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Gas Conditioning refers to the steps taken to prepare gas for transportation, sales or
further processing - such as recovery of natural gas liquids or chemical feed. This
fundamental session deals with dehydration and hydrate prevention. Natural gas as
produced normally contains water vapor. Water must be removed to a typical point of
achieving a content of 7 lb/MMSCF for US transmission systems to a few ppm water and
dew point of –150 °F for cryogenic processing feed pre-treatment.
The removal of water, or dehydration, is done to prevent hydrate formation (and potential
plugging) or corrosion in the gas gathering, transmission system, or processing plant.
Alternatively hydrate inhibitors may be injected into the gas stream to prevent or inhibit
the formation of hydrates. Dehydration is typically preceded by other gas conditioning
steps, separation of free hydrocarbons liquids and removal of acid gases, if present. Other
gas conditioning steps may be performed prior to sales are recovery of hydrocarbon
NGL’s or hydrocarbon dew-pointing.
Several process alternatives that can be utilized to accomplish dehydration are reviewed
in this Fundamentals Manual. The principle processes of tri-ethylene glycol (TEG)
dehydration, mole sieve desiccation, and new and advancing technologies will then be
discussed in some detail.
A widely accepted and used chart showing the quantity of water vapor which natural gas
at saturation can contain, under various conditions of pressure and temperature, was
developed by McKetta and Wehe. This is included in the GPSA Engineering Data Book,
11th Edition, Chapter 20 as Figure No. 20. It has been updated with recent research. The
chart shows when the temperature of gas is increased gas contains more water; this is
because water vapor pressure increases. If gas pressure decreases, the amount of water
vapor the gas will hold also increases, as water vapor pressure becomes a larger fraction
of the total pressure. An important factor influencing which process to choose is the
water content of the gas requiring dehydration
When the temperature of water-saturated natural gas is lowered, some of the water vapor
condenses. If the temperature is low enough the condensed water vapor can combine
with certain of the hydrocarbons (methane, ethane, propane, butane) and with H2S and
CO2 - if these components are present - to form solids known as hydrates. Hydrates are
cage like structures that can exist at temperatures well above the freezing point of water.
A quantity of hydrates can accumulate in gas transmission and processing equipment and
result in restriction or blockage. Conditions under which hydrates will form and a
method developed by Katz of calculating hydrate formation conditions using vapor-solid
equilibrium constants are also included in the GPSA Engineering Data Book, chapter 20.
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Gas hydrates will generally form when free (liquid) water is present and conditions are
favorable for hydrate, although in some cold gas conditions hydrates can form even
without free water. Once formed these hydrates can agglomerate and plug pipelines.
Therefore, gas pipelines usually require that most of the water vapor be removed from the
gas, down to a water content lower than the saturation water content at the lowest
expected pipeline temperature.
In the United States, the usual pipeline specification for water content is a maximum of 7
pounds of water per million standard cubic feet (lb/MMSCF); in Canada, this
specification is often about 4 lb/MMSCF. The constant of 21 ppm can be applied to
convert lb/MMSCF water to ppm (mole). A water content of 7 lb/MMSCF corresponds to
approximately 147 ppm water. The 7 lb/MMSCF also relates to about 32 °F water dew
point at 1000 psia. A 4 lb/MMSCF relates to 15 °F dew-point at 1000 psia.
Kinetic inhibitors have been a topic of recent hydrate research and innovation. The
advantage of kinetic inhibitors is that quantity of inhibitor that has to be injected is
significantly less (10%) of that with thermodynamic inhibitors. These work by one of two
methods:
Calculation methods for hydrate prediction and inhibition are described below. Modern
process simulation computer programs are available with good VLE correlations to make
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precise calculations of hydrate formation point. The programs INFOCHEM, HYSYS and
TSWEET have demonstrated the more accurate hydrate formation predictions, with and
without inhibitors. Predictions, however, are only as good as forecast of conditions.
