Selective Absorption of H2S From Sour Gas
R. w. Hohlfeld, SPE, Dow Chemical U.S.A.
Introduction
Hydrogen sulfide (H 2S) and carbon dioxide (C0 2)
are natural contaminants of gases from well casings,
combustion floods, geothermal steam, or process
streams. Because of safety, environmental or
corrosion considerations, it normally is desirable to
remove the H 2S from such gases. However, these
factors do not dictate the removal of CO 2, and it is
not desirable because of the cost involved. Safety
standards set by the U.S. Occupational Safety and
Health Admin. limit worker exposure to H 2S at 10
ppm for an 8-hour day. Environmental guidelines
require limited sulfur emissions, particularly of H2 S,
which has a characteristic "rotten egg" odor at levels
of 3 ppm. Corrosivity of wet H 2S gases is well known
because of its acidic character.
Many commercial methods exist to remove H 2S
from sour gas streams, though they all have their
limitations. Some processes may be limited by the
volume of gas they can handle or by the level of H 2S
or CO 2 in the gas stream. Others may prove to be
costly because of the capital investment or operating
expense. Still others are not suitable for the field
because of the complexity of operation, requiring
highly trained personnel.
In the H 2S removal system described in this paper,
these objections largely are overcome, as evidenced
by a number of production units based on this
0149·213618010006-7972$00.25
Copyright 1980 Society of Petroleum Engineers
Selective absorption of H 2 s from sour gas with caustic by gas/liquid scrubbing is a
new approach for oilfield operations to meet environmental and safety restrictions.
This technology demonstrates that by maintaining a very short contact time in a
gas/ liquid scrubber it is possible for caustic to react with and remove H 2 S from a
sour gas.
JUNE 1980
technology. Experience has shown that this system
(1) has a very low capital investment cost (2) has a
simple design based on gas/liquid scrubbing (3) has
straightforward installation and operation (4) will
remove H 2S efficiently, and (5) can treat gases
widely varied in composition and volume. These
units have proved effective in H 2S removal from
operations as widely divergent as pipeline-quality gas
plants to remote locations treating vent gases with
10070 H 2 S.
Theory
The principle of the technology presented here is
based on a patent issued to The Dow Chemical Co. 1
It states (and is reduced to practice in the method
discussed here) thatH 2S can be absorbed selectively
from sour gases also containing CO 2 by maintaining
a proper residence contact time between the gas and
an alkaline liquid. Normally, in a typical wet
scrubbing operation both acidic gases (H 2S and
CO 2) would be absorbed. However, the absorption
and reaction of H 2S in a strongly alkaline solution
(caustic soda) is virtually instantaneous while the
absorption of CO 2 is a much slower reaction. Thus,
if the gas is allowed to contact the liquid for a
controlled short time, the CO 2 absorption and
reaction with caustic will be insignificant. Because
H 2S does not have this limitation, it is absorbed
preferentially. Note these reactions:
.
1083
 SWEETENED GAS
i recycle stream complete the basic elements of this
SOUR GAS
---t>-
I CONTACTOR
L -_ _ _ _ _ _-'
SEPARATOR
i4_______ RE_CY_C_LE~______~L_~L~IQ~U~ID~EF~F=LU=EN~Tt>
CAUSTI C FEED
Fig. 1 - Scrubber schematic.
H 2S + 2NaOH'Na2S + 2H 20 ............... (1)
H2S+Na2S'2NaHS ...................... (2)
CO 2 +2NaOH'Na 2C0 3 +H 20 ............. (3)
Reaction 1 is an intermediate reaction that occurs
very rapidly and will be the dominant reaction when
solution pH is high (about 13), indicating excessive
caustic use. Reaction 2 is the dominant reaction at
lower pH (9 to 12). It indicates that the intermediate
product, Na2S, further reacts with H 2S to form
NaHS. This is most desirable, since it effects
maximum caustic utilization. Reaction 3 is least
preferred, as caustic is consumed needlessly in the
absorption of CO 2, It is minimized by maintaining a
very short gas/liquid contact. If CO 2 is absorbed,
