Liquefied Petroleum Gas

Senior Project 2017

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Natural gas is a mixture of many compounds, with methane
(CH4) being the main hydrocarbon constituent. When
natural gas is produced from an underground reservoir, it is
saturated with water vapor and might contain heavy
hydrocarbon compounds as well as nonhydrocarbon
impurities. In the raw state, natural gas cannot be marketed
and therefore must be processed to meet certain
specifications for sales gas. Additionally, it might be
economical to extract liquefiable hydrocarbon components,
which would have a higher market value on extraction as
Contents
compared with their heating value if left in the gas.
1-Introduction
2-Separation Process
3- Acid Gas Removal
4-Dehydration

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Some Problems of gas plants could lead to disaster include:
When pressure is reduced on certain types of crude oil, tiny spheres (bubbles) of gas
are encased in a thin film of oil when the gas comes out of solution this may result in
foam.

 Paraffin deposition in oil and gas separators reduces their efficiency and
may render them inoperable by partially filling the vessel and/or blocking
the mist extractor and fluid passages.

 If sand and other solids are continuously produced in appreciable

quantities with well fluids

Figure 1: Salts after removed

 Produced well fluids can be very corrosive and cause early failure of
equipment the two most corrosive elements are hydrogen sulfide and carbon
dioxide.

These two gases may be present in the well fluids in quantities from a trace
up to 40 to 50% of the gas by volume

Figure 2: corrosion in pipeline

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  The amalgamation of mercury and aluminum causes weak spots which
will fail and cause leak. in is difficult to continue the process of making
LNG when this occurs . To prevent this , mercury guard system have
been established which remove mercury according to the reaction

Hg + S HgS

 slug flow & erosion and reduce the line capacity ( reduces pipeline
efficiency ) because of Water condensation in pipe line

 Reduction of heating value of natural gas which reduce the selling price.

 Formation of hydrate (which can plug valves, piping, fitting and etc.)

Figure 3: formation of hydrate

SO to get rid of all these problems and increase efficiency

The pretreatment by the following process

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Separation

In an oilfield separation system the substances to be separated are oil, water

and gas. The difference in this case is density.
Before we go on to consider the oilfield separation process in more detail, let's
look at the components to be separated.
Natural Gas - which is associated with an oil accumulation may be termed free
gas or dissolved gas.
A- Free Gas is a hydrocarbon mixture which exists in a gaseous state at
reservoir conditions of temperature and pressure. It remains as a gas when it
is produced under normal conditions.
B- Dissolved Gas is dissolved in the oil at a certain temperature and pressure.
If the pressure is
reduced and/or the temperature is increased, the dissolved gas may be
liberated from the oil. When this occurs the gas assumes the characteristics of
free gas.
The density of the gas depends upon the pressure at which it is confined.
There is a relationship between the volumes of gas and oil produced from a
reservoir. This relationship is known as the Gas Oil Ratio (G.O.R.).
G.O.R. is defined as the volume of gas produced per unit volume of oil
production. The usual oilfield units for this ratio are standard cubic feet per
barrel (scf/bbl).
Water produced with oil or gas may be in the form of liquid or vapour. The liquid
water may also be in the form of free water or it may be emulsified in the oil.

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Principles of Separation
The objective of ideal separation is to separate the hydrocarbon stream into
liquid-free gas and gas-free-liquid.
Two factors are necessary for separators to function:
1- The fluids to be separated must be insoluble in each other.
2- One fluid must be lighter than the other.
Separations depend upon the effect of gravity to separate fluids. If they are
soluble in each other, no separation is possible with gravity alone.
Gravity Separation
Since a separation depends upon gravity to separate the fluids, the ease with
which two fluids can be separated depends upon the difference in the density
or weight per unit volume of the fluids.
In the process of separating gas from liquid, there are two separation
stages:
1- Separate liquid mist from the gas phase.
2- Separate gas in the form of foam from the liquid phase.
Droplets of liquid mist will settle out from gas, provided:
The gas remains in the separator long enough for mist to drop out.
the flow of the gas through the separator is slow enough that no turbulence
Occurs, which will keep the gas stream stirred up so that the liquid has no
chance to drop out.
Gas bubbles in the liquid will break out in most oilfield applications in 30 to 60
seconds. Consequently the separator is design so that the liquid remains in the
vessel for 30 to 60 seconds. The length of time that the liquid remains in the
vessel is called its residence or retention time.
Factors Affecting Separation
The factors that affect the operation and separation between the oil and
gas phases in a separator are:
Fluid stream composition.
Operating pressure.
Operating temperature.

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Changes in any one of these factors on a given fluid stream will change the
amount of gas and oil leaving the separator.
Foaming and emulsion are also affecting the capacity of separation in a
separator. Foam must be broken to obtain a good gas-oil separation. It takes
time (length) to breakout physically; chemical like silicon compounds may be
used. When foaming oil is separated, retention time should be increased to 5
to 20 minutes
dependent on the stability of the foam and on the design of the separator.
Effect of factors that cause separation

Separation factor Effect of factor

1. Difference in weight of fluid. Separation is easier when weight
difference is greater.
2. Residence time in separator. Separation is better with more time.

3. Coalescing surface area. Separation is better with more area.

4. Centrifugal action. Separation is better at higher

velocity.

5. Presence of solids. Makes separation more difficult.

Separation classification
Separators are classified into two ways:
1. The shape of the vessel.
2. The number of the fluids to be separated.
Separators are commonly manufactured in three basic shapes:
1. Horizontal Separator
2. Vertical Separator
3. Spherical Separator

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A. Horizontal Separators:
The horizontal separator is designed for processing well stream. The large
liquid surface area provides for efficient removal of gas from the liquid. This
type of vessel has a large interface area between the liquid and the gas phases.
Thus, adding more separation when the gas capacity is a design criterion, the
horizontal vessel is more economical in high pressure separators due to
increased wall thickness required with large diameters and, in general,
recommended for use with low gas-oil ratio fluid streams unless additional
factors dictate otherwise. However, the liquid level control replacement is more
critical than that in vertical separator.