Certainly the best means of hydrate control is to prevent their formation by elimination of
water from the system. This is accomplished by removal of water by the process called
dehydration.
Any one, or a combination of, five basic methods may reduce the water vapor content of
a gas. These are applied at the process pressure of the gas, except for the first one.
Any of these methods may be used to dry gas to a specific water content. Usually the
combination of the water content specification, initial water content, process character,
operational nature, and economic factors determine the dehydration method to be
utilized. The two most common dehydration methods presently being used in natural gas
processing beyond compression and cooling are liquid desiccant, i.e., glycol, or
adsorption with a solid desiccant, such as mole sieve or silica gel. These are discussed
briefly in this introduction and presented in depth in subsequent portions of this
Fundamentals Manual. In addition membrane systems with selective water permeation
have also been commercialized. These are not yet in widespread use.
The various dehydration processes, and their primary applications areas are briefly
summarized below. All of these systems can be employed in an unattended operation
situation, so there is no difference in requirement for surveillance between alternatives in
the production environment.
Compression and cooling with separation is typically part of a production system / gas
gathering and processing arrangement. For natural gas additional drying is usually
applied. However, in some cases this simple approach may be sufficient for field use in
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gas lift systems (though experience suggests operation is better if the free water is
prevented).
In the case of CO2 systems and some acid gas injection systems a judicious selection of
the compression pressure –temperature operating line can remove all the water that has to
taken out of the stream for satisfactory operation. Natural gas streams have the
characteristic that as the pressure increases at a fixed temperature the saturated water
content decreases. CO2 rich streams differ due to their high critical temperatures. At a
fixed temperature, increasing pressure will reduce the saturated water content until a
minimum in water content is reached at about 600 psig. At further increase in pressure
water holding capacity increases substantially. Thus a CO2-rich stream cooled to say
100°F at 600 psig can be compressed to higher pressure and it will become under-
saturated, or dry.
Cooling below initial dew-point. The lower the temperature, the lower the saturated water
vapor content of the gas. This method usually requires some means of hydrate
prevention and is applied as Low Temperature Separation, or LTS). Ethylene glycol is
usually used for the lower temperature LTS for hydrate prevention and simultaneous
dehydration of the gas. An example of a direct injection application is presented in a
following section.
This approach is often combined with direct glycol injection on the front end of
refrigeration plants or lean oil absorption plants. Also new expansion technologies such
as TWISTER have been combined with direct injection to achieve dehydration.
Absorption of water with a liquid desiccant. This usually uses one of the glycols, with
contacting in an absorber column at ambient temperature. It is also applied in
combination with cooling, at lower than ambient temperatures. It is the most widely
applied process, used extensively in production operations and in many refinery and
chemical plant operations.
Usually in field gas or plant residue gas dehydration either diethylene- or triethylene
glycol (DEG or TEG) is used. This type of contacting is commonly called glycol
dehydration. For lower than ambient temperature contacting, usually in conjunction with
an LTS or plant processing of the gas by refrigeration or refrigeration-adsorption type
process, ethylene glycol is used. This type of contacting is normally carried out by
injecting the glycol solution into the gas system before cooling takes place and is
commonly called glycol injection.
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like the DRIZO process, where glycol and BTEX compounds are used to conduct
azeotropic stripping to reduce water in lean glycol water to very low levels, gas water
contents to 1 lb/MMSCFD can be achieved.
In the design of glycol injection systems, the solution injection rate is best determined by
rigorous calculation methods available in qualified process tools; i.e. commercial
computer simulation programs listed previously. Manual methods are also available.
BTEX predictions in glycol systems are most accurate in GlyCalc from GRI.
Methanol has also been applied for dehydration. This is via direct injection or contact in
an absorber. However since methanol has a high vapor pressure, losses are considerably
higher to the vapor and liquid hydrocarbon phases than with glycols. Recovery methods
are applied and some special line-ups are licensed such as IFPEXOL.