the consumption of caustic could be prohibitively
expensive, because most sour gases contain much
higher levels of CO 2 than H 2S. In addition, the
resulting product Na2 C0 3 is relatively insoluble,
which could lead to plugging problems. With a
proper operation, CO 2 absorption in an H 2S/caustic
scrubbing unit should be from 1 to 5070.
Process Equipment
A schematic of the key elements for selectively
scrubbing H2 S from sour gas is given in Fig. 1. The
contactor normally is a suitably sized static mixer,
which is placed in-line with the gas stream. Caustic is
introduced immediately preceding the contact or ,
which empties directly into a gas/liquid separator.
Contact time is based on the residence time of the gas
in the contact or . The sweetened gas exhausts from
the separator, while liquid effluent is drawn off the
bottom of the separator equipped with a liquid-level
controller. Normally, the scrubber system is designed
with a recycle loop, which directs the bulk of the
spent liquor back into the feed line. The recycle
provides the system with flexibility to maintain an
optimum gas/liquid ratio to utilize more completely
any unreacted caustic and to generate a more con-
centrated effluent stream. However, if the unit is
intended to operate in a dilute mode (1 to 2070 solids
1084
concentration), the recycle loop would be eliminated.
Incorporation of pumps for the caustic feed and the
scrubbing system.
Desirable additional features normally included in
the scrubber design are pressure gauges, flow meters,
and sample ports with which to monitor operation.
In addition, a pH controller can be included to
regulate the caustic feed into the system, since H2 S
removal efficiency is a function of effluent pH.
Static mixers (mounted vertically or horizontally)
are recommended as contactors because of their
simplicity, effectiveness, low cost, and adaptability.
However, other contactors could be used if the
concept of short contact time is maintained. Ven-
turis, spray towers, and even small-diameter piping
could be adequate in some circumstances.
Contact Time
The key operating parameter for this technology is
the time during which the gas and liquid are in in-
timate contact. When the contact time is maintained
between 0.01 and 0.03 seconds, it has been deter-
mined that H 2S is absorbed selectively from gases
containing CO 2 , To maintain this contact time, a
static mixer must be sized suitably according to this
formula:
. void volume in contact or
contact tIme = - - - - - - - - - - - - - - - -
actual gas flow rate
In Fig. 2, static mixers are sized to maintain the
contact time of 0.01 to 0.03 seconds. Note that these
mixers are capable of treating gas flow rates ranging
from 10 to nearly 10,000 McflD (283 to 283 000
m 3 /d).
When contact time in the scrubber decreases below
the recommended minimum of 0.01 second, the
pressure drop in the scrubber becomes severe (Fig. 3).
Extremely short contact times further limit the ef-
fectiveness of H 2S removal.
On the other hand, when contact time exceeds the
maximum recommendation of 0.03 second, ab-
sorption of CO 2 is pronounced (Fig. 4). Absorption
of the CO 2 results in the formation of sodium
carbonate, which can lead to solubility problems.
However, the more obvious effect of CO 2 ab-
sorption is a dramatic increase in caustic soda
consumption (Fig. 5). Note that in this and sub-
sequent figures the term "relative caustic con-
sumption" is used. This term is a ratio of the moles
of caustic in the liquid feed to the moles of H 2S in
the gas feed.
pH Control
Observation of the pH of the liquid effluent provides
considerable insight into what occurs in the con-
tactor. Based on the equilibrium reactions (Fig. 6), it
is desirable to maintain a pH between 9 and 12 for
the effluent, which will consist primarily of sodium
bisulfide. If the pH of the liquid falls below 9, the
equilibrium shifts from sodium bisulfide to hydrogen
sulfide. This simply means that the alkaline liquid is
becoming too weak to absorb the acid gas. If the pH
JOURNAL OF PETROLEUM TECHNOLOGY
 2.5 (CM) 12.5