Figure 4: Horizontal Separators

Advantages of Horizontal Separators:

1. The horizontal usually will be cheaper than a vertical.
2. A horizontal configuration will be more adaptable to skid – mounting and on-
skid piping.
3. More area is available for settling in the liquid phase. Thus, the horizontal
conforms to there phase operation better than does a vertical.
4. If heating coils or sand jets are required, horizontal configuration is more
adaptable.
5. Foamy crudes are processed more effectively in a horizontal than in a
vertical.
Disadvantages of Horizontal Separators:
1. Horizontal separator normally have less liquid surge capacity than a vertical
of comparable oil and gas capacity, and.
2. Liquid level control is more critical than with a vertical type.

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B. Vertical Separators:
This type is capable of handling large slugs of liquid without carryover to the
gas outlet and is best suited for well streams with high liquid content and low
gas volume. The action of level control is not critical.
Due to the greater vertical distance between the liquid level and the gas outlet,
there is less tendency to re-vaporize the liquid into the gas phase. Vertical type
is most often used on fluid streams having considerably more liquid.
Advantages of Vertical Separators:
1. Liquid level and control not as critical as for horizontal;
2. Easier and cheaper to design for surge capacity
3. With certain designs, more strange material (for example, sand, mud, and
corrosion products) can be handled; and
4. Usually easier to clean.
Disadvantages of Vertical Separators:
1. More expensive,
2. Does not adapt to skid-mounted assemblies as well as do horizontals in most
case, and
3. Requires a larger diameter for the same gas capacity.

Figure 5: Vertical Separators

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C. Spherical Separators:
There types of separators are compact vessels arrangement and provide good
gas separation. However, they very limited surge space and liquid settling
section.
When a well stream can contain excess mud or sand be subjected to surging
foamy components, the spherical separator is not economical. The liquid level
control is very critical. These Separators are not as popular today because of
their limitations.
Advantages of Spherical Separators:
1. Ease of skid mounting
2. Excellent gas separation capacity per dollar, and
3. Its cleanout and drain features are better than those of a vertical separator
Disadvantages of Spherical Separators:
1. Is not economical for large gas capacities,
2. Its surge capacity is limited.

Figure 6: spherical Separators

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The Number of Fluids to be separated
The number of phases refers to the number of streams that leave the vessel,
and not the number of phases that are in the inlet stream.
A- Two-Phase Separators
The flow in horizontal or vertical separators is similar. The well stream enters
the inlet side and strikes a baffle. Forward motion is stopped temporarily with
the heavy liquids falling to the bottom of the vessel.
Gas and liquid spray continue through straightening vanes, which cause liquid
drops to form and drop intro the accumulation section.
flow in a centrifugal separator is somewhat different than that in conventional
types. The vessels are usually vertical and depend on centrifugal action to
separate the fluids. The inlet stream is directed to flow around the wall of the
vessel in swirling motion. The heavier liquid moves to the outside, and droplets
collect on the wall and fall to the bottom. The lighter of the fluids collects in the
middle of the vessel and flows up the outlet pipe.

This type handles gas plus two immiscible liquid phases. The two liquid phases
might be oil and water, glycol and oil, etc. The potential application of three
phase separators occurs where space is a major consideration
Techniques of separation
Separation with sorbents/solvents
Solvents
Amine scrubbing technology was established over 60 years ago in the oil and
chemical industries, for removal of hydrogen sulphide and CO2 from gas
streams Commercially, it is the most well established of the techniques
available for CO2 capture although practical experience is mainly in gas
streams which are chemically reducing, the opposite of the oxidising
environment of a flue gas stream.
There are several facilities in which amines are used to capture CO2 from flue
gas streams today, one example being the Warrior Run coal fired power station
in the USA where 150 t/d of CO2 is captured.
Mono-ethanolamine (MEA) is a widely used type of amine for CO2 capture.
CO2 recovery rates of 98% and product purity in excess of 99% can be
achieved. There are, however, questions about its rate of degradation in the
oxidising environment of a flue gas and the amount of energy required for
regeneration
Improved solvents could reduce energy requirements by as much as 40%
compared to conventionalMEA solvents. There is considerable interest in the

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use of sterically-hindered amines which are claimed to have good absorption
and desorption characteristics.
The conditions for CO2 separation in pre-combustion capture processes will be
quite different from those in post-combustion capture. For example, in a coal
IGCC process, modified for capture, the CO2 concentration would be about 35-
40% at a pressure of 20 bar or more. In that case, physical solvents, such as
Selexol®, could be used for pre-combustion capture of CO2, with the
advantage that the CO2 can be released mainly by depressurisation, thereby
avoiding the high heat consumption of amine scrubbing processes. However,
depressurisation of the solvent still results in a significant energy penalty.
Three basic methods to separate gases
Sorbents
Solid adsorbents, such as zeolites and activated carbon, can be used to
separate CO2 from gas mixtures.
In pressure swing adsorption (PSA), the gas mixture flows through a packed
bed of adsorbent at elevated pressure until the concentration of the desired gas
approaches equilibrium. The bed is regenerated by reducing the pressure.
In temperature swing adsorption (TSA), the adsorbent is regenerated by raising
its temperature. PSA and TSA are commercially practiced methods of gas
separation and are used to some extent in hydrogen production and in removal
of CO2 from natural gas.
Adsorption is not yet considered attractive for large-scale separation of CO2
from flue gas because the capacity and CO2 selectivity of available adsorbents
is low. However, it may be successful in combination with another capture
technology.
Membranes
Gas separation membranes allow one component in a gas stream to pass
through faster than the others.
There are many different types of gas separation membrane, including porous
inorganic membranes, palladium membranes, polymeric membranes and
zeolites Membranes cannot usually achieve high degrees of separation, so
multiple stages and/or recycle of one of the streams is necessary. This leads to
increased complexity, energy consumption and costs.
Several membranes with different characteristics may be required to separate
high-purity CO2. Solvent assisted membranes are being developed to combine
the best features of membranes and solvent scrubbing. Much development is
required before membranes could be used on a large scale for capture in power
stations

