NATURAL GAS ENGINEERING

Natural Gas Composition and Phase Behavior

Depending on where and from what type of reservoir the natural gasis produced, its
composition can vary widely. Generally, it containsprimarily methane (CH4) with decreasing
quantities of ethane (C2H6),propane (C3H8), butane (C4H10), and pentane (C5H12). Some
naturalgas mixtures can also contain nonhydrocarbon gases such as carbondioxide (CO2),
oxygen (O2), nitrogen (N2), hydrogen sulphide (H2S),and traces of rare gases (Ar, He, Ne,
Xe). No matter what the naturalcomposition of gas is, the product delivered and finally used
by theconsumers is almost pure methane.
Natural gas phase behavior is a function of pressure, temperature,and volume. Therefore it is
very often illustrated by the “PVT diagram” or phase behavior envelope. Understanding
phase behavior iscritical to the hydrocarbon recovery mechanism and production prediction.
Certain concepts, demonstrated in Figure 1–7, associatedwith phase envelopes are worth
introducing before we discuss different types of natural gas behaviors.

Bubble Point Curve-

The curve that separates the pure liquid(oil) phase from the two-phase (natural gas
and oil) region.This means that at a given temperature, when pressuredecreases and below the
bubble point curve, gas will be emitted from the liquid phase to the two-phase region.
Dew Point Curve
The curve that separates the pure gasphase from the two-phase region. It is the
connected points ofpressure and temperature at which the first liquid droplet isformed out of
the gas phase.
Critical Point
The point on the phase envelope where thebubble point curve meets the dew point
curve. At that givenpressure and temperature, gas properties are identical to liquid properties.
The pressure and temperature at the criticalpoint are called critical pressure and temperature,
respectively.
Cricondentherm
The highest temperature at which liquidand vapor can coexist. That means the
mixture will be gasirrespective of pressure when the temperature is larger
thancricondentherm.
Cricondenbar
The highest pressure at which a liquid andvapor can coexist.
Natural Gas Properties
It is clear that the fluid finds itself at differentpressures and temperatures during the
whole process of naturalgas production. Unlike those of oil, natural gas properties vary
significantlywith pressure, temperature, and gas composition. Below is anoutline of the gas
properties that play very important roles in gas production, prediction, and evaluation. These
include the gas specificgravity (often compared to air), the gas deviation factor, density,
viscosity, isothermal compressibility, and the formation volume factor.

Gas Specific Gravity

Gas specific gravity, γg, as commonly used in the petroleum industry,is defined as the
ratio of the molecular weight of a particular naturalgas to that of air. The molecular weight of
a gas mixture is the summation of the products of the individual mole fractions and molecular
weights of each individual component. Air itself is a mixture ofgases. It contains about 21%
oxygen, 78% nitrogen, and the rest arecarbon dioxide, water vapor, and some inactive gases.
So the molecular weight of air has been calculated as 28.97. Therefore, gg of a natural gas
can be defined as

where yi and MWi are the mole fractions and molecular weights,respectively of
individual components in the gas mixture.
n is thetotal gas components in the gas mixture.

Table 1–1 gives the molecular weights and critical properties formost hydrocarbon
and nonhydrocarbon gases likely to be found in natural gas reservoir. A lean or light gas
reservoir containsprimarilymethane and ethane with small traces of other gases. Pure
methanewould have a gravity equal to (16.04/28.97 =) 0.55. A rich or heavygas reservoir
may have a gravity equal to 0.75 or, in some rare cases,higher than 0.9.
Gas Deviation Factor
A natural gas mixture under reservoir conditions is non ideal and its behavior can be
approximated by the real gas law, a general equation of state for gases:
pV= ZnRT
where p is pressure in psi, V is the gas volume in ft3, n is the number of moles of the gas, T is
absolute temperature in R, R is the universal gas constant and equals to 10.73 psi ft3/lb-mol-
R. Z is the gas deviation factor or “Z-factor” in some petroleum literature. Chemical
engineers have called it the super-compressibility factor. It is defined asthe ratio of the real
volume (the volume actually occupied by a gas ata given p and T) to the ideal volume
(volume it would occupy had itbehaved as an ideal gas). It is a measure of how a real gas
deviatesfrom ideality.

