SPE 49522

Acid/Sour Gas Management in the Petroleum Industry

A.K.M. Jama/uddin, 0.8. Bennion, F.B. Thomas, Hyca/ Energy Research Laboratories Ud.
M.A. Clark, University of Ca/gaty

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P.O.b 8333838, sulphide ~S). The waste gas streamis commonly
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referredto as acid gas.
Abstract The economicsof recoveringsulphurfrom acid gas
Due to decreasing world demand for elemental sulphur, has becomeunfavorablebecauseof decreasingworld
the economics of recovering sulphur from sour natural demandfor elementalsulphur.Air emissionstandards
gas has become unfavorable. At the same time, air and regulationsare becoming increasingly stringent,
emission standards and regulations are becoming increasingdie needfor anenvironmentally-friendlyand
ina'eaSingiy stringent, increasing the economical strain cost-effective methodsfor dealing with the acid gas
on oil and gas companies producing sour natural gas. streams.Therearevariousalternativesto dealwith the
Hydrocarbon producing companies are in search of acid gasmixtures. Thesealternativesare:
environmentally-friendly and cost-effective methods . Injection of compressedacid gas into the porous
for dealing with acid gas, which is produced in formation.
association with sour natural gas. . Disposeacid gaswith disposablefonnation water.
In recent years. compressed acid gas re-injection . Solubilize acid gas into light hydrocarbonsolvent
into a porous formation has emerged as a viable and inject the solvent containing acid gas
alternative to sulphur recovery with the added componentinto the depletedreservoirasa miscible
advantage of eliminating air emissions. As an flood enhancedoil recovery(EOR) technique.
alternative, some operators also solubilize the sour/acid Acid gascompressionandre-injectioninto depleted
gas into disposable formation water and dispose acid resuvoirs or disposalzones,similar to producedwater
water into porous formation. In addition, to take disposal, is a viable alternativeto traditional sulphur
advantage of high solubility of acid/sour gas into light recovery processeswith the added advantagesof
hydrocarbon solvent, some operators are also injecting reducing greenhousegas emissions and providing
pressuresupportfor producingreservoirs.1-4
light hydrocarbon solvent containing acid/sour gas into
the depleted oil leg as a miscible flood enhanced oil Acid gas recovered from die amine process contains
recovery (EOR) technique. Laboratory tests and results water, and hence, proper strategic design is essential to
will be presented in this paper which illUSb'atethe pros address ilie issue of whether an acid gas stream needs
and cons of all these alternative processes to manage dehydration or not The appearance of a free liquid
the produced acid/sour gas in the petroleum industry. water phase due to changes in temperature and pressure
conditions can cause significant operating problems
Introduction (i.e. compressor damage,corrosion, hydrates formation,
Sournaturalgasesare producedaseitherfreegasor as etc.). Currently, most injection schemes include
liberatedsolution gasfrom sour oil. Thesegasesmust dehydration facilities to ensure ilie absence of free
2 ACID/SOURGAS MANAGEMENT
IN THE PETROlEUMINDUSTRY
water in die system and reduce corrosion and hydrate
concerns. Dehydration facilities comprise a major
portion of die capital cost of re-injection facilities.
Alternatively, stainless steel materials and med1anol
injection are used to combat corrosion and hydrate
formation conditions. However, diis alternative is also
expensive and poses significant operating problems. An
alternative and cost-effective approach would be to
keep die water in die vapor phase throughout the
injection circuit, eliminating die need to dehydrate.
To design an optimized injection strategy widiout
dehydrating the acid gas, detennination of
thermodynamic properties (i.e. water content,
dewpoint, bubble point, and hydrate points) of die acid
gas is necessary. The system may also be designed to
inject die mixture as a dense phase, above die critical
point, reducing die required injection pressure and
horsepower requirement due to die hydrostatic head of
die colwnn of fluid in die injection wellbore. The
hydrate curve information will ensure diat the system
never enters die hydrate region, reducing die risk of
pipeline plugging.
An alternative approach is to solubilize die acid gas
in produced or source water in a high pressure
contacting tower on the surface, followed by
subsequent injection of die sour water.s An
understanding of die solubility of die injected gas or in-
situ water phase is essential in order to quantify die
speed of migration of die injected gas (in a direct
injection scheme) and to design the contacting
apparatus and determine volumes of water required to
effect disposal in a sour water disposal scenario.
Anodier approach is to solubilize acid gas into light