Generally, liquid desiccants will not reduce the water content of the gas as low as the
solid desiccants, but when either can be applied the liquid desiccant dehydration system
usually has an appreciably lower cost of installation and operation than a solid desiccant
system for the same volume of gas. Solid desiccants are generally selected to achieve
dew-points below 0 °F and almost exclusively for processing below –40 °F down to
cryogenic temperatures of -150 °F.
Adsorption of the water with a solid desiccant Molecular sieves have found wide
acceptance in the gas processing industry for cryogenic plant feed conditioning
applications and some sour gas applications with special acid resistant binder
formulations. Dehydration of natural gas to the usual pipeline requirement of 7 lb water /
MMSCF is normally least costly utilizing a liquid desiccant such as glycol than using
solid desiccants.
Activated alumina and silica gel have been successfully also used for many years in
production and processing applications that require lower dew point than achieved by
conventional glycol. With silica gel it is possible to simultaneously remove
hydrocarbons and water in so-called short cycle units.
As a minimum, two bed systems are used with thermal regeneration. Multiple bed
systems are used on gases with relatively low water content. Typically one or more bed
is in service drying gas and one bed is in regeneration - heating; other beds may be in
various stages of cooling or in standby. Once a bed is loaded with water it is switched
into regeneration. In order to achieve high energy-efficiency multiple bed systems can
provide manifolds to switch a bed into cooling and allow its heat content to pre-heat the
bed going into regeneration. Regeneration system design is important and switching
valves must be of high quality to ensure wet gas is not bypassing the unit.
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hygroscopic. Water vapor is removed from natural gas as it flows through a bed of
desiccant tablets in a pressure vessel. Moisture is attracted to salts in the deliquescent
tablets, and coats them with hygroscopic brine. This brine continues to attract water,
forms a droplet, and then flows down the desiccant bed into a liquid sump. Since, the
desiccants dissolve upon attracting and absorbing water vapor (deliquesce), new
desiccant is simply added to the vessel when needed.
General process application selection is outlined on the map below. The axes are water
content in the wet gas, in lb/MMSCF and dry gas dew point, in °F.
1000
Compress
&
Cool
Wet Gas Water Content, lb/MMSCF
1
-60 -40 -20 0 20 40 60 80 100 120 140
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Economics usually favor compression and or cooling up to about 600 to 1000 psig and
100 to 120 °F; this relates to 50 to 150 lb/MMSCF water content at saturation. Glycol
based systems for are generally chosen for applications requiring water dew-points in the
range of 0 to 30 °F, i.e., 4 to 7 lb/MMSCF. For lower dew-points, down to 10 or 20 ppm
water adsorption with solid desiccant is generally applied. Both water content of the
inlet gas stream and the outlet stream dew-point (or outlet water content) affect choice of
system.
The liquid desiccants most commonly used at present are certain glycols – ethylene-,
diethylene-, and triethylene glycol, although other compounds have been utilized for
special circumstances, such as methanol or glycerol.
A key to understanding the reason glycol and methanol are effective in removing water
and inhibition hydrates lies in their chemical structure.
H H H
H- C – OH HO - C - C - OH
H H H
In each of these molecules there is a hydroxyl group (OH) which hydrogen–bonds with
water molecules. Glycol, having two hydroxyl groups, bonds even more strongly.
Factors that influence the selection of the particular glycol for a specific application
include:
Glycol Dehydration
The design glycol circulation rate is usually set at about 3 - 4 gallons of glycol per pound
of water to be removed. (Higher temperature gases, at say 120 – 130 °F with greater
water content, require the higher circulation rates.) Since the resulting gas water content
or dew-point depends primarily upon the water concentration of the circulated solution, it
is essential to maintain the water content of the glycol solution at a minimum with out
causing glycol degradation caused by excessively high still reboiler temperatures. The
maximum recommended reboiler temperatures for diethylene- or triethylene glycols are
350 °F and 400 °F, respectively, equivalent to glycol concentrations of 97-98 % wt.