The gas deviation factor is an important gas property and it isinvolved in calculating gas
properties such as the formation volumefactor, density, compressibility, and viscosity. All
these properties arenecessary in calculating initial gas-in-place (and, thus, reserves),
predicting future gas production, and designing production tubing andpipelines (Elsharkawy
and Elkamel, 2001).TheZ can be determined in a PVT laboratory. In common practiceit is
calculated from published charts such as the one shown inFigure 1–8 by Standing and Katz
(1942). To use this chart, it is necessaryto calculate the pseudoreduced properties (pressure
and temperature).

Pseudoreduced Properties
For gas mixtures, the gas critical pressure and temperature are calledpseudocritical
pressure and temperature to be distinguished from those of pure components, and can be
calculated as

where pciand Tciare critical pressures and temperatures of individual components,

respectively. The temperature must be absolute (R or K), which is simply °F + 460 or °C +
273. The pseudoreduced pressure and temperature of the mixture are simply

As can be seen from Figure 1–8, at the standard conditions of psc= 14.7 psi and Tsc=
60°F = 520 R, the gas deviation factor, Zsc, canbe taken as equal to 1.

Pseudocritical properties of gas mixtures can be estimated from the given gas specific
gravity if gas composition is not known.Figure 1–9 relates the gas specific gravity (to air)
with the pseudo critical properties of gas mixtures. This chart can be used as an
approximation when only the gas specific gravity is known or when a quick calculation is
indicated.
Gas Density
The gas density is defined as mass (m) per unit volume (V). It can becalculated from
the real gas law

In field unit, R is 10.73 psi-ft3/lb-mol-R, rgis in lb/ft3, and p and Tare in psi and R,

respectively. In SI unit, R is 8.314 m3-Pa/K-mol, is

in kg/m3, and p and T are in Pa and K, respectively.

Gas Formation Volume Factor

The formation volume factor relates the reservoir volume to the
volume at standard conditions of any hydrocarbon mixture. In the case of a natural gas, the
formation volume factor, Bg, can be related with the application of the real gas law for
reservoir conditions and for standard conditions. Thus,

LNG Liquefaction
The liquefaction process is the key element of the LNG plant. Liquefactionis based on
a refrigeration cycle, where a refrigerant by meansof successive expansion and compression,
transports heat from theprocess side to where the natural gas is. LNG plants often consist of
anumber of parallel units, called trains, which treat and liquefy natural gas and then send the
LNG to several storage tanks. The capacity of a liquefaction train is primarily determined by
the liquefaction process, the refrigerant used, the largest available size of the
compressor/driver combination that drives the cycle, and the heat exchangers that cool
the natural gas (Smaal, 2003).
The basic principles for cooling and liquefying the gas using refrigerants,involve
matching as closely as possible the cooling/heating curves of the process gas and the
refrigerant. These principles result in a more efficient thermodynamic process, requiring less
power perunit of LNG produced, and they apply to all liquefaction processes.Typical cooling
curves are shown in Figure 6–2. Observing thecooling curve of a typical gas liquefaction
process, three zones can benoted in the process of the gas being liquefied. A precooling zone,
followedby a liquefaction zone, and completed by a subcooling zone.All of these zones are
characterized by having different curve slopes, or specific heats, along the process. All of the
LNG processes are designed to closely approach the cooling curve of the gas being liquefied,
by using specially mixed multi-component refrigerants that will match the cooling curve at
the different zones/stages of the liquefaction process, to achieve high refrigeration efficiency,
and reduce energy consumption. The liquefaction process typically accounts for almost 45%
of the capital cost of the overall LNG plant (Knott, 2001),
Condensate stabilization
The condensate contains dissolved light hydrocarbons and H2S, which must be
removed to meet the export condensate specifications. A condensate stabilization unit is
designed to produce a condensate with 4 ppm H2S and RVP (Reid vapor pressure)
specifications, ranging from 8 to 12 psi. The stabilizer overhead vapor is compressed and
recycled to the HP separator. There are different design options in configuring the
stabilization unit, which are discussed in Chapter 5. The H2S content in the condensate from
the stabilization unit can typically meet 10H2S ppmv specifications. However, it may contain
higher levels of organic sulfurs such as COS and mercaptans. If condensate is exported as a
product, the total sulfur content must be met, and a separate unit for removal of the
mercaptans content may be necessary. If the condensate is sent to refineries, the condensate
can be blended with the refinery feedstock and treated in the refinery units.