hydrocarbon solvent (taking advantage of high
solubility of acid gas into light hydrocarbon solvent),
and subsequently, use die light hydrocarbon solvent
containing acid gas into die depleted hydrocarbon
reservoir as a miscible flood enhanced oil recovery
(EOR) tedmique.
Experimental tests and results of various processes
are discussed in this paper. In addition, advantagesand
disadvantages of all diese options are also discussed.
Characteristics of Acid Gas Streams
A summary of basic characteristics of acid gas
components are summarized in Table 1.6.7As seen in
the table, bodt gases have diatomic structme and
exhibit high propensity for solubilizing in both aqueous
and hydrocarbon solutions, a fact which can be used to
our advantage in some disposal operations.
Composition ofdte injected acid gasescan vary widely
and is a direct function of the acid gas content of the
oils/gases which are acting as the feedstocks for the
sweetening process. In general, most acid gas blends
contain at least 4Q8/.H.,S and often dte fraction ofHzS
SPE 49522
in the injection gas is considerably greater than dlis
value. In other instances, the H2S content in the acid
gas streams are seen to be lower as well (in die range of
100/0and the remaining component is COJ.
Injection of Compressed Acid Gas into the Porous
Formation. Sour natural gases are sweetened by
removing H2S and CO2 by absorption with a
regenerative solvent in an amine plant. The acid gas
mixture of H2S, CO2, and a small amount of light
hydrocarbons leaves the sweetening unit saturatedwith
water at the amine still conditions of low pressure and
high temperature. The gas mixture is then compressed
in 3 to 4 stages. After each stage, the gas mixture is
cooled, without entering the two-phase region.
Condensed water is removed after each stage. After
the last stage,the mixture travels down the pipeline into
the disposal well. Ideally at the fmal compressor
discharge pressure, the mixture will be supercritical.
Further cooling in the pipeline will increase the density
without a phase change, increasing the hydrostatic head
of fluid in the well and reducing the required injection
pressure. The operator must ensure d1at the mixture
does not cool below its water saturation temperature,
especially in the hydrate region, to avoid corrosion and
hydrate plugging of the pipeline and wellbore.
Corrosion and hydrates may occur when the gas is
saturated with water. Due to the safety hazard
associated with acid gas equipment failure, most
injection schemes currently include dehydration
facilities to ensure the acid gas is undersaturated
throughout the system. Unfortunately, dehydration
facilities and stainless steel comprise a major portion of
the capital cost of re-injection facilities. Methanol
injection is an option to combat corrosion and hydrate
fonnation, but can significantly increase operating
expenses.
Although there is little experimental data on acid
gas mixture, the solubility of water in pure H2S and
CO2 lead to some interesting hypotheses. The ability of
the pure c0mp01Dldsto hold water in the vapor phase
decreases as the pressure increases up to about 3000
kPa (400 psi) for H2S and 6000 kPa (900 psi) for CO2.
At higher pressures dte water holding capacity of the
gases increases, corresponding to a higher water
absorption capacity in dte liquid phase or dense phase
compared to the vapor phase. In both cases,inaeasing
the temperature allows more water to be absorbed in
the gas phase. Small amounts of methane substantially
reduce the water absorption ability of both components.
It is assumed d1at solubility of water in the gas
mixtures mimics the trend of dte individual
components, then a minimum water holding capacity
existsat somepressure.I In a re-injectionfacility, over
each compression stage, dte pressure and temperature
increase and after each compression stage die gas is
cooled. Initially, die water holding capability of die gas
decreasesfrom stage to stage, until d1eminimum water
holding capacity is reached. Ifdle condensed water is
removed at this point. the gas will be undersaturated
widl water throughout die rest of compression.
Stainless steel will not be required in the compressors
or coolers after die second last stage. If die
temperature of die compressed gas does not drop to the
new water saturation temperature in the pipeline or
wellbore, dehydration can be eliminated and stainless
steel materials and methanol injection will not be
necessary.
It is understood that dehydration may not be
completely eliminated due to a particular set of
conditions, for example in an extremely cold climate,
die experimental data will still be beneficial. The
operator will know the inlet water content and the
conditions of the lowest water solubility of die system.
The glycol contactor tower, regenerator and circulation
system can then be designed appropriately.
Aldlough experimental data is available for pure
H2Sand CO20little work has been done determining die
water content. density, phase behavior and hydrate