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Cryogenics
CO2 can be separated from other gases by cooling and condensation.
Cryogenic separation is widely used commercially for streams that already have
high CO2 concentrations (typically >90%) but it is not used for more dilute CO2
streams.
A major disadvantage of cryogenic separation of CO2 is the amount of energy
required to provide the refrigeration necessary for the process, particularly for
dilute gas streams. Another disadvantage is that some components, such as
water, have to be removed before the gas stream is cooled, to avoid blockages.
Cryogenic separation has the advantage that it enables direct production of
liquid CO2, which is needed for certain transport options, such as transport by
ship. Cryogenics would normally only be applied to high concentration, high
pressure gases, such as in pre-combustion capture processes or oxygen fired
combustion.
PHASES OF SEPARATION
The total process within the separator can be broken down into 4 parts which
we will follow now
1 Primary Separation
As the reservoir fluids enter the vessel an initial separation of gas and liquid
takes place. This happens because of:
 a reduction in velocity
 a reduction in pressure
 a change in flow direction
The velocity of the inlet stream is reduced as the fluids flow from a relatively
small diameter pipeline into the large volume separator the pressure is reduced
by maintaining a controlled pressure on the vessel lower than that of the inlet
stream.
The change in flow direction is accomplished by placing some form of deflector
At the inlet to the separator.

Figure 7: Primary Separation

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2 Secondary Separation

After the initial separation, gas will flow towards the outlet of the vessel.
However, it will still contain a certain amount of liquid in the form of droplets. In
the secondary separation process these liquid droplets are removed from the
gas stream.
Liquid droplets which are suspended in the gas stream will tend to fall or 'settle'
towards the bottom of the vessel. This is simply due to the force of gravity The
ease with which the droplets will settle out of the gas stream and fall into the
liquid accumulation section of the separator depends on a number of factors.
These include:
 The size of the droplets.
 The density of the liquid droplet compared to the density of the gas.
 The velocity at which the gas stream is traveling through the separator.
 The turbulence which exists in the flowing gas stream
Of these factors:
The difference in density between oil and gas and the droplet size will be
determined by the composition of the well stream.
The velocity of the gas stream is determined by the size of the separator and
its throughput.
Turbulence can be reduced by having devices called straightening vanes
built into the separator to make the gas flow more streamlined

Figure 8: Secondary Separation

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Mist Extraction
The secondary separation of liquid droplets from the gas by gravity settling will
not usually remove very small particles. These particles tend to remain in the
gas stream in the form of a mist. In order that the gas leaving a separator as
free as possible room liquid, a final mist extraction section is built into the
vessel.
Mist extraction is accomplished using either an impingement or a centrifugal
force mechanism.
Liquid Accumulation Section
The lowermost section of a separator is where the liquids from the other three
sections accumulate before being discharged from the vessel. Initially, this
liquid will have gas bubbles entrained within it which must be removed.
Just as liquid droplets tend to fall through a gas stream, gas bubbles tend to
rise to the surface of liquids due to density differences.
The time required for the bubbles to reach the surface and re-enter the gas
stream will vary. However, for most oilfield applications it will occur in one to
four minutes. This means that the liquids must stay in the vessel for this period
of time, which is known as the retention time.
If the separator is of a sufficiently large capacity, this will ensure that the
reservoir fluids stay in the vessel for the required retention time.
You will remember that a 3 phase separation process not only removes gas
from liquid, as we have just seen, but also separates oil and water.
This, in effect, adds a fifth part to the total process within the separator.
Oil and Water Separation Section

Oil and water do not mix. If these liquids are left long enough in a vessel,
separation will occur and the oil will float on top of the water.
Oil and water will separate faster than gas will be liberated from the oil. So, if
the separator is large enough to allow efficient gas separation, then the
retention time required for oil and water separation will be exceeded.

Figure 9: Oil and Water Separation Section

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Troubleshooting
Possible causes for the more common problems are listed:

Low liquid level

Fluid dump valve opening too wide.
Drain valve open or leaking.
No fluid entering.

High liquid level

Fluid dump valve closed or plugged.
Block valve around dump valve closed.
Inlet valve to next vessel closed.
Separator overloaded.

Low pressure in separator

Leaking safety-relief valve.
Inlet valve closed.

High pressure in separator

Valves downstream of separator closed.

All the oil going out gas line

Dump valve not open.
Block valve closed on piping to tank.
Separator or piping plugged

Mist going out gas line

Vessel too small.
Plugged mist extractor.
Improper liquid level (too high or too low).
Foaming problem.

Free gas going out oil valve

too low level in separator.
Dump valve not seating.
No vortex breaker or breaker plugged or damaged.

Condensate and water not separating in 3-phase separator

Adjustable weir out of adjustment.
Not enough retention time.
Leak in adjustable weir.