Acid gas removal unit

The acid gas removal unit is designed to remove the acidic components to meet sales
gas sulfur and CO2 specifications. H2S must be removed to meet the sales gas specification
of 4 ppmv, or ¼ grains per 100 scf of gas. In addition, COS, mercaptans, and other organic
sulfur species must be removed. Considering today’s stringent emission regulations, acid gas
removal unit alone may not be
sufficienttomeettherequirements.Treatedgasfromtheacidgasremovalunitmay need to be further
treated with additional units, such as molecular sieves or sulfur scavengers.

Gas dehydration unit

Treated gas from the acid gas removal is fed to the gas dehydration unit to meet the
water dewpoint specification for pipeline transmission, typically 7 lbs water/ MMscf. In
colder climate areas, the water dewpoint specification can be as low
as 40 F in order to avoid hydrate formation in the pipeline.
Depending on the plant capacity and extent of drying, different types of dehydration methods
are available, including glycol dehydration and solid desiccant (i.e., molecular sieves, silica
gels, activated alumina) dehydration.

CO2 removal
CO2 removal is required to meet the sales gas CO2 specification, typically limited to
2–3 mol%. CO2 may need to be removed to even a lower level to avoid CO2 freezing in the
cold section of the NGL recovery unit. Typically, in propane recovery process, 2 mol% of
CO2, can be tolerated as the NGL columnoperates at a warmer temperature. Deep CO2
removal may not be required, unless the gas is sent to a liquefaction unit, which, in this case,
would require CO2 to be removed down to 50 ppmv. If the NGL recovery unit is used for
ethane recovery, the demethanizer column would operate at a much lower temperature, which
is prone to CO2 freeze. Even CO2 freezing may not be a problem, a good portion of the CO2
will condense with the ethane product, which may not meet the CO2 specification in the
ethane product (typical Y-Grade NGL limits CO2 content in ethane to 500 ppmv). When
ethane recovery is required, design must ensure that CO2 in the feed gas to be removed
sufficiently to avoid CO2 freezing as well as meeting the CO2 specification of the ethane
product.

Dehydration
For NGL recovery, the deethanizer or demethanizer must operate at low temperatures.
This would require sufficient water to be removed to avoid hydrate formation in the columns.
If only propane recovery is considered, the column operates at a warmer temperature, at
about 60 F. In this case, the use of DRIZO triethylene glycol
(TEG) dehydration may be sufficient. TEG unit is more compact than molecular sieve unit
and is more suitable for offshore design. If ethane recovery is required, then molecular sieve
dehydration is necessary.

Drawdown Tests. Pressure drawdown tests are conducted by: (1) having an oilor gas well
shut in for sufficient time to establish a stabilized pressure distribution,
(2) putting the well on production at a constant rate, and (3) recording
the resulting decrease in bottomhole pressure. An ideal time to run a drawdowntest is when
the well is initially put on production because in addition toobtaining information on wellbore
conditions and formation permeability,estimates of reservoir volume can be made also. A
long, constant flow rateis required.

Well deliverability
The flow of gas from the reservoir into the wellbore, described above, is oftencalled the
inflow performance relationship (IPR). It is usually represented as agraph of flowing bottom-
hole pressure versus gas rate (see Figure). Thisgraph demonstrates that the flow rate depends
on the flowing pressure.From a production perspective, the flowing pressure is controlled at
the surface.The bottom-hole (sand-face) flowing pressure that corresponds to thewellhead
flowing pressure depends on the flow rate, the pressure level, the gascomposition, the pipe
diameter, and the depth of the well. For a given wellbore

configuration and a specified wellhead pressure, the flowing bottom-hole pressurecan be