formation conditions of acid gas mixtures.1-12
Currently, estimates of the density, water content and
phasebehavior of acid gas mixtures are being predicted
with equation of state models, as experimental data is
unavailable. The equations can produce considerable
error and result in over or underdesigned facilities.
Experimental data results in proper decisions on the
equipment and materials required for each particular set
of conditions, which can lead to considerable cost
savings. In this section of the paper, the results of a
study in which water content. dew point. bubble point
and hydrate formation conditions are presented. The
example acid gas mixture contains 100/0H2S/900/oCO2
and a minor amount of methane. The mixture was
saturated with water at 2800 kPa and 24OC(400 psia
and 75°F).
Experimental procedure and apparatus. The
apparatus consists of a temperature controlled air bath.
a high-pressure cell widl sight glass, a positive
displacement pump, a gas volume meter, a cooled water
trap, a mass balance and a Hewlett Packard 5890 gas
chromatograph (GC). The sight cell has an internal
volume of approximately 80 cm] (5 in]) and a
maximum working pressure of 70 MPa at 1500c
(10000 psi at 3000F). The 2.5 cm (I in.) dlick sight
glass located on the front and back of the cell allows
visual observation of the cell contents dtroughout
experimentation. As shown in Figure I, the high
pressure sight cell is mounted in the centre of the oven
as are the cylinders containing gas mixtures and
distilled water. The oven can be heated up to 1500c
(3000F) and the temperature is measuredand controUed
to within %IOC (2°F).
The sight ceU volume and pressureare controlled by
the addition and withdrawal of mercury through a port
at the bottom of the sight ceU. Sample fluids are
pumped in and out of a port at the top of the cell. The
pump measures volume displacement with a precision
of %0.02 an) (0.001 in2). A dead-weight calibrated
digital pressure gauge is connected to the pump outlet.
The oven is connected to a motor via a steel arm. The
motor rotates the ann, rocking the oven and its contents
in a 1800arc. The mercury in the sight cell agitates the
fluids and enhances the fluids and enhances mixing
when the oven and cell are rocked.
The apparatus is contained in a sour gas laboratory.
The lab is continuously flushed with fresh air pumped
in from die ceiling and drawn out of vents located in
the bottom four comers of the room to an incinerator
stack. A pem1anentH~ monitor is located close to the
floor, below the apparatus. If the monitor detects 10
ppm H~, an alarm sounds outside the sour gas lab and
the incinarator fires up. At 20 ppm the main lights in
the lab shut off and emergency lights flash. Personnel
working in die lab with supplied air breathing apparatus
(SABA) may not hear the alarm and the flashing lights
ensure their evacuation. The lab is equipped with a
video camera for continuous remote monitoring of
personnel performing dangerous work. An "H2S Panic
Button" which summons emergency rescueand medical
services is located immediately outside the sour gas lab.
A gas mixture is synthesized from pure components
in the laboratory using partial pressures.
Concentrations are verified using the GC. The system
is purged and gas is transferred to the sight cell. The
gas in die cell is saturated with water at the desired
temperature and pressure and allowed to equilibrate
while rocking. At equilibrium. usually reached within
a few hours. a stable free water phase should be visible
in the cell. ensuring the gas is fully saturated.
Water content analysis is performed by flashing a
sample of gas dtrough a valve to a cooled water trap
while maintaining constant ceU temperature and
pressure. The trapped. condensedwater is weighed and
the dried gas volume is measured. The average water
content is obtained over several samples. This method
of water content analysis has not proved reliable due to
the very small quantities of condensed water being
measured. The water content data obtained for this
report can be regarded as accurate only within an order
of magnitude. A control experiment with pure CO2
was within 200/0of accepted values and the average
difference between samples was %200/0.
ExperimentJ. The objective of this study was to
establish the phase behavior, water content and hydrate
conditions of an acid gas mixture saturated at die
compression inlet conditions of2.8 MPa (400 psi) and
24°C (75°F). A mixture of 100/0H2S and 900/. CO2
was prepared. A small amount of CH. was added and
the exact composition verified with dte OC. The
mixture was saturated widt water at 2.8 MPa (400 psi)
and 24 °C (75°F). After several hours of rocking, dte
average water content was detennined.
Several isodtenns were obtained to establish the
phase envelope. The cell temperature was set and
allowed several hours to equilibrate. The cell mercury
volume was increased incrementally, resulting in 15-30
