SPE 59765
Effect of Carbon Dioxide on Hydrogen Sulfide Scavenging
T. Salma, SPE, Baker Petrolite
Copyright 2000, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 2000 SPE/CERI Gas Technology Symposium
held in Calgary, Alberta Canada, 3–5 April 2000.
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Abstract
Effective removal of hydrogen sulfide (H2 S) is one of the
challenging problems associated with the production of natural
gas. Since H2 S is often present in natural gas along with
varying levels of carbon dioxide (CO2 ), selective removal of
H2 S from sour gas in the presence of CO2 is very important for
cost effectiveness of a scavenging operation. For over ten
years, triazine based scavengers have been successfully
applied in the sweetening of natural gas. However,
observations of the effect of CO2 on the scavenging capacity
of triazine based scavengers have not been very consistent.
Initial documentation and case histories on performance of
triazine based scavengers by Dillon [1,2] reported that CO2 did
not have any effect on the H2 S scavenging capacity of triazine.
However, recent studies by GRI [3] indicate that CO2
significantly reduces the H2 S removing capacity of triazine.
To address this discrepency, this paper critically evaluates the
effect of CO2 on the scavenging performance of a triazine
based H2 S scavenger. Results from controlled laboratory
experiments, using a wide range of CO2 partial pressure and
H2 S to CO2 ratios indicate that CO2 has very little effect on the
H2 S scavenging performance of a triazine based H2 S
scavenger. Field data supports the observations made in the
laboratory experiments.
Introduction
H2 S and CO2 are two contaminants that naturally exist in sub-
quality natural gas. Removal of H2 S from the gas is often
required because of safety, environmental or corrosion
considerations. However, these factors do not dictate the
removal of CO2 . Chemicals that react with H2 S, very often
also have an affinity for CO2 . The concentration of CO2
relative to H2 S in natural gas is often very large (percent levels
CO2 compared to a few parts per million (ppm) of H2 S), which
further makes removal of CO2 less attractive and more
uneconomical. The need for selective removal of H2 S
therefore emerged as a key criterion for cost effective
sweetening of natural gas.
Triazines form an important class of non-regenerable H2 S
scavengers. They are produced from the reaction between
formaldehyde and an alkanolamine comprising 1 to 6 carbon
atoms [1]. Various sour gas-sweetening processes have been
used for a number of years. Incentives for use of triazine based
scavengers include:
a) Selectivity towards H2 S
b) Cost effective removal of H2 S
c) Simplicity of operation
d) Adaptability to existing process equipment
e) Low toxicity and non-hazardous waste characteristics of
the spent scavenger generated by the hydrogen sulfide
reaction.
Factors Affecting H2 S Scavenging. A. Y. Al-borno [4]
provides a thorough review of the various factors affecting
hydrogen sulfide scavenging some of which are:
- production ratios between gas/water/condensate
- phase distribution
- operating temperature and pressure
- H2 S levels, actual and desired
- mixing efficiency
- contact time between the scavenger and the gas
- chemical interference (if any)
Early case histories of hexahydrotriazine reported high
selectivity for H2 S [2]. However, recent studies indicated that
CO2 can a exert significantly adverse effect on the scavenging
performance of triazine based H2 S scavengers [4]. The current
study was designed to critically evaluate the effects of CO2 on
H2 S scavenging by triazine based scavengers.
The H2 S scavenger selected for this paper was a
hexahydrotriazine, which is a reaction product of
formaldehyde and monoethanol amine. Controlled laboratory
experiments were conducted to study the effect of CO2 on the
scavenging capacity of triazine for H2 S. Performance data on
this triazine-based scavenger was also collected from various
fields with a wide range of CO2 concentrations to evaluate the
effect of CO2 on the scavenging capacity of the chemical for
H2 S. Results from laboratory studies as well as the field
2 T. SALMA
survey clearly indicate that H2 S scavenging capacity of the
triazine based scavenger is independent of the CO2
concentration and the ratio of CO2 to H2 S in the feed gas.
Experimental Procedure
Figure 1 shows the experimental setup used in this study to
determine the effect of CO2 on the scavenging capacity of
triazine. The contact tower, made from plexiglass was fitted
with a 70micron diffuser gasket to homogeneously disperse
the gas into the liquid scavenger solution. The contacting
section of the tower was 1.25” in diameter and 14” tall,
opening into a disengagement zone 3” diameter x 5” high to
separate the gas from the liquid. Methane (CH4 ), carbon
dioxide (CO2 ) and hydrogen sulfide (H2 S) were metered into
the line using three individual rotameters. The first step was to
establish the flow rates of individual gas components using 3-