calculated at various arbitrary flow rates. This is shown in Figure (b),and is called a “tubing
performance curve” (TPC).
Since the reservoir and the wellbore must interact, the “operating point” isobtained by
overlaying the TPC and the IPR curves (see Figure(c)). The pointof intersection is the
production rate from the well at the specified conditions.Several TPCs can be generated by
varying the specifications of the wellheadconditions or the tubulars.
These are overlain on the reservoir’s IPR and differentoperating points will result. The choice
of operating conditions is based on the
economic factors associated with each TPC.Calculation of the TPC is based on the friction
and hydrostatic pressure dropcalculations outlined in Chapter 2. In general, for single-phase
flow of gas, thebigger the tubing diameter the larger the operating point flow rate, and the
choice
of tubing diameter is straightforward and is directly linked to the cost of tubing.However,
many gas wells produce gas and liquids (water or condensate).Multiphase calculations are
complex and often show that the operating point ratecan be increased by “reducing” the
tubing diameter.When a gas well produces liquids, care must be taken to efficiently remove
allthe liquids; otherwise, they accumulate in the wellbore, and eventually theincreasing
hydrostatic back pressure “kills” the well. Various mechanisms existfor removing the liquids.
These range from “siphon strings” (small-diametertubing) to “plunger lift,” to reducing the
wellhead pressure, and to bottom-holepumps. Many gas wells stop producing (die), even
though there is still a lot ofgas left in the reservoir. They die simply because it is not
economically viable to
remove the liquids from the wellbore.The production rate of a gas well decreases with time,
because the reservoirpressure depletes. Eventually, the flow rate becomes uneconomic and
the well is
abandoned. Typically, to maintain a gas supply contract, additional wells aredrilled over time
to supplement the decreasing deliverability of the wells.

Gas treating processes

The natural gas treating processes can be grouped in several categories as shownin Figure. If
the sulfur content is relatively low, direct conversion processesare an option. These processes
use an alkaline solution for absorption of H2S andthen a chelating agent and oxidation with
air to form elemental sulfur.
There are two types of indirect acid gas removal adsorption and absorption.

Adsorption
Adsorption is a physicochemical phenomenon, in which impurities of the gas aretrapped and
removed physically or chemically by the surface of a selective solid.Absorption is the
removal of acid gases by physical

Absorption
Absorption by physicalsolvent toward acid gases or by chemical reaction with the
acid gases using achemical alkaline solvent.The dry-bed processes, which use a fixed bed of
solid materials to remove acid
gases through either ionic bonding or chemical reactions, can be divided into twocategories:
physical adsorption (i.e., molecular sieve process) and chemicalabsorption.

The gas treating processes shown in Figure

Chemical absorption processes
The chemical absorption processes can be broadly classified into two groups:
1.Alkanolamine solution
2.Potassium carbonate solution
In chemical solvent processes, absorption of the acid gases is achieved mainly bythe use of
alkanolamines or alkaline salts of various weak acids such as sodiumand potassium salts of
carbonate. Regeneration (desorption) can be brought aboutby use of reduced pressures and/or
high temperatures, whereby the acid gases arestripped from the solvent. Chemical absorption
processes chemically absorb the
H2S, CO2, and to some extent COS. Organic sulfur components do not chemicallyreact with
the solvent. Chemical solvents are specifically suitable whencontaminants at relatively low
partial pressure have to be removed to very lowconcentrations. Chemical solvents will not
remove mercaptans down to lowlevels due to the low solubility of these components. An
advantage, however, isthat there is minimum coabsorption of hydrocarbons.

Alkanolamine solvents
The chemical solvent process using the various alkanolamines is the commongas treating
process. Amines are well suited for applications where the acid gaspartial pressures are low
and low acid gas contents are required on the treated gas.The application of alkanolamines as
solvents for acid gas removal began in1930. In earlier applications, these amines were
represented by monoethanolamine(MEA) and diethanolamine (DEA). Later, other amines
like diglycolamine(DGA) and diisopropanolamine (DIPA) gained commercial recognition.
In recent years, various methyldiethanolamine (MDEA) and specialty solventsblends were
developed which take advantage of the low-energy characteristicsof MDEA.
Amines are compounds formed from ammonia (NH3) by replacing one ormore of the
hydrogen atoms with another hydrocarbon group. Amines are categorizedas primary,
secondary, and tertiary, depending upon the degree of substitutionof the hydrogen atoms by
organic groups. Replacement of a singlehydrogen atom produces a primary amine (MEA,
DGA), replacement of twohydrogen atoms produces a secondary amine (DEA, DIPA), and
replacement of
all three hydrogen atoms produces a tertiary amine (MDEA).
The chemical solvent processes are characterized by relatively high heat ofacid gas
absorption. A substantial amount of heat is required for solvent regeneration.
Amines are thermally stable, but are sensitive to degradation by oxidationand high
temperatures, and may have various side reactions with CO2, COS, andCS2. The degraded
amine can be recovered thermally or by ion exchange, asspecified by the solvent suppliers.