psi pressure steps. Transient and stabilized phase
behavior was observed and recorded. The change in
mercury volume was recorded as a function of
pressure. At pressures close to dte dew and bubble
points, dte volume/pressure increment was reduced. By
taking a series of data points immediately above and
below the appearance and disappearance of the two-
phase region, the dew and bubble points were
established.
Isobaric cooling experiments were perfonned to
establish the hydrate fonnation conditions for this acid
gas/water mixture. The oven temperature was raised to
50°C (122 oF) and dte gas was pressurized to between
9000 kPa (1305 psia) and 17700 kPa (2567 psia) and
allowed to stabilize. Since the gas was saturated widt
water at 2800 kPa (400 psia) and 24 °C (75 oF) and dte
water content was not changed as the temperature and
pressure were raised, the gas was undersaturated at dte
conditions of high temperature and pressure. The
temperature was dten reduced in 1.6°C (3 OF) steps
every 30 to 45 minutes until a hydrate was visually
observed in dte cell.
The hydrate fonnation temperature measured in this
manner differs from dte traditional hydrate temperature
obtained by cooling gas in contact widt a liquid water
phase. When liquid water is present, hydrate fonnation
is predicted to occur at elevated temperatures in dte
order of 20°C (68°F) at 9000 kPa (1305 psia). When
dte gas is not in contact widt a water phase and is
undersatw'ated, hydrates cannot fonD until dte
temperature drops sufficiently dlat dte gas can no
longer bold all the water in solution and wfreewwater is
available for dte fonnation of hydrates. Hydrates fonD
preferentially to a liquid water phase, since dte gas is
already below its satmated hYdratetem perature at these
conditions.
Res"lts, observations and discussion. As recorded
in Table 2, dew points were observed at 7°c/41 00 kPa,
9°C/4342 kPa, 15°C/5045 kPa, 26°C/6355 kPa,
34 °C/7479 kPa and 37°C/7955 kPa. Bubble points
w~ observed at 7°c/4528 kPa, 9°C/4755 kPa,
16°C/55 10 kPa, 27°C/6900 kPa and 34°cn844 kPa.
Above 37.5°C (99.5 OF), a stable two-phase region
was not observed. Some droplets, and elongated
bubbles appearedduring a volume/pressure change and
while the system was stabilizing, but upon reaching
equilibrium, the system was single phase at all
pressures.
At 37.5°C (99.5 oF) and 8253 kPa (1197 psia), the
critical point was observed. At all other temperatures
the contents of the cell were clear and colorless in the
vapor, liquid and two-phase regions. In the critical
region, a small change in pressure (3-5 psi) resulted in
the entire cell contents becoming a murky, grey cloud
and then stabilizing out into a variety of shades of
yellow. Above 8303 kPa (1205 psia) the contents were
single phase, clear and colorless. At about 8274 kPa
(1200 psia), the see-through single phase took on a
slightly yellow tint. At the critical point of 8253 kPa
(1197 psia), two phases appeared with an indistinct
thick yellow interface, a darker yellow color at d1e
bottom of the cell and a lighter yellow color on top. At
8212 kPa (1191 psia) the bottom half of the cell was a
distinct dark orange liquid and the top half a colorless
vapor. At 8198 kPa (1189 psia) the liquid phase faded
to yellow and below 7957 kPa (1154 psia) the cell
contents were again a colorless single phase.
In Figure 2, the calculated equation of state phase
envelope is plotted along with the experimental data.
The widths of the two phase envelopes are similar, but
the calculated envelope falls below and to the left of
the experimental data. The calculated critical point
occurs at 34.9 °C and 7633 kPa (94.8 of, 1107 psia),
2.6°C and 620 kPa below the experimentally
determined critical point of 37.5°C and 8253 kPa
(99.5°F, 1197 psia). The deviations between actual
and calculated phase behavior emphasize the
importance of obtaining an experimental data set for
acid gas mixtures. The equation of state was regressed
to fit d1ephasebehaviour data obtained experimentally.
The regressed curves and critical point match the
measured data within the experimental error. The
modified equation of state allows some extrapolation to
different conditions, but experimental verification will
be necessary until more data becomes available and a
general regression is completed.
The Sa11D'ated water content of the gas mixtW"Cat
2860 kPa and 24°C (415 psia and 75°F) over four
samples was measured to be 0.6 mole percent or 270 Ib
water/MMSCF. This value is over three times d1e
value that analysis of accepted pure component data
and equation of state calculations predict. The
difference is attributed to experimental error and
reflects on inaccuracies inherent in dte gravimetric
water content measurement.
Figure 3 summarizes dte phase behavior and
hydrate formation data obtained for dtis acid gas
mixture. The two-phase region can be avoided during
compression by cooling the gas to a minimum of
SPE49522 A.KM. JAMALUDOIN.D.B. BENNION.F.B. THOMAS.MA CLARK
