chemistry. Here are some definitions you should know:

Matter – anything that has mass and occupies space. Energy – the capacity to do work or
transfer heat.
Elements – substances that cannot be decomposed into simpler substances by chemical
changes. There are approximately 112 known elements. Examples: carbon, oxygen, and
nitrogen.
Atom – the smallest unit in which an element can exist. Atoms are composed of electrons,
protons, and neutrons. Compounds – pure substances consisting of two or more different
elements in a fixed ratio. Examples: water and methane.
Molecule – the smallest unit in which a compound can exist or the normal form in which an
element exists. Example: One molecule of water consists of two hydrogen atoms and one
oxygen atom. One molecule of nitrogen consists of two atoms of nitrogen.
Mixture – combination of two or more pure substances in which each substance maintains its
own composition and properties. Examples: natural gas, gasoline, and air.
Bonds – The attractive forces that hold atoms together in compounds are called chemical
bonds. There are two major classes of bonds–ionic bonds and covalent bonds. Most of the
bonds involved in natural gas components are single covalent bonds. A single covalent bond
consists of a pair of electrons shared by two atoms. A double bond is two pair of electrons
shared between two atoms. Some minor components of natural gas may contain both single
and double bonds.
Aromatic molecules, such as benzene, contain covalent bonds where multiple electrons are
shared among more than two atoms.

States of Matter
Matter exists mainly in three physical states–gas, liquid, and solid. Solids are rigid and have
definite shapes. The volume a solid occupies does not vary much with changes in temperature
and pressure. In liquids, the individual particles are confined to a given volume. A liquid flows
and assumes the shape of its container. Liquids cannot be easily compressed. Gases are much
less dense than liquids and solids. They occupy all parts of any vessel in which they are
confined. Gases are capable of infinite expansion and are easily compressed. They consist
primarily of empty space because the individual particles are so far a part. Units of
Measurement Quantities of matter can be expressed in a variety of ways depending on the
nature of the substance being measured. For example, solids are generally measured by weight
while liquids are measured by volume or weight. Gas is most commonly measured in units of
volume but can also be measured by weight. The standard unit of volume used in natural gas
measurement is a cubic foot corrected to a standard ( stated ) pressure and temperature. Large
volumes of natural gas are usually expressed in units of one thousand cubic feet (Mcf). A
million cubic feet is indicated by MMcf. When a gas sample is analyzed, however, the
composition is usually expressed in mole percent –the percent ( by number ) of moles of the
particular substance out of the total molecules of the gas. This is roughly equivalent to volume
percent. A mole is defined as the amount of a substance that contains the same number of units
as the number of atoms in 12 grams of Carbon12 which is 6.022 x 10-23, otherwise known as
Avogadro’s number. Therefore, a mole of any element or compound is simply the molecular
weight of that substance in grams. For example, the molecular weight of water is 18, so a mole
of water is 18 grams and contains 6.022 x 10-23molecules. Moles are often used in chemistry
because they make it easier to keep track of quantities of substances involved in chemical
reactions. One mole of oxygen will react with 2 moles of hydrogen to form one mole of water.
However, there would be an excess of hydrogen if one gram of oxygen were reacted with 2
grams of hydrogen.

Natural Gas
Natural gas is a mixture of many compounds which can be classified into three major groups–
hydrocarbons, inerts, and miscellaneous trace compounds. Hydrocarbons are compounds
which contain hydrogen and carbon. Most of the hydrocarbons in natural gas are saturated,
meaning that each carbon atom is bonded to four other atoms while each hydrogen atom is
bonded to only one carbon atom. This group of compounds is also known as alkanes, paraffins,
and aliphatics. The most abundant alkane in natural gas is methane, commonly referred to as
C1 because it contains one carbon atom. Next is ethane (C2) with two carbons, followed by
propane (C3), iso-butane and normal butane (C4), iso-pentane and normal pentane (C5), and
hexanes and heavier hydrocarbons (C6+). The C6+ fraction can contain up to 100 or more
compounds including aromatics such as benzene, toluene, ethyl benzene and xylenes
(BTEX).Deposits of natural gas are usually found with petroleum deposits. Most of the natural
gas and petroleum being produced, today, was formed by the decay of plants and animals
buried deep within the earth millions of years ago. A small fraction of natural gas is also being
produced by the decomposition of residential and commercial waste in land fills. Petroleum
products are complex mixtures of aliphatic and aromatic compounds, including sulfur and
nitrogen compounds. Some of the most common refined petroleum products include methane
gas, natural gas liquid or NGL (the ethane and heavier gas components), liquefied petroleum
gas or LPG (mostly propane and butane), gasoline (C5-C10), kerosene (C11-C12), diesel fuel
(C13-C17),heating oil (C18-C25), and lubricants (C26-C38). Heavier residues of refining are
referred to as asphalts. In addition to hydrocarbons, natural gas components include the inerts,
nitrogen and carbon dioxide, which do not combust. Therefore, they do not contribute to the
heating value of the gas, making them undesirable. Trace components commonly include
hydrogen sulfide, water vapor, and helium. Hydrogen sulfide is highly toxic and is
characterized by a very strong, foul odor.It is also referred to as sour gas. Helium is a true inert
gas that is non reactive with other compounds. Most of the nation’s helium production comes
from natural gas deposits in Texas. Other less common trace components include oxygen,
hydrogen, and carbon monoxide.