Acid gas loading of amines is not very sensitive to changes in acid gas partialpressure as
compared to physical solvents. While acid gas loading of a physicalsolvent increases with
partial pressure of the acid gases, amine acid gas loadingstays fairly constant regardless of the
operating pressure and cannot takeadvantage of the high operating pressure.Different amines
have different reaction rates with respect to the various acidgases. In addition, different
amines vary in their equilibrium absorption characteristicsfor the various acid gases and have
different sensitivities with respect tosolvent stability and corrosion characteristics.

Monoethanolamine: MEA is a primary amine, and is the most aggressive

amine among the group. MEA is also the lowest cost solvent.

MEA can remove both H2S and CO2 from gas streams to meet sales gasspecifications. MEA
solvent is very corrosive at high acid gas loadings and highsolution concentrations. It reacts
irreversibly with carbonyl sulfide (COS) andcarbon disulfide (CS2), which can degrade the
solvent and form heat-stable salts.MEA has a higher vapor pressure than other amines, and
the high equilibriumlosses can be a problem. Amine losses can typically be minimized using
a waterwash section in the upper section of the amine absorber.

Diglycolamine
DGA was developed in the late 1960s by Fluor Corporation and Jefferson Chemical
Company, a predecessor to Texaco Chemical and laterHuntsman Corporation. The advantage
of DGA in gas treating is that it canoperate with air cooling in hot climate locations, and was
chosen as the soletreating solvent for the Saudi Aramco gas projects in the 1970s. Fluor
patentedthis technology as the Fluor Econamine process that includes a side cooler on
theamine absorber.
As a primary amine, DGA is similar in many respects to MEA except that itexhibits lower
vapor pressure, lower solution corrosion tendency, and improvedsolution properties and can
operate at higher concentrations than MEA.
Thehigher operating concentration (up to 60 wt%) results in significantly lowercirculation
rates and energy consumption.DGA can remove COS, CS2, and (partially) mercaptans but
also formsdegradation products that are not reversible at normal amineregenerator
temperature.Degradation reactions produce N,N0,bis-(hydroxyethoxyethyl) urea,
andN,N0,bis-(hydroxyethoxyethyl)thiourea. To maintain the amine activity,
thermalreclaiming of a slip stream of the circulating amine is required.

Diethanolamine:
DEA is a secondary amine. Its amine reactivity and corrosivity are lower than those of
primary amines. The vapor pressure and heat ofreaction are also lower. DEA is a common
amine used for H2S and CO2 removalin refineries due to its stabilities with contaminants in
the refinery gas streams.
DEA can partially remove COS and CS2. However, the reaction rate of DEAwithCOS and
CS2 is lower than with MEA. The solution strength of DEA solvent istypically 25–30 wt%.

Diisopropanolamine:
DIPA is a secondary amine and its reactivity with acid
gases is similar to that of DEA. DIPA is more widely used in gas processingindustries in
Europe and Asia. As it also has some steric hindrance, it can be usedselectively either to
remove H2S (at low pressures) or to remove both CO2 andH2S (at higher pressures). DIPA
can be used to partially remove COS and CS2.The solution strength of DIPA solvent is
typically 20–40 wt%.