37.5°C between compression stages. The fluid is in
the supercritical, dense phase above 8253 kPa and
above 37.5°C.
The hydrate formation temperature is below the
traditional hydrate temperature since the gas is not in
contact with a liquid water phase. With undersaturated
gas, hydrate fonnation is expected to coincide with dte
water saturation temperature. In this study, hydrates
were observed at temperatures above the expected
water saturation temperature of the gas. At 9000 kPa
(1305 psia) and 17700 kPa (2567 psia) predictions
basedon pure component water saturation data indicate
the gas will be saturated at approximately -9°C (15°F)
and -18°C (0 oF), while hydrates were observed at -2 °C
(28°F) and 8°C (46°F). The difference can be
attributed either to experimental error or the
inaccuracies inherent in predicting mixture saturation
temperatures from pure component data. In either case,
since the observed hydrates occurred at higher
temperatures than expected, a conservative design
would not require dehydration of the gas unless the
temperature in the pipeline or wellbore dropped below
the observed hydrate formation temperature.
Disposal of Acid Gas with Disposable
Fonnation Water
Sour water injection has advantages and disadvantages
in comparison to direct injection. The technique results
in better containment of the sour gas as it is dissolved
in the injected aqueous phase and, excepting diffusive
forces which act very slowly in porous media, the sour
wattt moves only as the injected phase spreads into the
reservoir. This also lessenssafety concerns with respect
to rate of release and volume of release in the event of
blowout of a sour disposal well. Compression costs are
reduced, as the effluent is pumped down the well as a
liquid phase using conventional equipment (with
appropriate corrosion inhibition). Disadvantages
include concerns about corrosion in the surface and
injection equipment, hydrate in the contacting
equipment, cost and safety of the surface contacting
equipment, and the fact that the phase behaviour of the
sour water must be precisely detem1medto ensure that
sour gas is not liberated from solution as temperature
increases as the fluid is heated by contact with the
fonnation. The water-contacting process also suffers
from the fact that it is not a perfect method for removal
of acid gases and preferentially tends to adsorb H2S
over CO2. A relatively large volume of water is also
required to dissolve an acid gas stream of any
appreciable volume. The technique can still be
advantageous in systems where a large volume of
produced water is available and must be disposed in
any event, and can be used as a technique to extract a
large fraction of the sour gas component from a rich
5
acid gas Sb'eam. This reduces the cost. volume and H2S
content of the remaining residual gas which
subsequentlywill be processedby more conventional
means.
Solubility of acid gasesin aqueoussolution is a
function of the following parameters:
. Acid gas composition
. Contacting pressure
. Contacting temperature
. Water salinity
Solubility increases with increasing H2S
concentration and increasing pressure (although
solubility generally levels out near the critical pressure
of the mixture (about 7000-10000 kPa). Solubility is
reduced by inaeasing temperature and increasing
salinity of the contacted water. Figure 4 provides an
illustration of the solubility of pure carbon dioxide in
fresh and salt water at various pressures at 100°C.
There are virtually no published data on the solubility
of mixtures of acid gases in water. Table 2 provides a
summary of some limited selected solubility data
available for different concentrations of acid gases at
varioustem perature and pressure contacting conditions.
Detailed experimental solubility studies should be
conducted prior to any acid gas injection study. This
will quantify the compatibility and expected solubility
of the target acid gas stream in the specific aqueous
phase present in the reservoir or contemplated for co-
injection.
Problems may be associated with solubility of
hydrogen sulphide into water. Water solutions
containing H2S are not stable and reaction with
adsorbed oxygen can cause the precipitation of
elemental sulphur\) and turbidity. This may result in
plugging of the injection zone by the suspended solid
precipitate. The turbidity can be reduced by filtration or
stabilized with various inhibitors (ie. glycol), but both
techniques may increase the cost of the injection
operation significantly thus reducing the economic
viability of d1esour water injection operation.
Solubilize Acid Gas into Light Hydrocarbon
Solvent and Inject the Solvent Containing Acid Gas
Component into tbe Depleted Reservoir as a
Miscible Flood Enhanced Oil Recovery (EOR)
Technique. Rich acid gases exhibit extreme solubility
in liquid hydrocarbons at elevated pressures (gas-oil
ratios of acid gases in hydrocarbons. particularly light
condensates.can be in excess of300 m3/m3).Solubility