10 .01 - .03 SEC. 238

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DIAMETER OF CONTACTOR (INCHES) CONTACT TIME (SEC)

Fig. 2 - Gas capacity of contactor. Fig. 4 - C02 absorption.

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VARIED

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CONTACT TIME (SEC) RELATIVE CAUSTIC CONSUMPTION

Fig. 3 - Contactor pressure drop. Fig. 5 - Contact time effect on caustic consumption.

JUNE 1980 1085

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efficiency.

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Fig. 7 - pH range for scrubber operation. Fig. 9 - Caustic concentration influence on consumption.

1086 JOURNAL OF PETROLEUM TECHNOLOGY

is allowed to rise above 12, the equilibrium shifts
from sodium bisulfide to sodium sulfide. When this
occurs, twice as much caustic is consumed in forming
the sulfide. A high pH indicates that the caustic feed,
instead of reacting with the H 2S gas, merely is raising
the pH. This will occur if virtually all of the H 2S has
been absorbed or if the contact or is inefficient.
In practice, each scrubber design and operation
follows these pH principles, although the curve will
shift depending on the efficiency of operation (Fig.
7). Thus, it is possible to maintain a given scrubbing
efficiency by proper pH control. Normally, an ef-
fluent pH between 10 and 11 is recommended. When
pH must be maintained at a higher level it generally
indicates that (1) the scrubber is poorly designed, (2)
the contact time is too short, (3) a high caustic feed
concentration is being used, or (4) high H 2S removal
rate is being achieved.
H 2 S Removal Efficiency
Removal of H 2S from sour gas can be achieved from
gas streams of virtually any level of H 2S con-
centration. In practice, field scrubbing units
presently operate on gas streams with inlet H 2S
concentrations as low as 25 ppm to as high as 50070 by
volume. As one would expect, it is much easier to
remove a mole of H 2S from a gas containing 20,000
ppm of H 2S than it would be to remove that same
mole from a gas containing 200 ppm H 2S. It simply
is easier for a mole of caustic to find the H2 S when
the H 2S is more concentrated. Thus, note in Fig. 8
that more caustic per mole of H 2S is needed to scrub
gases with lower inlet H 2S concentrations. This
explains why on a percent removal basis it is easier to
scrub gas with high levels of H 2S and to do so using
nearly theoretical amounts of caustic.
With this technology under normal operation it is
typical to achieve H 2S removal efficiency on the
order of 90% H 2S removal per stage. However, if
greater H 2S removal is-desired, it is possible to do so
by feeding an excess amount of caustic or by adding a
second or even third stage in the scrubber design. In
either case, field scrubber efficiencies exceeding 99%
H 2S removal have been achieved.
If the CO 2 level in the sour gas is not too great
(abou t 1%) it may be advantageous to increase the
contact time to greater than 0.03 second so that more
of the H 2S can be removed. In this way, virtually all
the H 2S is reacted (to less than 4 ppm if inlet H 2S
generally is below 500 ppm) while sacrificing some
caustic for partial absorption of CO 2 .
Operation Parameters
In addition to the primary variables affecting caustic
consumption that already have been addressed, there
are operating variables that must be controlled for
optimum scrubber performance.
One of these operating variables is the con-
centration of the caustic feed and the corresponding
effluent concentration (Fig. 9). As the caustic
concentration increases, more caustic (as measured
by moles of caustic per mole of H 2S in the gas) is
needed to achieve equivalent scrubbing efficiency. In
JUNE 1980
o 1 3 4
60
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=
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40L-----L-____ ~ ____ ~ _____ L_ _ _ _ ~ __
5 10 15
L/G RATIO (GAL/McF)
Fig. 10 - Liquid/gas ratio for contactor.
practice, caustic concentrations up to 25% by weight
have been run satisfactorily, although concentrations
of about 10% by weight are run more commonly
because of potential solubility problems if sub-
stantial CO 2 would be absorbed.
Another important design parameter is the ratio of
liquid to gas in the contactor. Experience has shown
that a liquid/gas ratio of 5 to 15 gal/actual Mcf
(0.795 to 2.39 Llm 3 ) is the desirable operating range
(Fig. 10). If the ratio is too low, there is not sufficient
liquid to contact the gas. With a high ratio the
pressure drop across the contactor increases and
scrubbing efficiency drops off.
In most gas scrubbing operations the gas tem-
perature is not very high, as is typical of the data in
this report. However, for gases at higher tem-
perature, the reactivity of CO 2 increases so caustic
consumption will be greater. A rough correlation of
10% more caustic for an increase of 25°C is typical.
This consideration is significant for geothermal
operations.
Pressure of the gas stream appears to have little
effect on the scrubbing efficiency of this system.
Because of the compressibility of gas and because
contact time is based on actual gas flow rate, pressure
must be an important factor in contactor sizing. A
properly operating scrubber should experience a
pressure drop of about 2 psi (13.8 kPa). Field systems