Physical Properties
Physical properties are those which can be observed without causing any changein the
chemical composition of the specimen. One of the most important physical properties used in
the petroleum industry is density. Density is the mass (weight) per unit volume of a substance
and may be expressed as specific gravity or relative density. In liquids, the specific gravity is
the ratio of the density of the liquid to the density of water. In gases, it is the ratio of the
density of the gas to the density of air. The specific gravity of natural gas varies from less than
.600 for gas containing mostly methane to greater than 1.000 for gas containing a high
percentage of heavy end components. Other important physical properties of gases include
boiling point, hydrocarbon dew point, odor, toxicity, and thermal conductivity. Boiling point is
the temperature at which the vapor pressure of a liquid equals the atmospheric pressure.
Hydrocarbon dew point is the temperature at which hydrocarbons start to condense from a gas
stream. This is important in gas production and transmission because condensation in a natural
gas line will lower the capacity of the line to carry gas. Consequently, there will be problems
with compressors, dehydrators, and other processing equipment. More importantly, liquids in a
gas line make it impossible to accurately measure the gas. The dew point also allows the
heavier gases to be liquefied by processing. They are generally more valuable as liquids than
gas. Odorizing is important in gas processing and transportation as a relatively inexpensive
way of determining the location of leaks. Unless it contains high concentrations of hydrogen
sulfide or other contaminants, natural gas is normally odorless and nontoxic when it comes out
of the ground. Nontoxic odorants,
such as mercaptans, are added during processing to make it detectable by sense of smell.
Thermal conductivity is the property which enables the detector on a chromatograph to
quantify the amount of each component in a gas mixture. Simply stated, it is the ability of a
substance to conduct heat. Thermal conductivity usually decreases with increasing particle
size. For this reason, helium makes a good carrier gas for gas chromatographs. Its molecules
are very small, allowing it to effectively draw heat away from the detector.

Heating Value
The Btu, or British thermal unit, is a measure of the energy produced by burning natural gas. A
Btu is equal to the amount of heat required to raise the temperature of one pound of water one
degree Fahrenheit at 62? F. The Btu may be expressed as dry, wet, or as delivered. The dry Btu
calculation assumes that there is no water vapor in the gas. As might be expected, the wet Btu
is calculated on the assumption that the gas is saturated with water vapor at standard
conditions (60º F and atmospheric pressure). Hence, the wet Btu is less than the dry Btu. The
as delivered or actual Btu is calculated by accounting for the actual amount of water in the gas
based on delivery conditions. The Btu factors of the individual components in natural gas,
increase with the number of carbon atoms. The table in Figure 1 illustrates the Btu of the most
common components in natural gas. The inerts commonly found in gas, carbon dioxide and
nitrogen, do not participate in combustion and contribute no heating value or Btu to a gas.
Water vapor, though it does not burn, has a heating value as defined by this industry. Water
vapor has a heating value of 50.4 Btu per standard cubic foot.
Compressibility
Compressibility is a measure of a real gas’s deviation from ideal gas behavior. Real gases
behave like ideal gases at low pressures and high temperatures. Because they deviate
significantly at high pressures and low temperatures, the deviation should be accounted for
when calculating Btu. An ideal gas is one that obeys the Ideal Gas Law — it occupies half its
initial volume at twice the initial pressure and twice its volume at twice its
(absolute)temperature.