of pure CO2 in 40° API gravity oil at 100°C is
provided in Figure 4. Many potential injection zones
contain a residual mobile or immobile liquid
hydrocarbon saturation. This would include depleted
oil reservoirs. transition zones containing an immobile
oil saturation. watertlooded zones at a residual oil
saturation, depleted gas reservoirs containing an initial
irreducible or sub-irreducible oil saturation, and
depleted retrograde condensategas zones containing a
trapped irreducible or sub-irreducible critical
condensate saturation. Two potential concerns arise
with respect to the contact of these hydrocarbon liquids
with the acid gas as follows:
Compatibility. Many oils may de-asphalt when
contacted with diatomic gases such as CO2 and H2S.
The precipitation of granular solid asphaltenescan lead
to plugging of the pore system and restricted injectivity
in the near wellbore region. If injection into a zone
containing liquid hydrocarbons is contemplated,
detailed compatibility testing should be conducted
between the live hydrocarbon liquid and the proposed
injection gas over the range of expected downhole
injection conditions to ensure that destabilization of
asphaltenes from the liquid hydrocarbon phasedoes not
occur.
Swelling. Due to the extremesolubility exhibited
by rich acid gases in most hydrocarbons a large
formation volume factor increase(expansion of the size
of the liquid hydrocarbon phase) occurs when the acid
gas contacts the insitu oil. If pressure is sufficient, the
acid gas may actually be miscible with the insitu crude
which will result in miscible displacement of the
residual oil saturation away from the wellbore area,
potentially creating an advantageousincrease in relative
permeability to the injected acid gas and an increase in
injectivity. In many situations, the composition of the
acid gas, liquid hydrocarbon gravity and downhole
temperature and pressure conditions are not conducive
to the establishment of miscibility. In this situation, a
portion of the injection gas is absorbed into the trapped
liquid hydrocarbon phase, causing a large increase in
formation volume factor of the oil. Figure 5 provides a
pressure-composition diagram for a typical insitu
retrograde condensate phasewith a molecular weight of
approximately 110 when contacted with a 50%
H2S/500/oCO2 acid gas stream at 10000 kPa and 60 °C.
It can be seen at the saturation point (ie. point where
the saturation pressure of the liquid is equivalent to the
injection pressure of 12000 kPa representing the
maximum degree of swelling expected to occur) that an
increase in condensate volume of over 27% occurs due
to solubility effects.
If the expanded oil saturation is already at the
irreducible level, the problem may not be significant.
When the oil saturation expands, it is basically akin to
increasing the oil saturation, and the portion of the
increased liquid hydrocarbon saturation in excessof the
irreducible value should be mobilized and displaced
deeper into the formation. Problems may occur if the
original oil saturation is relatively small and is at a
subirreducible level. This often occurs in depleted gas
condensate reservoirs or some gas reservoirs which
have been created by gas migration over geological
time into previously oil bearing strata. As the liquid
saturation increases in value, it still remains below the
irreducible value and hence is not mobilized, but
expands and occludes space previously available for
gas to be injected. The end result can be a significant
reduction in gasphaseinjectivity if the configuration of
the gas phase relative penneability curve is very steep
at low liquid saturation values. Figure 6 provides an
illustration of this phenomena.
This problem is very difficult to diagnose without
direct field or lab testing. Conventional gas-liquid
relative penneability curves can provide some insight,
but the parameters and configuration of nonnal gas-
liquid relative penneability curves are generally
significantly altered when considering an acid gas-oil
or acid gas-water system. Dissolution of the acid gas in
the liquid phase significantly reduces its viscosity (by
an order of magnitude or more for some hydrocarbon
liquid systems) and also can substantially reduce
interfacial tension between the gas and liquid phases.
Potential Side Benefits. Acid gas re-injection may
have potential side benefits in addition to the direct
disposal of unwanted sour gas. Some of these factors
have been alluded to previously, but will now be
discussed in greater detail. They include:
Potential stimulative nature caused by carbonate
dissolution. In the absence of adverse precipitation
effects and dissolution induced fmes mobilization and
plugging, long-term acid injection may actually
improve injectivity in some disposal wells due to low
pH induced dissolution effects.
Desiccation. In most direct acid injection projects,
the injected acid gas will have been dehydrated to
minimize hydrate problems at surface. Due to higher