Diaphragm operated dump valve not opening

- Supply gas failure.
- Broken valve stem.
- Plugged tubing.
- Ruptured diaphragm

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Start up
If the vessel is empty, close a block valve in each liquid outlet line from the
vessel to prevent possible leakage through a control valve in the liquid line.
If the vessel has a pressure controller, it should be set at about 75% of the
normal control pressure, and slowly bring it up to a normal pressure after the
vessel is in service.
If the vessel has low level shutdown devices, they must be deactivated or liquid
must be added to the vessel to a point above the low level devices.
Check the flow lines out of the vessel to see that each stream leaving the vessel
flows in the proper direction.
Slowly open the inlet stream to the vessel.
When the liquid level reaches the range of level controller, place level
controllers in
service and open the block valves that were closed in step 1.
Adjust level and pressure controllers to stabilize their operation
Shutdown
 Close a valve in the inlet stream.
 2a. Close valves in liquid outlet line to prevent liquid from leaking out.
 2b. If the vessel must be drained, open the by-pass line on the level
control valves.
 Close block valves in the liquid outlet lines after draining.
 If the vessel must be depressurized, close a block valve in the gas
outlet line.
 Depressurize the vessel by opening a valve in the line from the vessel
to the vent or blow down system.
 If possible, leave a small positive pressure on the vessel while it is
shutdown to prevent air from entering so it will not have to be purged
prior to start-up.

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Acid Gas Removal
In addition to heavy hydrocarbons and water vapor, natural gas often
contains other contaminants that may have to be removed. carbon dioxide
(CO2) , hydrogen sulfide(H2S) , and other sulfur compound such as
mercaptans are compounds that may require complete or partial removal for
acceptance by gas purchaser.
These compounds are known as “acid gases”. H2S combined with water
forms a weak form of sulfuric acid, while CO2 and water forms carbonic acid,
thus the term acid gas.
Natural gas with H2S or other sulfur compounds present is called“sour gas”
,while gas with only CO2 is called “sweet” .
Hydrogen sulfide, carbon dioxide, mercaptans and other contaminants are
often found in natural gas streams. H2S is a highly toxic gas that is corrosive
to carbon steels. CO2 is also corrosive to equipment and reduces the Btu value
of gas. Gas sweetening processes remove these contaminants so the gas is
suitable for transportation and use.

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Operation Problems
Corrosion
Corrosion is an operating concern in nearly all sweetening installations.
The combination of H2S and CO2 with water practically ensures that corrosive
conditions will exist in portions of the plant. In general, gas streams with
highH2S to CO2 ratios are less corrosive than those having low H2S to CO2
ratios.
Because the corrosion in sweetening plants tends to be chemical in nature, it
is strongly a function of temperature and liquid velocity. The type of sweetening
solution being used and the concentration of that solution has a strong impact
on the corrosion rate. Increased corrosion can be expected with stronger
solutions and higher gas loadings.
Several forms of stress corrosion cracking are possible in amine sweetening
systems. Amine stress corrosion cracking can occur and is worst in hot
solutions, but cracking can occur in cooler lines and both rich and lean streams.
Many corrosion problems may be solved using corrosion inhibitors in
combination with operating practices which reduce corrosion. Following are
some guidelines to minimize corrosion.
Maintain the lowest possible reboiler temperature.
o Minimize solids and degradation products in the system through
reclaimed operation and effective filtration.
o Keep oxygen out of the system by providing a gas blanket on all storage
tanks and maintain a positive pressure on the suction of all pumps.
o Ensure deionizer water or oxygen/chemical-free boiler condensate is
used for makeup water. If available, steam can be used to replace water
loss.
o Maintain adequate solution level above reboiler tube bundles and fire
tubes a minimum tube submergence of 6" is recommended

Figure 10: corrosion problem

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Foaming
A sudden increase in differential pressure across a contactor often indicates
severe foaming. When foaming occurs, there is poor contact between the
gas and the chemical solution. The result is reduced treating capacity
and sweetening efficiency.
Some reasons for foaming are:
Suspended solids
Organic acids
Corrosion inhibitors
Condensed hydrocarbons
Soap-based valve greases
Makeup water impurities
Degradation products
Lube Oil
Foaming problems can usually be traced to plant operational problems.
Contaminants from upstream operations can be minimized through
adequate inlet separation. Condensation of hydrocarbons in the
contactor can usually be avoided by maintaining the lean solution
temperature at least 10°F above the hydrocarbon dew point temperature
of the outlet gas. Temporary upsets can be controlled by the addition of
antifoam chemicals. These antifoams are usually of the silicone
or long-chain alcohol type.

Figure 11: Foaming problem

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Techniques
 Chemical solvent processes
 Physical solvent processes
 Hybrid solvent processes
 Adsorption and membrane processes.
 Cryogenic processes.

Chemical Solvent Processes

Amines with stronger base properties will be more reactive towards H2S and
CO2 and will form stronger chemical bonds. As the amine reactivity
increases,. from tertiary amine to primary amine, then the acid gas vapour
pressure over the amine will be lower for a given loading and a higher
equilibrium loading may be achieved.
The reactions between an amine and H2S and CO2 occur according to the
following equations (shown for a primary amine):
2RNH2 + H2S  (RNH3)2S .....Amine Sulfide
CO2 reacts predominantly via the reaction below, forming a carbamate with
primary and secondary amines.
2RNH2 + CO2  RNHCOONH3R.....Amine Carbamate
The main difference with tertiary amines compared to primary and
secondary amine is that CO2 does not react to form carbamate.
Amine Solvent Chemistry
There are many amines available and the particular choice of amine will
depend on the composition of the feed gas and specification required.
Amines can be categorised by the number of organic groups bonded to the
central nitrogen atom, as primary, secondary or tertiary.
Examples are listed below:
Primary
 Monoethanolamine (MEA) HOCH2CH2NH2
 Diglycolamine (DGA) HOCH2CH2OCH2CH2NH2
Secondary
 Diethanolamine (DEA) HOCH2CH2NHCH2CH2OH
 Diisoproapanolamine (DIPA) (CH3CHOHCH2)2NH
Tertiary
 Triethanolamine (TEA) (CH2CH2OH)3N
 Methyldiethanolamine (MDEA) (CH2CH2OH)2NCH3