Methyldiethanolamine:
MDEA, a tertiary amine, is the most widely usedgas treating agent today. Unlike primary
and secondary amines, MDEA cannotreact with CO2 by the carbamate reaction. It can only
absorb CO2 by the slow
bicarbonate formation. This property allows MDEA to selectively remove H2Swhen treating
a gas stream containing both H2S and CO2. The slippage of CO2opens up more capacities in
debottlenecking gas treating units. By reducing CO2absorption, more solvent is available for
H2S removal. Other advantagesof MDEA solvent include low vapor pressure and solution
losses, low energy forsolvent regeneration, low corrosiveness, and resistance to
degradation.However,generic MDEA process would require low absorption temperature to
improve the
amine–H2S equilibrium for absorption in order to meet low H2S specification.Alternatively,
MDEA that is acidified with phosphoric, sulfuric, or other acids,can be regenerated more
easily, and can be used to produce an ultralow H2Scontent lean amine for treating. However,
the level of acidification has a certainlimit, as there is an impact on the pH value of the amine
solution and the equilibriumcurve of the acid gas solubility in the solvent Generic MDEA has
minimal COS and CS2 removal capability. The solutionstrength of MDEA solvents is 35–50
wt%.

Amine processes
The basic flow scheme of amine treating units has remained unchangedthroughout the years.
Amine unit requires steam for solvent regeneration and is amajor steam consumer in a gas
plant. In some designs, the amine regenerator isactually used as a heat rejection method to get
rid of excess steam in the gas plant.

A typical process flow diagram of the amine unit is shown in Figure

Typically, sour feed gas to the amine unit is filtered and cleaned of entrainedliquids and pipe
scales using an inlet filter separator. The separator gas is fed tothe amine absorber where the
acid gas content is removed by an aqueous aminesolution, producing a rich amine at the
bottom and a H2S-depleted gas from thetop. Depending on the applications some CO2, as
much as 2 mol%, can be left in the treated gas if the gas is used as pipeline gas. If the gas is
sent to an NGLrecovery unit or an LNG production plant, deeper CO2 removal is
required.The rich amine is let down in pressure to the rich amine flash drum. The richamine
flash drum is a three-phase separator designed for hydrocarbon liquids andamine separation.
Hydrocarbon liquids are removed from the flash drum using askimming device to avoid
buildup that would cause foaming.The flashed gas containingsomeH2S is treated using a
small packed section and recovered as fuel gas.

The flashed amine is preheated in the lean/rich exchanger, typically a

plate and frame heat exchanger, to about 200–215 _F, before entering theregenerator. The
regenerator typically operates at about 10–15 psig producingan acid gas to the sulfur recovery
unit. The rich amine is heated in theregenerator and stripped with steam, producing a lean
amine. The lean amineis cooled in the lean/rich exchanger and lean amine cooler and filtered
priorto returning to the absorber. The filter system typically includes a particulatefilter for
removal of corrosion materials and a carbon filter for removal ofheavy hydrocarbons. The
filtration system is typically installed on the leanamine side, which is easier for maintenance
as the system is free of H2S.Alternatively, it can also be installed on the rich amine side,
which has theadvantage of protecting the amine regenerator from fouling. In this design,
proper operating procedure must be exercised because of the H2S content in therich
amine.The amine storage tank acts as a surge for the amine system, which dampensout flow
fluctuation, maintaining a constant circulation. The storage tank istypically designed to hold
the volume of the entire amine inventory. The aminetank content should be periodically
checked for active amine and purity, andshould be adjusted by makeup as necessary.If the
feed gas contains ammonia, it will be stripped off in the overheadsystem, which will combine
with acid gases to form ammonia salt, such asammonia bisulfate. Excessive buildup of
ammonia salt will cause severe corrosion,causing hydrogen blistering on piping and
exchangers. The ammoniacontent inthe overhead system should be maintained at below 1
wt% by purgingthe reflux water.
Physical solvent processes
Physical solvent processes can remove acid gases and organic sulfur based onphysical
absorption, and no chemical reaction occurs.
Physical solvents have an advantage over chemical solvents when treatingsour feed gas
streams with high acid gas content. The physical solvent’s acid gasholding capacity increases
with the partial pressure of acid gas (Henry’s law).Thus, they are more economical than
chemical solvents in treating high-pressurehigh-CO2-content gas.
Unlike chemical solvents, physical solvents operate at ambient to subambienttemperature.
They are noncorrosive and do not require stainless-steel material tocombat corrosion.
Unless operating at cryogenic temperatures, only carbon steelis required.
Physical solvents can be regenerated by reduction in solvent pressure.Compared to
chemical solvents, physical solvents absorb more hydrocarbons,and have high hydrocarbon
losses. For this reason, physical solvents are morecommon in treating synthesis gas, which
has no hydrocarbons. When used innatural gas treating applications, flash gas compressor
recycle is required tominimize the hydrocarbon losses.
Some of the more common physical solvents used in gas treating are:
1. n Propylene carbonate (PC)
2. n Dimethyl ether of polyethylene glycol (DEPG)
3. n Methanol (MeOH)
4. n N-Methyl-2-pyrrolidone (NMP)
These solvents are used to remove CO2 from high-pressure sour gases. During theabsorption
processes, they also coabsorb other components.