This glycol concentration is adequate for obtaining water dew-point depressions of 55-65
°F; if dew-point depressions of more than 65 °F are desired, gas stripping is usually
utilized to lower the water content of the glycol solution, thus increasing the dew-point
depression attainable. A chart showing the effect of gas stripping on the water content of
TEG is included in the GPSA Engineering Data Book.
Because of the extreme difference in boiling points of water and the glycols, a sharp
separation can be accomplished in the still with a relatively short column. Some water
reflux normally is provided at the top of the columns to effect rectification of the vapors
and to minimize glycol losses. This reflux can be supplied by means of a rich glycol-
cooled condensing coil inserted in the top of the column, an air-cooled finned section at
the top of the column, or an external water source, such as demineralized water or steam
condensate. The quantity of reflux is not critical, between 15 – 25 percent of the glycol
circulation, on a mol basis, is generally adequate.
When sour gases are dehydrated with glycol an extra stripping step usually is
incorporated in the rich glycol work-up to remove acid gas from the rich glycol before
the regenerator. This prevents discharge of acid gas to the atmosphere in the water vent.
Recompression is used to recycle the stripping gas and acid gases to the inlet.
If high BTEX content natural gas is dehydrated then prevention of discharge of BTEX to
atmosphere in the water vent is accomplished by one of the following methods:
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Dehydration with Solid Desiccants
Dehydration of natural gas with solid desiccants is usually limited to those cases where
essentially complete water removal is desired, for example in cryogenic plants operating
in the region of –100 to – 150 °F or to where relatively small volume of gas are involved
(ex fuel gas system).
• Silica gel
• Activated Alumina
• Molecular Sieves
Solid desiccants may be divided into two classes: those that owe their activity to surface
adsorption and capillary condensation and those that react chemically with water. The
first type still has wide use in gas conditioning and production applications when there
are reasons not to use glycol-based or methanol-based dehydration.
With the exception of molecular sieves, which normally require somewhat higher
regeneration temperatures, the equipment and process flow arrangements for all these
desiccants are essentially identical. In most cases, equipment designed for one desiccant
can be readily operated using another, although the desiccant used can affect the capacity
of the dehydration facilities markedly. The selection of desiccant depends, therefore,
upon such factors as absorbing capacity and desired dew-point, cost of initial charge of
desiccant, desiccant bed life, utility requirements, etc., with due consideration for the
process limitations of each desiccant.
For normal natural gas dehydration applications, the following design loadings or water
absorbing capacities should be assumed:
These design loadings are usually reduced somewhat for unusual situations, such as
cryogenic plants where a water dew-point of minus 100 °F and lower is desired.
Some other factors that may affect the selection of the desiccant to be used are:
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2) Presence of H2S. Alumina-type desiccants catalyze the formation of COS for
H2S. Therefore, silica-type or molecular sieve desiccants are recommended
for gases containing H2S. A caution should be noted on the formation of
elemental sulfur on the bed during regeneration if oxygen is present in the gas.
3) Other contaminants. The presence of heavy hydrocarbons, often compressor
oils, in the gas can seriously affect the capacity of all the desiccants, although
it affects molecular sieves less.
The following sample illustrates the conditions, which must be defined for design
calculations for a typical solid desiccant unit. Details will be provided in mole-sieve
presentation.
Conclusion
This introduction has covered overview of dehydration and hydrate formation. The
concerns are integrity of pipeline and transport systems from flow blockages or
corrosion. An example of hydrate inhibition with direct injection glycol has been
provided. Now more detail discussion of TEG, mole-sieve and innovations will be
presented.