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In the recent years, MDEA has gained a large share of the gas treating market.
Many companies are offering their own version of MDEA (BASF’s aMDEA,
Union Carbide’s UCARSOL, Shell’s SCOT process, etc.).It has a relatively
low energy requirement, low vapour pressure, degradation resistance and it is
selective to H2S in the presence of CO2.
Normally selectivity is achieved by using the reaction rate kinetic differences
between H2S and CO2 with MDEA. H2S reacts quickly with MDEA while CO2
reacts relatively slowly.
By controlling the time of reaction (i.e. residence time in the absorber),
selectivity is achieved. Thus, it is important to limit the number of trays in the
absorber to ensure selectivity. Also accelerators/promoters can be added to
increase the reaction rate. MDEA has a disadvantage in that it tends to be
relatively foamy.
MDEA has been used in small and large scale tests and found to be the most
selective of the amines for removal of H2S in the presence of CO2.
The increasing demand for a selective H2S removal process has focused
attention to the merits of MDEA. The principle application in recent years has
been for the selective removal of H2S from CO2 used for Enhanced Oil
Recovery.
Cost comparisons for a sample application show a similar capital cost to a DEA
plant but 50% of utility cost with removal of only 15-18% of CO2 compared to
DEA which removes 99% of CO2.
Activated MDEA can be used for the removal of CO2, H2S and COS from
natural gas and other gases.

Figure 12: Activated MDEA

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 Absorption vs. Adsorption

Absorption is the process in which a fluid is dissolved by a liquid or a solid

(absorbent). Adsorption is the process in which atoms, ions or molecules
from a substance (it could be gas, liquid or dissolved solid) adhere to a
surface of the adsorbent. Adsorption is a surface-based process where a
film of adsorbate is created on the surface while absorption involves the
entire volume of the absorbing substance.

Comparison chart

Absorption versus Adsorption comparison chart

Absorption Adsorption
Definition Assimilation of molecular species Accumulation of the molecular
throughout the bulk of the solid or species at the surface rather than in
liquid is termed as absorption. the bulk of the solid or liquid is termed
as adsorption.
Phenomenon It is a bulk phenomenon It is a surface phenomenon.
Heat Endothermic process Exothermic process
exchange
Temperature It is not affected by temperature It is favoured by low temperature
Rate of It occurs at a uniform rate. It steadily increases and reach to
reaction equilibrium
Concentration It is same throughout the material. Concentration on the surface of
adsorbent is different from that in the
bulk

Process
Adsorption and absorption are both sorption processes.
Absorption occurs when atoms pass through or enter a bulky material.
During absorption, the molecules are entirely dissolved or diffused in the
absorbent to form a solution. Once dissolved, the molecules cannot be
separated easily from the absorbent.

Figure 13: Absorption process

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Physical Absorption
The various amine and potassium carbonate processes rely on chemical
reaction to remove acid gas from sour gas streams.
Removal of acid gas by physical absorption also possible and there are a
number of commercially competitive processes based on this principle .
Physical absorption results from a physical contact between the gas to be
treated and a solvent .
The solvent is used as a pure product. As a result, there is no need for water
make up in a physical absorption process.
The physical absorption is highly dependent upon the feed gas pressure or
the partial pressure of acid gas present in the feed gas.
The solvents used for gas sweetening have generally a strong affinity with
water therefore the solvent will simultaneously sweeten and dry the gas.
However, the solvent water build-up will require a stripper to remove absorbed
water from the solvent.
The efficiency of a physical absorption increases when the operating pressure
increases and/or the operating temperature decreases. Therefore, the
physical absorption process for Gas Sweetening is generally carried out at
low temperatures; sometimes, an external mechanical refrigeration cycle
(propane cycle for instance) is required.
Solvent regeneration (stripping) is usually accomplished by flashing at lower
pressure than absorption with moderate heat input (the efficiency of the
stripping operation increases when operating pressure decreases and/or
operating temperature increases).
.Physico-Chemical Absorption
The principle of this process aims at combining the high absorption potential
of alkanolamine (chemical absorption) and the low regeneration energy
requirement of the physical solvent (physical absorption).
The SULFINOL process is the sole process with large industrial references.
SHELL is the licenser of the SULFINOL process.
SULFINOL Process
The SULFINOL process is based on the use of an aqueous mixture of
alkanolamine (diisopropanolamine or methyldiethanolamine) and sulfolane
(tetrahydrothiophene dioxide). The process is called SULFINOL-D when DIPA
is used, and SULFINOL-M when MDEA is used.
SULFINOL-D generally is a mixture It combines the chemical absorption
effect of the amine and the physical absorption effect of the sulfolane.

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Physical Adsorption
Physical adsorption relates to the use of molecular sieves for the removal of
acid gases. This process is not suitable for the removal of high quantities of
acid gases. It can be envisaged only to removed traces (in terms of ppm) of
H2S and/or CO2. It can be also envisaged as a downstream gas polishing
treatment to remove sulfur compounds from the feed gas (mercaptans).
The process is identical to the process considered for the gas drying but the
type of molecular sieve used is different : the 3A type is suitable for water
removal but CO2 and H2S cannot enter the pores of the adsorbent. To
remove these components, 4A ,5A or 13 X type will be selected since it will
adsorb the three components : H2O first, H2S second and CO2 third.
The process operates under the adsorption/regeneration cycle (generally 8 to
12 hours for both sequences). Regeneration of the beds of sieves generally
through the use of a side stream of treated gas. Once the bed has been
regerated (Its acid cpompounds having been removed), it is ready for a new
adsorption cycle. When both H2S, CO2 and water vapor are present in the
Feed Gas to the molecular sieves, the water can promote the formation of
COS (carbonyl sulfide) through inter reaction between CO2 and H2S (this
sulfur compound can be a contaminant of the Treated Gas). High pressures,
low temperatures, high gas velocities tend to reduce the formation of COS. In
this case, COS depressant molecular sieve type must be considered.
Another problem relates to the disposal of the regeneration gas (mainly if
used as fuel gas). The cyclic nature of an adsorption operation could result in
dumping peak CO2 and/or H2S loads in the regeneration gas which would
produce bumps as great as 30 to 40 times the initial acid gas concentration.