Dimethyl ether of polyethylene glycol

DEPG is a mixture of dimethyl ethers of polyethylene glycol. Solvents
containingDEPG are manufactured by several companies including Coastal
ChemicalCompany, Dow, or Clariant. DEPG is marketed by Dow as the Selexol_ solventand
by Clariant as the Genosorb_ solvent. The DEPG solvent process can belicensed from UOP
as the Selexol process or from Fluor as the EconoSolvsprocess.
Similar to PC, the DEPG solvent can be regenerated by successive pressureletdown and/or
stripping with air or nitrogen for deeper CO2 removal.
DEPG candehydrate feed gas and remove hydrogen cyanide (HCN), mercaptans, and
heavyhydrocarbons from natural gas.
While PC can operate at 10 to _20 _F temperature, operation of DEPG islimited to 32 F. The
difficulty with DEPG operating at low temperature is theviscosity problem. At lower
temperatures, DEPG viscosity will greatly increase,which will impede the heat and mass
transfer operation in heat exchangers,separators, and columns, making absorption more
difficult.
The other difference between the PC process and the DEPG process is thesolvent
concentration. PC can operate as a pure component, while the DEPGprocess requires
maintaining 95 wt% concentration. This is necessary to maintainthe regenerator bottom
temperature at about 300 _F in order to avoid solventdegradation.
Compared to other physical solvents, DEPG requires higher solvent circulationmainly due to
the high operating temperature.

DEPG process
DEPG has been used in gasification projects to selectively remove CO2 from
thesynthesis gas, to produce a clean fuel for integrated gasification combined cycle(IGCC)
power plants. In these plants where the syngas feed to the DEPG processis unshifted (without
converting CO to CO2 and hydrogen), a single-stageDEPG unit can be used.
The basic DEPG process flow diagram is shown in Figure.The feed gasat about 600
psig pressure is first cooled by heat exchanged with the cold treatedgas and enters the
absorber where its H2S content and a portion of the CO2content are absorbed by the lean
DEPG. For H2S selective removal, the absorbermust contain sufficient trays, and the solvent
flow must be minimized to avoidexcessive coabsorption of CO2. The absorber typically
requires four or more
sections of packing.
The rich solvent from the absorber is letdown in pressure to a flash drum.The flash
gas containing the absorbed hydrogen is recycled back to theabsorber for recovery. The
flashed solvent is then heated in the lean/richexchanger and then regenerated in a solvent
regenerator, similar to the designof an amine unit.
Heavy hydrocarbons and sulfur compounds such as mercaptans are preferentiallyabsorbed by
DEPG. These components may be removed in theregenerator by steam stripping and end up
in the reflux drum. However, the DEPGregenerator typically operates at 300 _F, which may
not be high enough to boil offthe heavier compounds. If this is the case, the heavier
compounds will accumulatein the system, which may cause foaming problems. Since DEPG
is solublein water, the heavy hydrocarbons can be removed by extraction with water by
processing a slip stream of the rich solvent from the process.