have been installed up to 150 psig (1035Kpa), while
pilot test units have operated at pressures to 1,000
psig (6900 kPa).
The type of contactor chosen for the scrubber and
the configuration in which it is placed allow a great.
deal of flexibility in designing each system. The
standard design simply would be one static mixer
module installed horizontally. Other options are
available to suit specific requirements, including (1)
1087
 TABLE 1 - COMPARISON OF CAUSTIC SCRUBBER
UNIT EFFICIENCY
0.25-in.
Laboratory Unit
Gas flow rate, McflD
Mm 3 /d
Contact time, seconds
H2 S in gas, ppm
Maximum absorption, residual ppm H2 S
Pressure drop across contactor, psi
kPa
Liquid/~as ratio, gal/Mcf
(Um)
Caustic consumption, % excess
at 50% H 2 S absorbed
Effluent pH, at 50% H2 S absorbed
Caustic concentration, %
two contactors in series for more thorough con-
tacting and scrubbing efficiency, (2) two contactors
in parallel to improve the turndown rate of the
system for variable gas flow rates, (3) a contact or
with stacked elements that can be added to increase
scrubbing efficiency or removed to lessen the
pressure drop, and (4) a vertical contact or if design
considerations warrant.
Scale-Up
Data supporting the recommended operating
parameters in this work are an accumulation of data
gathered from a laboratory scrubber, a field pilot
unit, and production field operations_ Scale-up
through these units has resulted in excellent
correlation of data.
The laboratory scrubber utilizes either a static
mixer of 0.25- or 0.5-in.(6.35- or 12.7-mm) diameter
that has a capacity to treat up to 1.5 actual McflD
(35.7 m 3 /d). This unit is precision-controlled to
measure accurately all gas flow rates as well as liquid
flow rates. It is equipped with a recycle line with
variable speed pumps to control liquid flows. The
unit has been designed so it has maximum flexibility
in testing various contactors and configurations. The
unit allows duplication of field gas composition and
preliminary optimization of operating variables.
Temperature, pressure, pH, H 2S concentration, and
effluent composition can be monitored closely.
A portable field-scale pilot unit has been con-
structed and used for field demonstrations. This unit
utilizes I-in. (2.54-cm) diameter piping with a
corresponding I-in. (2.54-cm) diameter six-element
static mixer module capable of handling up to 80
McflD (I904 m 3 /d). It is modeled after the
laboratory-scale unit so that it permits maximum
flexibility. The unit can be disassembled and
reconstructed easily to tap directly into the gas
system proposed for treatment. In this way, a small-
scale field operation actually can be run to facilitate
any necessary design adjustments. Scale-up to larger
units is normally straightforward.
Oilfield Experience
An application of this process in a California oil field
1088
1-in. Pilot 4-in.
Field Unit Production Unit
0.9 56.7 940
(0.02) (1.35) (22.4)
0.015 0.01 0.03
10,000 13,000 8,000
600 400 20
1 4 2
(7) (28) (14)
2 3 5
(0.3) (0.5) (0.8)
30 44 45
9.7 11.0
10 4.3 6t025
was for the removal of H 2S from a well casing vent
gas. This gas contains approximately 10,000 ppm of
H 2S and about 65OJo CO 2 , flowing at a rate of 1,300
MscflD (30 940 std m 3 /d). Although environmental
restrictions called for an emission limitation of 2,000
ppm H 2S, it was desired to reduce the emission level
even further. In addition, a key design parameter was
to minimize pressure drop so that little backpressure
would be exerted on the producing wells.
Initial evaluation with this gas composition in the
laboratory scrubber indicated that the desired
scrubbing efficiency could be achieved easily (Table
1). The H 2S concentration was reduced to 600 ppm
with a pressure drop of only 1 psi (6.894 kPa).
With this initial data, the I-in. (2.54-cm) pilot field
unit was set adjacent to the gas plant, and a side
stream was drawn from the main pipeline. This unit
was designed to operate at a contact time of 0.01
second, achieving an H 2S reduction down to 400
ppm. However, the pressure drop across the static
mixer increased to 4 psi (27.6 kPa). It was decided to
design the production unit for a longer contact time
to minimize this pressure drop.
The production unit was constructed (Fig. 11) and
designed to embody only the basic elements of the
proposed scrubber technology. It consists of a single-
pass static mixer contactor with a constant feed rate
caustic pump and a gravity tank gas/liquid separator
equipped with liquid-level control. The unit has no
provision for recycle. The only controllable variable
in this system is the concentration of the caustic feed
which is a function of the H2 S removal rate:
Initially, this unit was equipped with a 3-in. (7.6-cm)
diameter static mixer; however, because of fluc-
tuations in the gas flow rate, it became apparent that
this would lead to a higher-than-desired pressure
drop of 4 psi (27.6 kPa). Thus, a 4-in. (I0.2-cm)
diameter static mixer was substituted into the line
and operated under the conditions of Table 1. It
meets the intended design requirements of low H 2S
emissions and minimal pressure drop. Furthermore,
its design simplicity results in a low maintenance
operation. This unit was constructed and made
operational in approximately 1 month. Reported
capital investment was less than $10,000.
JOURNAL OF PETROLEUM TECHNOLOGY
 WASTE GAS STACK
3~'