way valves installed on each line. Once the flow rate of each
component was stabilized, the next step was to charge a 100ml
solution of known concentration of triazine into the bubble
tower. A mixture of H2 S, CO2 and methane at known
concentrations, 5 SCFH flow rate and 40 psia pressure was
sparged through the solution. Concentration of H2 S was
monitored in the outlet gas as a function of time. An H2 S
monitor (Model HS50) was used to determine the initial
breakthrough. Breakthrough time was defined as the time for
the outlet gas to reach 10ppm H2 S after passing through the
scavenging solution and was used as the main performance
criteria for effective scavenging.
Gas compositions were selected and blended in the laboratory
to include a wide range of CO2 , H2 S and CH4 ratios ranging
from 1000 ppm H2 S, 500 ppm CO2 and the balance CH4 to
20,000 ppm H2 S, 98% CO2 and no CH4 . Table 1, summarizes
the various compositions tested in the laboratory.
Results
Laboratory Studies. Table 2 provides a summary of the
breakthrough times observed for various concentrations of
CO2 , H2 S and CH4 .
Set 1. The H2 S concentration was maintained at 1000ppm
with a 5% triazine formulation charged to the tower for each
experiment. The ratio of CO2 :H2 S was 15:1 in composition 1
compared to 500:1 in composition 2. For a 5% triazine
formulation, comparison of breakthrough times for
composition 1 (t = 53 min) and composition 2 (t = 60 min)
demonstrate that there was no reduction in the H2 S scavenging
capacity at higher concentrations of CO2 . In fact, the
breakthrough time was slightly higher for higher CO2 levels in
composition 2. The slight positive effect at higher
concentration of CO2 was within the range of experimental
error.
Set 2. The H2 S concentration was maintained at 10,000ppm
with a 50% triazine formulation charged to the tower for each
experiment. The concentration of CO2 was varied from zero
to 99% CO2 in the gas mixture passing through a 50%
scavenger solution. Breakthrough times with no CO2 (t = 15.5
SPE 59765
± 0.5 min) were slightly shorter than those obtained with
higher concentrations of CO2 (t = 16.5 ± 0.5 min).
Set 3. The H2 S concentration was maintained at 20,000ppm
with a 50% triazine formulation charged to the tower for each
experiment. At 2% (20,000 ppm) H2 S, variation of CO2 from
10 to 98% yielded breakthrough times of t = 8.5 ± 0.5 min.
Results from sets 2 and 3 supported the observations in set 1
that increasing the concentration of CO2 and/or increasing the
CO2 partial pressure does not have any adverse effect on the
scavenging capacity of the triazine. These results also
confirmed that the selectivity for H2 S of the triazine
(hexhydrotriazine) formulation tested in this study is
independent of the partial pressure or concentration of CO2 in
the natural gas.
Field Evaluation. To verify the observations made in the
laboratory experiment, performance data was also collected
from various field locations using the same triazine scavenger
for removal of H2 S with different concentrations of CO2 in the
natural gas.
Table 3 summarizes the operating conditions encountered at
the different fields and the mode of application of the
scavenger. In general, the optimum capacity of the triazine
based scavenger (hexahydrotriazine) used in this study is
determined to be 2 lbs of H2 S removed per gallon of scavenger
in contact tower applications and ~ 1lb of H2 S removed per
gallon of scavenger in flow line injection. One of the primary
reasons for lower performance in flow line applications is
mass-transfer limitations and relatively poorer mixing
efficiencies than those available in contact tower applications.
Flow Line Applications. Inspection of field data shows that
for CO2 partial pressures (p CO2 ) varying from 0.8 psi (Kansas)
to 40.7 psi (Louisiana), scavenging performance of triazine
was within the expected range for flow line applications.
Furthermore, increasing the ratio of CO2 to H2 S did not
adversely affect the scavenging performance. For example, at
CO2 :H2 S of 2000:1 (Michigan 1), the scavenging performance
is 0.98 lb of H2 S removed per gallon of scavenger compared
to the scavenging performance of 0.94 lbs H2 S removed per
gallon of scavenger with a CO2 :H2 S of 1000:1 (Louisiana).
Contact Tower Applications. Field data on contact tower
applications further illustrated the independence of scavenging
performance relative to CO2 concentration in the feed gas. For
example, for zero ppm CO2 (W. Virginia 1, pCO2 = 0) in the
feed gas, ~ 1.85 lbs of H2 S were removed by 1gallon of the
scavenger compared to 1.63 lbs of H2 S removed per gallon for
a CO2 :H2 S ratio of 290:1 (W. Virginia 2, p CO2 = 19.5 psi) and
only 1.0 lb H2 S removed per gallon of scavenger for CO2 :H2 S
ratio of 25:1 (Michigan 2, p CO2 = 4.6 psi).
Evaluation of field data, in agreement with laboratory
observations, confirmed that the H2 S scavenging performance
and capacity of the triazine formulation used in this study was
independent of the carbon dioxide levels in the field gas.
SPE 59765 EFFECT OF CARBON DIOXIDE ON HYDROGEN SULFIDE SCAVENGING 3