downhole temperatures, hydrate formation willl&ely
not be problematic, but the dry nature of the injection
gas may result in a gradual desiccation of the trapped
irreducible or connate water saturation from the region
adjacent to the injection zone. This is analogous to a
phenomenon which often occurs during injection of
conventional dry gas into gas storage reservoirs. The
reduction in initial water saturation can cause an
increase in injectivity due to a lessening of adverse
relative permeability effects associated with the
presence of the initial water saturation in the porous
media. This effect may also be damaging if the insitu
water being desiccated is highly saturated with soluble
salts (for example, in a typical deep carbonate
formation). Desiccation of fluid by the injection gas
results in precipitation of these soluble salts within the
pore system which may have a counteracting effect on
the expected increase in penneability due to water
saturation removal, depending on the location of the re-
precipitation within the pore system.
limited Or Fun Miscibility with In-situ Oil Most
acid gas streams represent excellent miscible injection
solvents (from a phase behaviour point of view) and
very low or zero interfacial tension can be obtained
with these gases with many oils at relatively low
pressures. This makes these gases potential EOR
injectant candidates for the miscible displacement of
oils (which are generally in and of themselves already
sour). Due to the supercritical nature of the gas, actual
volume available for injection is usually too small to be
an effective consideration for voidage replacement for
an EOR process. Situations do exist. however, where
the rich acid gas, extracted from produced solution gas
from a large oil reservoir or directly from a sour gas
reservoir, could be used to miscibly inject into adjacent
smaller oil pools or isolated zones of the source oil
pool. Detailed lab and numerical studies would be
required in this situation to confinn miscibility with the
insitu crude, pressure required to maintain low
1FT/miscibility and potential compatibility concerns
with the gas-crude system and injectivity issues as
discussed previously. Contingency plans for premature
ultra-sour gasbreakthrough at a producing well are also
a necessity in this situation.
Summary
Acid gas or water injection has proven to be a viable
technology for the disposal of large volumes of waste
acid gas. For compressed acid gas injection, either as
a disposal or miscible solvent, the operating company
must avoid the two-phase region during compression.
Water condensation and hydrate formation in the post-
compression equipment must be prevented to ensure a
safe, cost-effective operation. Experimental data on the
water content, density, hydrate and phase behavior of
acid gas mixtures is therefore necessary. In the case of
the studied acid gas mixture of 9.90/0H2S, 89.5% CO2
and 0.6% CR., dehydration is not required unless the
temperature drops below 8 °C at 17700 kPa. The two-
phase region will be avoided during compression by
maintaining the gastemperature above 37.5 °C between
stages.
Acknowledgments
The authors would like to thank Union Pacific
Resources Company for permission to publish the
experimental data. The authors also express
appreciation to Vivian Whiting for her assistance in the
preparation of the manuscript and figures.
References
1. Wichert,E. andT. Royan,"Sulphur Disposalby
Acid Gas Injection," SPE 35585, Gas
Technology Conference, Calgary, Alberta,
Canada, May 1996.
2.
Keushnig,H., "HydrogenSulfide - If You Don't
Like It, Put It Back," Journal of Canadian
Petroleum Technology, 34(6), June 1995, 18-20.
3. Longworth,H.L., G.C. Dunn andM.Semchuck,
"UndergroundDisposalof Acid Gasin Alberta,
Canada: Regulatory Concerns and Case
Histories," SPE 35584, Gas Technology
Conference, Calgary, Alberta, Canada, May
1996.
4. Clark, M.A., W.Y. Svrcek, W.D. Monnery,
A.K.M. Jarnaluddin. D.B. Bennion, F.B.
Thomas, E. Wichert, A. E. Reed, and D.J.,
Johnson, "Designing and Optimized Injection
Strategy for Acid Gas Disposal widtout
Dehydration," paper presented at dte 11m
Annual Convention of dte Gas Processors
Association,Dallas,Texas,March 16-18,1998.
5. Duckworth, G.L., D. Kopperson,S. Home, G.
Kohn, D. Romansky, and C. ChaD,"Dispoal of
Acid Gases with Oilfield Produced Water,"
paperpresentedat the 7~ Annual Convention
of the Gas Processors Association, Dallas,
Texas,March 16-18,1998.
6. "Natural Gas Processors Association
Handbook," Gas Processing Suppliers
Organization,Tulsa, O.K., 1980.
"Merck Chemical Index, " Ill" Edition. Merck &
7.
Co. Inc., Rahway, N.J., USA, 1983.
8. Song,K. and R. Kobayashi,"Water Contentof
CO2in Equilibrium with Liquid Water and/or
Hydrates", SPE Formation Evaluation,
December1987,500-508.
9. Selleck,F.T., L.T. Cam1ichaeland B.H. Sage,
"PhaseBehaviorin the HydrogenSulfide-Water
System", Ind Eng. Chem., September,1952,
44(9),2219-2226.
8 ACID/SOURGASMANAGEMENTIN THE PETROLEUMINDUSTRY SPE 49522