GAS
I
RECYCLE

200 BARREL
CAUSTI C
STAmr
MIXER 12' X 4'
SEPARATOR
STORAGE

II,9 r~
100 BID
PUMP GAS L1QU ID

~4-~--------~>I~ EFFLUENT;

100 BBL
SUMP

Fig. 11- Mobil Oil Corp. San Ardo H2S scrubber.

Economics H 2S/caustic scrubbing are unique among pollution-

Depending on system refinements, capital cost of the control devices. The simplicity of design, con-
H 2S/caustic scrubbing system has ranged from struction, and operation provide a system that can be
$10,000 to $30,000. The operating cost of these units constructed, put into operation quickly and be
is primarily the chemical expense of the caustic soda, maintained on-line with minimum attention. This
which itself is dependent on the amount of H 2S to be technology particularly is suited to oilfield ap-
removed from the sour gas. Assuming ideal plications where minimal service is available. It is a
scrubbing efficiency and a caustic price of $180/ton forgiving system that can maintain efficient H 2S
($198/Mg), the cost to remove H 2S from sour gas by removal even in the face of widely fluctuating gas
means of caustic scrubbing is about $O.lO/lbm flow rates or levels of H 2S. This unique application
($0.221kg) of H 2S removed. Other operational of acid-gas/alkaline-liquid scrubbing technology is
expenses. such as water, power for one or two pumps, fulfilling a need wherever H 2S emissions need to be
and mamtenance are small because of the basic controlled.
simplicity of the operation.
Acknowledgments
Effluent Disposal We acknowledge and appreciate the cooperation of
This H 2S/caustic scrubbing system produces a Mobil Oil Co. and especially Jim Sklar in compiling
nonregenerable waste, which is primarily sodium the case history for this paper.
bisulfide. The material must not be discharged in-
discriminately into wastewater systems or acidified as References
H2 Scan reevolve if the pH of the liquor is reduced.
Sodium bisulfide has commercial value and can be 1. Heitz, Robert G. and Rocklin, Albert L.: "Removal of Other
Acid Gases From Mixtures Containing Carbon Dioxide," U.S.
sold for various uses. In addition, it has utility as an Patent No. 2,747,962 (May 29, 1956).
oxygen scavenger for oilfield waters. Common
oilfield practice is to reinject this scrubber waste into SI Metric Conversion Factors
deep wastewater wells. It also is possible to oxidize bbl x 1.589 873 E - Ol
the waste to more stable sulfur salts. degree F ("F - 32)/1.8
ft x 3.048* E-Ol
Conclusions in. x 2.54* E+oo cm
The method of removing H 2S from sour gases that Ibm x 4.535 924 E-Ol kg
has been described here is instrumental in assisting U.S. ton X 9.071 847 E-01 Mg
the petroleum industry to meet safety and en- ·Conversion factor is exact.
JYf
vironmental guidelines. In several oilfield in-
stallations these units have demonstrated their value Original manuscript received in SOCiety of Petroleum Engineers office Feb.
over other more costly and sophisticated H 2S control 19, 1.979. Paper accepted for publication Dec. 18, 1979. Revised manuscript
received. March 25, 1980. Paper (SPE 7972) first presented at the SPE 1979
technologies. The low capital and operating costs of California Regional Meeting, held in Ventura, April 18-20.

JUNE 1980 1089