Reactions and Processes Involving Natural Gas

Under normal conditions, the hydrocarbon components in natural gas are unreactive because
saturated carbons form chemically stable molecules. However, at high temperatures and in the
presence of oxygen, alkanes will undergo combustion, giving off heat in the process. This
capacity to produce heat, otherwise known as heating value, is what makes natural gas and
crude oil two of the most precious energy sources in the world. The two major by-productsof
combustion, water vapor and carbon dioxide, also occur naturally as individual compounds.
Other reactions and processes include corrosion, hydrate formation, and condensation.
Corrosion is the process in which metals are oxidized in the presence of moisture or some
other corrosive agent such as carbon dioxide or hydrogen sulfide. The degree of corrosion in
pipelines can be significantly reduced by removing these components from the gas during
production. The removal of water vapor (dehydration) is commonly accomplished by bubbling
the gas stream through a vessel containing a chemical, such as glycol, which has an affinity for
water. Similarly, carbon dioxide and hydrogen sulfide are removed by passing the gas through
chemicals, such as amine, that have an affinity for each of them. Natural gas hydrates are
solids that form from natural gas molecules and water. The water molecules form a
honeycombed structure with a molecule of one of the natural gas components occupying each
void. Because these solids are denser than water ice, their formation is favored at higher
pressures. They are favored so much to the extent that natural gas hydrates may form at
temperatures up to 70 degrees F. Like liquids, they interfere with the flow of gas and cause
operational problems. One of the places hydrates often form is in the sensing lines to the
orifice recorder. When formed in these lines, hydrates cause incorrect recording of the
differential pressure. This is what is often called meter freeze and is a major cause of
measurement errors.

Gas Laws
Accurate measurement of natural gas must take into account a variety of gas laws involving
relationships between temperature, pressure, and volume. Pressure is defined as force per unit
and is commonly expressed in a variety of ways including psi, atmospheres, bars, mm of Hg,
inches of water, and pascals. The quantitative relationship between volume and pressure is
summarized by Boyle’s Law which states that the volume of a sample of gas varies inversely
with the pressure under which it is measured, given a constant temperature. If the pressure is
doubled, the volume is reduced by half. If the pressure is cut in half, the volume is doubled.
Charles’ Law states that the volume of a sample of gas varies directly with the absolute
temperature, given a constant pressure. Absolute temperature is measured in degrees Kelvin
and starts with absolute zero, representing a complete absence of heat. Thus, on the Kelvin
scale, the freezing point of water is 273ºK and on the Celsius scale, absolute zero is -273º C. If
the absolute temperature of a gas is doubled, its volume will double. Combining Boyle’s Law
and Charles’ Law results in a single expression known as the Combined Gas Law Equation:

Boyle’s Law P1V1 = P2V2

Charles’ Law V1/T1 = V2/T2
Combined Gas Law P1V1/T1 = P2V2/T2
Based on Avogadro’s Law, equal volumes of gases, at the same temperature and pressure,
contain the same number of molecules. A standard molar volume of an ideal gas is 22.4 liters
per mole at STP (standard temperature and pressure, 0º C and 1 atm.).

According to the kinetic theory, gas pressure is caused by molecular collisions with the walls
of the container. Therefore, the larger the number of molecules per unit volume, the greater the
number of collisions and the higher the pressure. The average kinetic energy of the molecules
is also proportional to the absolute temperature.

While the molecules are at rest at absolute zero, at high temperatures, the molecules move at
increasing speeds, resulting in higher pressures. Combining these concepts into one equation
produces what is known as the ideal gas equation:

PV = nRT

where
P = pressure (atmospheres)
V = volume (liters)
N = number of moles
R = the ideal gas constant (.08206 liter atm/ºK mol)
T = temperature (degrees Kelvin)

Conclusion
Natural gas measurement and processing is based largely upon on the fundamental principles
of chemistry and physics. The intent of this presentation was to bring forth some of the basic
concepts helpful to personnel involved in the industry

In petroleum engineering, the following volume units are used:

Billion
Unit Thousand Million
(10E9)
cubic meter m3 E3m3 E6m3

barrel bbl Mbbl MMbbl

(Kbbl is also used at Santos but is generally
avoided.)
Standard cubic
scf Mscf MMscf Bcf
feet

Conversion factors:

 Oil conversion factor from m³ to bbl(or stb) is 6.28981100

o from m³ to Mbbl is 6.28981100E-3
o from m³ to MMbbl is 6.28981100E-6
 Gas conversion factor from standard m³ to Bcf is 35.493710E-9
o from m³ to MMscf is 35.493710E-6
o from m³ to Mscf is 35.493710E-3
Note that the m³ gas conversion factor takes into account a difference in the standard
temperature base for measurement of gas volumes in metric and imperial units. The standard
temperature for metric measurement is 15 degrees Celsius (i.e. 59 degrees Fahrenheit) while
for English measurement, the standard temperature is 60 °F. Gas undergoes a slight expansion
when the temperature is raised from 15 °C (59 °F) to 60 °F. This expansion is built into the
above factor for gas.

The standard temperature and pressure (STP) for gas varies depending on the particular code
being used. A good discussion can be found on
http://www.chemeurope.com/lexikon/e/Standard_conditions_for_temperature_and_pressure/ .
It is just as important to know the standard pressure as the temperature. Formerly, OPEC used
101.325 kPa (14.696 psia) but now the standard is 101.560 kPa (14.73 psia).