Figure 14: Dehydration by Adsorption

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Troubleshooting
Check amine solution concentration:
 Too low : Check make up water addition.
Check amine flow rate:
 Too low : Open by pass valve.
Check amine regeneration:
 Increase firing rate.
Check reflux rate and temperature:
 Probably too low: Increase firing rate.
Check stripping column pressure:
 It may be too low
Check for foaming:
Carry over into outlet separator and / or pressure fluctuations across absorber
Gas contains oxygen
 Storage - tank blanket - gas valve is not functioning:
- Repair.
 Make up water contains free oxygen:
- Add oxygen scavenger.
 Sparge amine with sweet gas to strip oxygen.
 Foaming is a very unpredictable phenomenon. It can be caused by any
or a combination of the following conditions:
 Dirty amine (solids) – check filter elements.
 Degraded amine.
 Liquid hydrocarbon in gas or amine.

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Sulphur Recovery
General
Sulphur is present in natural gas principally as hydrogen sulphide (H2S). The H2S
present is removed from natural gas by means of one of the acid gas treatment
processes described earlier. The resulting H2S-containing acid gas can be converted
to elemental sulphur by means of the Claus process.
Claus Process
The Claus process is split into two parts.
1. A thermal or combustion reaction section in which most of the overall heat of
reaction (from) burning 1/3 of the H2S and essentially 100% of any hydrocarbons and
other combustibles in the feed) is released and removed
H2S + 11/2 O2 SO2 + H2O
2. A moderately exothermic catalytic reaction section in which sulphur dioxide
(SO2) formed in the combustion section reacts with unburned H2S to form
elemental sulphur.
2 H2S + 11/2 SO2 3/x Sx + 2 H20

Figure 15: Claus Process

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Gas Dehydration Process
Most natural gas streams leaving the reservoir contain water vapor. In many
cases free water is also produced along with e natural gas.
Natural gas cools as it travels up the wellbore to the surface due to pressure
reduction and conduction of heat through the pipe to cooler formation walls.
Since the ability of gas to hold water vapor decreases as gas temperature
decreases, produced natural gas is nearly always saturated with water vapor
when it reaches the surface.
Additional cooling of saturated gas will cause free water to form. If the gas is
further cooled, hydrates will form and serious equipment damage or flow
restrictions will result. This is why it is so important to remove water vapor
from natural gas.

Figure 16: water in natural gas

Acid Gas
Removal

Gas
Dehydration

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Operation Problems
 Corrosion (particularly if gas contains H2S, CO2
 Water condensation in pipe line which cause slug flow & erosion and

Figure 17: Erosion

 reduce the line capacity ( reduces pipeline efficiency )

 Water reduces accuracy in measurement

 Reduction of heating value of natural gas which reduce the selling

price.
 Formation of hydrate (which can plug valves, piping, fitting and etc.)
 To Meet Product Specification ( ONSPEC )
 Water Freezing (Ice Formation ) In Cryogenic Process

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Gas Dehydration
Natural gas dehydration is the process of removing water vapor from the
gas stream to lower the dew point of that gas. The dew point is defined
as the temperature at which water vapor condenses from the gas stream.
The sale contracts of natural gas specify either its dew point or the
maximum amount of water vapor present.
There are three basic reasons for the dehydration of natural gas streams:
1. To prevent hydrate formation.The primary conditions promoting
hydration formation are the following:
Gas must be at or below its water (dew) point with ‘‘free’’ water
present.
Low temperature.
High pressure.
2. To avoid corrosion problems.
3. Downstream processing requirements. In most commercial
hydrocarbon processes, the presence of water may cause side reactions,
foaming, or catalyst deactivation. Consequently, purchasers typically
require that gas and liquid petroleum gas (LPG) feedstocks meet certain
specifications for maximum water content. This ensures that water-based
problems will not hamper downstream operations.

Figure 18: Hdrate formation

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Dehydration Methods
Absorption (Glycol Dehydration Process):
The basic principles of relevance to the absorption process are as follows:
1. In this process, a hygroscopic liquid is used to contact the wet gas to
remove water vapor from it. Triethylene glycol (TEG) is the most
common solvent used.
2. Absorption, which is defined as the transfer of a component from the
gas phase to the liquid phase, is more favorable at a lower temperature
and higher pressure. This result is concluded by considering the following
relationship (which is a combination of Raoult’s law and Dalton’s law):

where Pi is the pressure of pure component i, P is the total pressure of the

gas mixture (system), Xi is the mole fraction of component i in the liquid
phase, Yi is the mole fraction of component I in the vapor phase, and Ki is
the equilibrium constant, increasing with temperature and decreasing with
pressure.
3. The actual absorption process of water vapor from the gas phase using
glycol is dynamic and continuous. Therefore, the gas flow cannot be
stopped to let a vapor and the liquid reach an equilibrium condition.
Accordingly, the system under consideration must be designed to allow
for a close approach to equilibrium while the flow continues.
The three major methods of dehydration are 1) direct cooling, 2) adsorption,
and 3) absorption. Molecular sieves (zeolites), silica gel, and bauxite are the
desiccants used in adsorption processes. In absorption processes, the most
frequently used desiccants are diethylene and triethylene glycols. Usually, the
absorption/stripping cycle is used for removing large amounts of water, and
adsorption is used for cryogenic systems to reach low moisture contents.
Direct Cooling
The saturated vapor content of natural gas decreases with increased pressure
or decreased temperature Thus, hot gases saturated with water may be
partially dehydrated by direct cooling. Gases subjected to compression are
normally "after cooled", and this cooling may well remove water from the gas.