Mixed physical and chemical absorption processes

Some chemical manufacturers have developed processes that take advantage ofthe
benefits of physical and chemical solvents. These mixed solvents or “hybridsolvents” have
different formulation of the solvent mixtures, and are trademarkedby the solvent
manufacturers. These solvents take advantage of physical solventproperties, such as high acid
gas solubility at high pressure and high solubility ofmercaptans and organic sulfur. It also has
the acid gas reactivity of a chemicalsolvent to meet tight specifications.
The use of hybrid solvents is more beneficial at high acid gas partial pressures.By
using various amine combinations with the physical solvents, thehybrid solvents can be
formulated to allow for complete CO2 removal, bulk CO2
removal, or CO2 slip, while achieving H2S removal comparable to alkanolamines.In hybrid
systems, mercaptans and organic sulfur can be removed bythe physical solvent portion.
However, the hybrid solvent system also inheritssome of the drawbacks of a physical solvent
system, such as more absorberstages, high hydrocarbon losses, and ineffective treating at low
pressures.Examples of hybrid solvents include Sulfinol.Sulfinol solvent to treat various levels
of acid gases and
different sulfur contaminants. The solvent contains sulfolane, which can beformulated
according to feed gas compositions and product gas specifications.
The formulation combines the chemical reaction properties of amines and thephysical
absorption properties of sulfolane. Three different solvents are availablefor the Sulfinol
process:
1. n Sulfinol-X consists of sulfolane, MDEA, piperazine, and water
2. n Sulfinol-M consists of sulfolane, MDEA, and water
3. n Sulfinol-D consists of sulfolane, DIPA, and water
Glycol dehydration

Among the different natural gas dehydration processes, absorption is the

mostcommon technique, where the water vapor in the gas stream becomes absorbed ina
liquid solvent stream. Although many liquids possess the ability to absorb waterfrom gas, the
liquid that is most desirable to use for commercial dehydrationpurposes should possess the
following properties:
1. High absorption efficiency
2. Easy and economic regeneration
3. Noncorrosive and nontoxic
4. No operational problems, such as high viscosity when used in high Concentrations.
5.Minimum absorption of hydrocarbons in the gas, and no potential
contamination by acid gases.
Glycols are the most widely used absorption liquids as they approximate theproperties
that meet the commercial application criteria. Several glycols havebeen found suitable for
commercial application.

Conventional TEG dehydration process

Figure shows the scheme of a typical TEG dehydration unit. As can be seen,wet natural gas is
processed in an inlet filter separator to remove liquid hydrocarbonsand free water. The
separator gas is then fed to the bottom chamber of anabsorber where residual liquid is further
removed. It should be cautioned thathydrocarbon liquids must be removed as any
entrainments will result in fouling ofthe processing equipment and produce carbon emissions.
The separator gas isthen contacted countercurrently with TEG, typically in a packed
column.Typically, the liquid loading on the tray (GPM per square foot) is very low,
due to the low liquid to gas ratio. To avoid liquid maldistribution, structuredpacking or
bubble cap trays should be used.
TEG will absorb the water content, and the extent depends on the lean glycolconcentration
and flow rate. TEG will not absorb heavy hydrocarbons to anydegree; however, it will
remove a significant portion (up to 20%) of the BTEX(benzene, toluene, ethyl benzene, and
xylenes) components. BTEX is consideredas a volatile organic compound (VOC), which
must be incinerated to comply withemissions requirements.
Dry natural gas exiting the absorber passes through a demister, and sometimesthrough
a filter coalescer to minimize TEG losses. Because of the relatively lowTEG flow rate, there
is not much sensible heat exchange, hence the dried gastemperature is almost the same as that
of the feed gas.
The rich glycol is used to cool the TEG regenerator overhead, minimizingglycol
entrainment and losses from the overhead gas. Rich glycol is furtherheated by the glycol heat
exchanger and then flashed to a flash tank. The flash gascan be recovered as fuel gas to the
facility.
The rich TEG is filtered with solid and carbon filters, heated, and fed to
theregenerator. The filtration system would prevent pipe scales from plugging thecolumn and
hydrocarbons from coking and fouling the reboiler. The water contentin the glycol is
removed with a reboiler. Heat to the reboiler can be by a fireheater or an electrical heater.
Electric heater is preferred as it would avoidemission problems, particularly in smaller units.
The water vapor and desorbednatural gas are vented from the top of the
regenerator.The dried glycol is then cooled via cross-exchange with rich glycol; it is
pumpedand cooled in the gas/glycol heat exchanger and returned to the top of the absorber.
The glycol regeneration is typically designed as a skid mounted unit that canbe prefabricated
and shipped to the site.