Conclusions Hexahydrotriazine”, paper presented at the 1992 GRI 4th

1. Based on laboratory and field data, it is concluded that the
scavenging performance of the triazine formulation is
independent of the concentration and partial pressure of
carbon dioxide in the feed gas.
2. Increasing the ratio of CO2 to H2 S has no adverse effect
on the scavenging capacity of the triazine based
scavenger.
References
1. E. T. Dillon, “Composition and Method for Sweetening
Hydrocarbons”, United States Patent No. 4,987,512, (Dec
1990).
2. E. T. Dillon, “Gas Sweetening with a Novel and Selective
Sulfur Recovery Conference, Austin, Texas, October 4-6.
3. K. S. Fisher, S. J. Killion, J. E. Lundeen, “GRI Field
Testing of Direct-Injection H2 S Scavenging”, presented at
the 78th Annual GPA Convention, Nashville, Tennesse
March 1-3, 1999.
4. Al-borno, A. Y., R. Ryel, “ Solid Formation in H2 S
Scavenging and Recent Development”, paper presented at
the 1995 GRI 7th Sulfur Recovery Conference, Austin,
Texas, September 24-27.

Figure 1: Experimental Setup for Measurement of Breakthrough Times for Triazine Solutions

Pressure Gauge
@ 40 psia

3” ID Plexiglass
~ 5” Tall to serve as
Disengagement Zone

Gas Outlet

H2 S Monitor

1.25” ID Plexiglass
~ 14” Tall

Diffuser Gasket
70 microns

Gas In

CH4 CO2
H2 S
4 T. SALMA SPE 59765

Table 1

Molar Composition of Gas Mixtures Tested in the Laboratory

Composition Concentration of Pressure CO2 CH4 H2 S H2 S

No. Triazine Solution (psia) mole% mole% mole% (ppm)
(%)
SET 1
1 5 40 0.05 99.4 0.1 1000
2 5 40 50 49.9 0.1 1000
SET 2
3 50 40 0 99 1 10,000
4 50 40 10 89 1 10,000
5 50 40 20 79 1 10,000
6 50 40 50 49 1 10,000
7 50 40 99 - 1 10,000
SET 3
8 50 40 10 88 2 20,000
9 50 40 19 79 2 20,000
10 50 40 98 0 2 20,000

Table 2
Breakthrough Times For Different CO2 :H2 S and Partial Pressures of CO2

Composition CO2 Partial Pressure Ratio of CO2 :H2 S H2 S Breakthrough Time ± 0.25
No. (psia) (ppm) (min)
SET 1
1 0.02 15:1 1000 53
2 20 500:1 1000 60
SET 2
3 0 - 10,000 15.5
4 4 10:1 10,000 15.8
5 8 20:1 10,000 16.0
6 20 50:1 10,000 17.0
7 39 99:1 10,000 17.0
SET 3
8 4 5:1 20,000 8.5
9 8 10:1 20,000 9.0
10 39 49:1 20,000 8.5
SPE 59765 EFFECT OF CARBON DIOXIDE ON HYDROGEN SULFIDE SCAVENGING 5

Table 3
Field Locations – Operating Conditions

Location Flow Rate Operating Operating H2 Sin H2 Sout CO2

(MMSCFD) Pressure Temperature (ppm) (ppm) (ppm)
(Psia) (o F)
Flow Line Injection
Kansas 0.20 40 75 29 4.5 20,000
Michigan (1) 150 740 80 10 3 20,000
Louisiana 30 1135 120 35 2.0 35,000
Contact Tower Application
W. Virginia (1) 1.2 30 30 200 15 0
Michigan (2) 1.0 915 120 200 15 5,000
Alberta, Canada 12.7 595 82 21 6 5,000
W. Virginia (2) 3.1 150 70 450 0 130,000

Table 4
Scavenger Performance in the Field for Varying CO2 to H2 S Ratios

Location CO2 Partial Pressure CO2 :H2 S Pounds of H2 S Removed per

(psia) Ratio gal of scavenger
Flow Line Injection
Kansas 0.80 690:1 1.20
Michigan 1 14.8 2000:1 0.98
Louisiana 40.7 1000:1 0.94
Contact Tower Application
W. Virginia 1 0 0 1.85
Michigan 2 4.6 25:1 1.00
Alberta, Canada 3.0 238:1 1.30
W. Virginia 2 19.5 290:1 1.63