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Absorption of Water in Glycols
Absorption dehydration involves the use of a liquid desiccant to remove water
vapor from the gas. Although many liquids possess the ability to absorb water
from gas, the liquid that is most desirable to use for commercial dehydration
purposes should possess the following properties:
1. High absorption efficiency.
2. Easy and economic regeneration.
3. Non-corrosive and non-toxic.
4. No operational problems when used in high concentrations.
5. No interaction with the hydrocarbon portion of the gas, and no
contamination by acid gases.
The glycols, particularly ethylene glycol (EG), diethylene glycol (DEG),
triethylene glycol (TEG), and tetraethylene glycol (T4EG) come to closest to
satisfying these criteria to varying degrees. Water and the glycols show
complete mutual solubility in the liquid phase due to hydrogen-oxygen bonds,
and their water vapor pressures are very low. One frequently used glycol for
dehydration is triethylene glycol, or TEG:

Figure 20: Contactor / Absorber

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Adsorption of Water by a Solid
Adsorption (or solid bed) dehydration is the process where a solid desiccant is
used for the removal of water vapor from a gas stream. The solid desiccants
commonly used for gas dehydration are those that can be regenerated and,
consequently, used over several adsorption-desorption cycles.
The mechanisms of adsorption on a surface are of two types; physical and
chemical. The latter process, involving a chemical reaction, is termed
"chemisorption". Chemical adsorbents find very limited application in gas
processing. Adsorbents that allow physical adsorption hold the adsorbate on
their surface by surface forces. For physical adsorbents used in gas
dehydration, the following properties are desirable.
1. Large surface area for high capacity. Commercial adsorbents have a
surface area of 500-800 m2/g.
2. Good "activity" for the components to be removed, and good activity
retention with time/use.
3. High mass transfer rate, i.e., a high rate of removal.
4. Easy, economic regeneration.
5. Small resistance to gas flow, so that the pressure drop through the
dehydration system is small.
6. High mechanical strength to resist crushing and dust formation. The
adsorbent also must retain enough strength when "wet".
7. Cheap, non-corrosive, non-toxic, chemically inert, high bulk density, and
small volume changes upon adsorption and desorption of water.

Figure 21: Process describtion

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Alumina
A hydrated form of aluminum oxide (Al2O3), alumina is the least
expensive adsorbent. It is activated by driving off some of the water
associated with it in its hydrated form ((Al2O3.3H2O) by heating. It produces an
excellent dew point depression values as low as -100 F, but requires much
more heat for regeneration. Also, it is alkaline and cannot be used in the
presence of acid gases, or acidic chemicals used for well treating. The tendency
to adsorb heavy hydrocarbons is high, and it is difficult to remove these during
regeneration. It has good resistance to liquids, but little resistance to
disintegration due to mechanical agitation by the flowing gas.
Silica Gel and Silica-Alumina Gel
Gels are granular, amorphous solids manufactered by chemical reaction. Gels
manufactured from sulfuric acid and sodium silicate reaction are called silica
gels, and consist almost solely of silicon dioxide (SiO2). Alumina gels consist
primarily of some hydrated form of Al2O3. Silica-alumina gels are a combination
of silica and alumina gel.
Gels can dehydrate gas to as low as 10 ppm, and have the greatest ease of
regeneration of all desiccants. They adsorb heavy hydrocarbons, but release
them relatively more easily during regeneration. Since they are acidic, they can
handle sour gases, but not alkaline materials such as caustic or ammonia.
Although there is no reaction with H2S, sulfur can deposit and block their
surface. Therefore, gels are useful if the H2S content is less than 5-6%.
Molecular Sieves
These are a crystalline form of alkali metal (calcium or sodium) alumina-
silicates, very similar to natural clays. They are highly porous, with a very
narrow range of pore sizes, and very high surface area. Manufactured by ion-
exchange, molecular sieves are the most expensive adsorbents. They possess
highly localized polar charges on their surface that act as extremely effective
adsorption sites for polar compounds such as water and hydrogen sulfide.
Molecular sieves are alkaline and subject to attack by acids. Special acid-
resistant sieves are available for very sour gases.
Since the pore size range is narrow, molecular sieves exhibit selectivity towards
adsorbates on the basis of their molecular size, and tend not to adsorb bigger
molecules such as the heavy hydrocarbons. The regeneration temperature is
very high. They can produce a water content as low as 1 ppm. Molecular sieves
offer a means of simultaneous dehydration and desulfurization and are
therefore the best choice for sour gases.
Solid desiccants or absorbents are commonly used for dehydrating gases in
cryogenic processes. The use of solid adsorbent has been extended to the
dehydration of liquid. Solid adsorbents remove water from the hydrocarbon
stream and release it to another stream at higher temperatures in a
regeneration step.

Page 34 of 39
The movement of an adsorption zone front as a function of time. In a dry
desiccant bed, the adsorbate components are adsorbed at different rates. A
short while after the process has begun, a series of adsorption zones appear.
The distance between successive adsorption zone fronts is indicative of the
length of the bed involved in the adsorption of a given component. Behind the
zone, all of the entering component has been removed from the gas; ahead of
the zone, the concentration of that component is zero. Note the adsorption
sequence: C1 and C2 are adsorbed almost instantaneously, followed by the
heavier hydrocarbons, and finally by water that constitutes the last zone. Almost
all the hydrocarbons are removed after 30-40 min and dehydration begins.
Water displaces the hydrocarbons on the adsorbent surface if enough time is
allowed. At the start of dehydration cycle, the bed is saturated with
methane as the gas flows through the bed. Then ethane replaces methane, and
propane is adsorbed next. Finally, water will replace all the hydrocarbons.
For good dehydration, the bed should be switched to regeneration just before
the water content of outlet gas reaches an unacceptable level. The regeneration
of the bed consists of circulating hot dehydrated gas to strip the adsorbed water,
then circulating cold gas to cool the bed down.