10. Carroll, J.J. and A.E. Mather, "Phase

Equilibrium in die SystemWater-Hydrogen
Sulfide: ExperimentalDetenn ination of die LL V
Locus", Canadian Journal of Chemical
Engineering.,67, June,1989, 468-470.

Ng, H., D. Robinson and A. Leu, "Critical

Phenomenain a Mixture of Methane,Carbon
Dioxide and Hydrogen Sulfide", Fluid Phase
Equilibria, 19, 1985,273-286.

12. Huang. S.. A.D. Leu. H.J. Ng and D.B.

Robinson. " The Phase Behavior of two
mixtures of Methane. Carbon Dioxide.
Hydrogen Sulphide. and Water". Fluid Phase
Equilibria. 19. 1985. 21-32.

13. Mussumeci,A., "Computationin Gas Hydrate

Fonnation", SPE 21112, presentedat die SPE
Latin America Petroleum Engineering
Conference,Rio de Janeiro,Oct. 14-19,1990.

14. Dodds, W.S. et aI, "CO2 Solubility in Water",

Chern.Eng. Data Series1, 1956,p. 92.

IS. Munjal, P. and P.B. Stuwart, "Solubility of

Carbon Dioxide in Pure Water, SynfueticSea
Water and SynfueticSeaWaterConcentratesat
-5°C to 25°C and 10 to 45 ATM Pressure",
Journal of Chemical Engineering Data, 15,
1970,67.

16. Simon, R. and D. Graue, "Generalized

Correlationsfor PredictingSolubility, Swelling
and Viscosity Behavior of CO2-Crude Oil
Systems",Journal of Petrolewn Technology,
Ian 1965,p. 102.
 Table 2: 10% Nominal D,S With \ .68/0 C. and CO.. Experimental Data

Dry Gas Composition:9.90/0HzS,89.5%,COz,0.6% CH.

Wet Gas Com sition: 9.7% H 0
 Figure 1: Experimental Apparatus for Acid Gas Study

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