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GAS DEHYDRATION FUNDAMENTALS
1) it has the lowest molecular weight of the glycols and, therefore, less is
required;
2) it has a lower viscosity than the other glycols at the temperatures involved;
3) the freezing point of its water solution is appreciably lower than for the other
glycols; and
A quick estimate can be made by calculation with the Hammerschmidt equation. This
equation can also be used for estimation of inhibitor requirements for direct injection in
flow lines. This equation is based on the phenomenon that addition of a solute lowers
the freezing point of the solvent:
2335W
d= 100M – M × W
Normally, the condensed hydrocarbons and the diluted glycol solution containing the
condensed water are separated in a conventional phase separator. The heavier glycol
solution phase is then regenerated in a reboiled still column for re-use, in much the same
manner as in the glycol dehydration system. Because the re-circulated, lean glycol
solution is only about 80 percent glycol by weight, compared to 97 – 98 percent by
weight for the dehydration system, reboiler temperatures are appreciably lower, e.g.,
about 260 °F for 80 percent ethylene glycol solution. As for the dehydration system, the
amount of reflux to the still is not critical, between 5 – 10 percent of the lean glycol
solution, on a mol basis, will be adequate.
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The following sample problem illustrates the steps taken in design calculations for a
glycol injection system.
Design Basis:
1,200 MMSCFD of gas at 1000 psia and 90 °F
Molecular weight of gas 17.45 (equivalent to 0.6 gravity)
Water content6 15 lb/MMSCF
Final gas temperature -40°F
Use 80 percent ethylene glycol that has molecular weight of 62.1
From Figure No. 20-15 in the GPSA Engineering Data Book, 11th Edition, the hydrate
temperature for 0.6 gravity gas at 1000 psia is approximately 61 °F. Therefore, the
desired minimum dew-point depression is 101 °F (61 + 40).
2335 W
d= --------------------------
100 M - M * W
2335 W
101 = ----------------------------
100 * 62.1 – 62.1 W
Solving:
X
-------------------- = 0.73
1.25 X + 750
Add 25 to 50% to theoretical requirement for a design basis. Therefore the glycol
requirement = 1.5 * 6257 = 9385 pounds per hour. The density of 80% ethylene
glycol is 9.125 pounds / gallon (60 °F).
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Therefore:
9385
-------------------------- = 22 gpm glycol injection rate
0.8 * 9.125 * 60
Separation of the rich glycol and the condensed hydrocarbons is always imperfect at low
temperatures (- 40F in the present example) because a stable dispersion, or even some
emulsion, is formed due to the turbulence in the piping system and equipment. The
stability and long break time for this mixture is due to the high viscosities of the fluids at
the low temperature. It has been found that heating to about 170F effectively breaks this
emulsion mixture. This is usually accomplished by heat exchange between the hot re-
circulating lean glycol solution and rich glycol solution. Sometimes it is necessary to
supplement the cross heat exchange with external heat in a pre-heater. This is to limit the
lean glycol to 60 – 80 °F, preferred to obtain good distribution in the injection sprays.
Heat load on the lean glycol – rich glycol heat exchanger is:
= 1,530,000 Btu/hr
1,530,000 Btu/hr
∆T = -------------------- = 180 °F
12,450 lb/hr * 0.680 Btu/lb-°F
and
T2 = -40 + 180 = 140 °F
= 280,000 Btu/hr
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Lean glycol solution (regenerator bottoms) consist of:
For design, assume a reflux rate of 5% overall or 14 mol/hr. For comparison this is 250
lb/hr against water removed of 750 lb/hr or about 25% reflux (250/(750+250)).
Reboiler temperature at 80% MEG and atmospheric pressure is 260 °F (per industry data
temperature-composition chart for ethylene glycol-water).
Btu / hr
Lean glycol, sensible heat
11,700 lb/hr * ( 260 °F – 170 °F ) * 0.770 Btu/lb-°F= 810,000
Water, vaporization
750 lb/hr * ( 1150.4 – 137.9 ) Btu/lb = 760,000
Reflux
250 lb/hr * 1000 Btu/lb = 250,000
----------
Total 1,920,000
This illustrates the process design of the glycol injection system for a LTS system.
Design criteria for sizing the vessels and heat exchange equipment follows industry
standards.
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