Figure 22: adsorber

Page 35 of 39
The operating problems most frequently encountered in a glycol plant are:
 Foaming
This is possibly the most common problem. Glycol tends to foam easily due to
its viscosity. This tendency is promoted by liquid hydrocarbons
(particularly aromatics), the presence of small solid particles, and
contaminants. Poor tray design which uses too high vapor velocity through
the bubble cap slots may be a contributing factor.
 The main problems associated with foaming are:

• Improper gas dehydration

• Excessive glycol losses when the glycol foams out of the contactor
• Additional equipment problems down- stream of the contractor from
glycol carryover
 To prevent glycol foaming, it is required:
• Use cartridge filter to keep glycol solution clean.
• An inlet gas separator to separate hydrocarbons entrainment.
•Use a foam inhibitor (trioctylphosphate is the most common foam
inhibitor), too much foam inhibitor can promote foam.
• PH control are also very important.
Foaming losses will be minimised by proper mist eliminators, in most
cases two in series at least 6-8 inches apart, are recommended .
A third one can sometimes show advantage.
 Degradation
Degradation is a natural occurrence and is accelerated in the presence
of sulfur compounds.
 The answer is effective filtration. Degradation products contribute to
foaming but they also are major sources of corrosion problems.
 The best filtration system uses a regular filter to remove the large
"chunks" and then an activated carbon filter to remove hydrocarbons
as well as fine contaminants that pass through the firs filter.

Page 36 of 39
  Corrosion
Glycol will react with sulfur compounds to form undesirable degradation
products “gunk” which is very corrosive and glycol decomposition
products are primarily acidic. This condition can be controlled by
good filtration and glycol reclaiming.
The PH of the glycol solution should be maintained from 6.5 to 8.5 by
suitable materials, small amounts of base chemicals such as
amines may be used.
Corrosion control chemicals used are:
1. Sodium mercaptobenzohiazole (sodium MPT) is usual used at 0.3 - 0.5
Wt.% concentration plus 1.5 Wt % dipotassium phosphate. The
MP concentration may be maintained by adding 1 quart of MPT to
each 55 gallon drum of glycol.
2. Monoethanolamine (MEA) normally about 1% in solution
3. Coroval, usually used at about 40 PPm by weight.
 Inadequate separation ahead of the absorber
Salt is a continuing problem. Good separation ahead of the absorber is
mandatory. Any salt arriving at the regenerator deposits either in the
still column or in the reboiler. It is common for packed still
columns to plug up to the point glycol is lost overhead. If this does
not occur, salt can plug the reboiler and cause failure
 Water/ vapor in Gas
The water vapor in gas is relatively fresh but is slightly saline. NaCl is soluble
in TEG to some degree. At 50°C about 3.3 kg will dissolve in l00 kg of
TEG. So, some salt is always present. The soluble salt hydrolyses to HCI and
lowers the pH of the glycol.

 Puking
 It is almost always caused by a slug of liquid hydrocarbons entering the
stripper. The hydrocarbons will flow down the stripper as a liquid, and
when they reach the reboiler, they will vaporise almost
instantaneously. The vapor flow up the stripper with sufficient velocity
to carry out most of the liquid in the tower. Liquid HCs should be
removed from the rich glycol in the flash tank, or a similar vessel.

Page 37 of 39
Prior to the initial start up of a new plant. The vessels and lines should be
thoroughly washed out with water to remove debris and corrosion products
that accumulated during construction. After the system has been cleaned,
startup is accomplished in three phases:

 .Establish glycol circulation throughout the plant .

 .Apply heat to the reboiler and bring it up to operating temperature .
 .Open the wet gas stream to the contactor and begin dehydrating the
ga .

In order to circulate glycol throughout the system, it will be necessary to

pressurize the vessels in the system. Pressuring can be done with wet gas or
dry gas. The contactor pressure should be raised to at least 10 bars (l50 psi)
and the flash tank pressure should be raised to at least 3 bars (45 psi). When
the vessels have been pressured, startup procedure is
1. Fill the reboiler and surge tank with fresh glycol solution Also add to
the flash tank
2. Pressure up the contactor column by very slowly opening the gas inlet
valve.
3. Prime and start glycol pump.
4. When liquid appears at the bottom of the contactor put the bottom level
controller in service so the glycol will flow to the flash tank.
5. Put the flash tank level controller in service when liquid appears in the
bottom, so that liquid will flow to the stripper.
6. Keep surge tank level half full by adding glycol when needed.
7. When desired circulation rate is established, light the reboiler or put
the heat source in service and slowly bring reboiler temperature up to
250°F (121°C). Leave temperature at 250°F (121°C) until all
water has been boiled out of glycol.

Page 38 of 39
Recommended steps for safely lighting a gas-fired glycol dehydration
unit:
1. Close pilot valve, gas burner valve, and main gas supply valve.
2. Be sure all gas is vented from firetube and flame arrestor is in place.
Make sure gas is off five minutes prior to lighting.
3. Be sure firetube is covered with fluid.
4. Stand to one side while inserting burning torch. This protects the
operator from ignition of residual vapors.
5. Adjust torch position to ignite pilot.
6. Open main Supply valve.
7. Slowly open Pilot valve.
8. Open burner valve after pilot is lighted and torch removed.
9. Adjust gas and air mixture to obtain proper flame.
10. Set fuel pressure as low as possible to maintain proper temperature.
Slowly switch gas stream through contactor column by opening the outlet line
and slowly closing the by-pass line.
Slowly raise the reboiler temperature to around 380°F to 400°F (193°C to
204°C).
Inspect unit for leaks and other abnormal operating conditions.
Check gas dew point after the unit has been operating for about four hours
Shut Down Procedures
This procedure is used to shut down a glycol plant:

1. Block gas to contactor column,

2. Shut off heat (leave pump running),
3. When unit cools to safe temperature, 150°F (66°C), shut off pump.
4. Drain glycol, if necessary.

Page 39 of 39