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MODELING AND SIMULATION OF

HYDROGEN SULFIDE REMOVAL FROM
PETROLEUM PRODUCTION LINES BY
CHEMICAL SCAVENGERS
a

Krishnaswamy Rajagopal , Rogrio Lacerda , Ivan Slobodcicov &

Eugenio Campagnolo

Laboratrio de Termodinmica e Cintica Aplicada (LATCA),

Escola de Qumica, Universidade Federal do Rio de Janeiro , Rio de
Janeiro, Brazil
b

Departamento de Engenharia Qumica e do Petrleo , Escola de

Engenharia, Universidade Federal Fluminense , Niteri, Brazil
c

Centro de Pesquisa e Desenvolvimento (CENPES), Tecnologia

de Recuperao e Anlises de Reservatrios e de Elevao e
Escoamento, PETROBRAS , Rio de Janeiro, Brazil
Published online: 12 May 2009.

To cite this article: Krishnaswamy Rajagopal , Rogrio Lacerda , Ivan Slobodcicov & Eugenio
Campagnolo (2009) MODELING AND SIMULATION OF HYDROGEN SULFIDE REMOVAL FROM PETROLEUM
PRODUCTION LINES BY CHEMICAL SCAVENGERS, Chemical Engineering Communications, 196:10,
1237-1248, DOI: 10.1080/00986440902832100
To link to this article: http://dx.doi.org/10.1080/00986440902832100

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Chem. Eng. Comm., 196:12371248, 2009

Copyright # Taylor & Francis Group, LLC
ISSN: 0098-6445 print=1563-5201 online
DOI: 10.1080/00986440902832100

Modeling and Simulation of Hydrogen Sulfide

Removal from Petroleum Production Lines
by Chemical Scavengers
KRISHNASWAMY RAJAGOPAL,1
ROGERIO LACERDA,2 IVAN SLOBODCICOV,3 AND
EUGENIO CAMPAGNOLO3

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Laborat
orio de Termodinamica e Cinetica Aplicada (LATCA), Escola de
Qumica, Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil
2
Departamento de Engenharia Qumica e do Petr
oleo, Escola de
Engenharia, Universidade Federal Fluminense, Niter
oi, Brazil
3
Centro de Pesquisa e Desenvolvimento (CENPES), Tecnologia de
Recuperacao e An
alises de Reservat
orios e de Elevacao e Escoamento,
PETROBRAS, Rio de Janeiro, Brazil
The in-line scavenging of hydrogen sulfide is the preferred method for minimizing the
corrosion and operational risks in offshore oil production. We model hydrogen sulfide removal from multiphase produced fluids prior to phase separation and processing by injection of triazine solution into their gas phase. Using a kinetic model and
multiphase simulator, the flow regimes, amounts, and composition of three phases
are determined along the horizontal and vertical flow path from subsea well to
separator tank. The flow regimes were found to be slug flow or intermittent flow.
The highly reactive triazine is destroyed on contact with water phase flowing near
the wall. We have simulated the hydrogen sulfide concentration profiles for different
amounts of gas injection. The results are compatible with the available field
data from an offshore oil well and are useful in determining the injection rates of
expensive chemical scavengers and optimal gas injection rates.
Keywords Hydrogen sulfide removal; Gas lift injection; Multiphase flow reactor;
Sour oil production; Triazine scavenger solution

Introduction
In several petroleum reservoirs, the concentration of hydrogen sulfide (H2S) has been
observed to increase unexpectedly in gaseous, oil, and aqueous phases of produced
fluids. This concentration is typically measured in parts per million by volume
(ppmv) in the gas phase relative to a partition from oil and an aqueous phase with
a pH equal to or less than 5 at standard temperature and pressure (STP), of 20
C and
1 atm absolute pressure. When the concentration of H2S exceeds 3 ppmv in the gas
Address correspondence to Krishnaswamy Rajagopal, Laborat
orio de Termodinamica e
Cinetica Aplicada (LATCA), Escola de Qumica, Universidade Federal do Rio de Janeiro, Av.
Horacio Macedo, 2030. Ed. do Centro de Tecnologia, Bloco E sala 209, C.P. 68502, Cidade
Universitaria, CEP 21949-900, Rio de Janeiro RJ, Brazil. E-mail: raja@eq.ufrj.br

1237

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1238

K. Rajagopal et al.

phase, the oil well is deemed to be sour, and precautions are necessary in design and
operation of production, transport, and storage equipment due to H2S toxicity, corrosion, plugging of reservoir formations, and increased sulfur content of produced
oil. Some oil fields in the North Sea and Campos Basin (Brazil) have turned sour
after a few years of injection of seawater for improved recovery of oil (Eden et al.,
1993). Many studies have attributed this souring to the activity of sulfate-reducing
bacteria and resultant production of biogenic H2S, except in a few cases of very high
pressure reservoirs where there is evidence for a geochemcial mechanism as well
(Farquhar, 1998). Many production facilities were unfortunately previously designed
and built without considering the effect of these organisms on their operation and
maintenance. From the experience of North Sea oil fields, we can expect about
10% of the oil wells to suffer from increased corrosion of tubing, casing, and production facilities, iron sulfide deposition, and injection and wellbore plugging, as well as
safety, health, and environmental concerns during the economic production life of
the field.
The souring of petroleum reservoirs caused mainly by sulfate-reducing bacteria
can increase the concentration of hydrogen sulfide in produced fluids to the point of
making it necessary to inject expensive chemical scavengers in production pipelines
so that the corrosion and operational risks can be minimized. In-line scavenging of
hydrogen sulfide is the preferred method for production of crude oil containing low
hydrogen sulfide levels from subsea wells, especially where the well is tied back via a
flowline to a host facility at which there is no provision for H2S scavenging and=or
where a H2S removal facility is too expensive and=or impractical to install (Nagl,
2001). As a result of this method, the hydrogen sulfide content of the crude oil that
is delivered to the platform is reduced to safe and commercially acceptable levels and
reaction by-product formation is manageable. The formation water provides a carrier phase for some of the reaction products and enhances the dispersion of some
insoluble reaction products in the coproduced aqueous phase.
We model this chemical process using available field data so that the cost of
removal of hydrogen sulfide (H2S) can be reduced by determining optimal gas injection rates as well as the rate of injection of chemical scavengers in production lines.
The proposed methodology is also useful in selecting alternative scavengers. In the
literature, models have been proposed for treating single-phase natural gas with
liquid scavengers (Fisher et al., 2003). There is little information about in situ
removal of hydrogen sulfide from multiphase streams.

Chemical System
The chemical system considered is a subsea flowline connecting a mature subsea oil
well to an offshore production facility, schematically shown in Figure 1. The reservoir fluids, namely, formation water, crude oil, and its associated gas, flow into
production lines at point 13. The oil phase is initially above the bubble point pressure, and the gas lift process is used to transport and lift the reservoir fluids from
the well to the production platform. The widely used liquid chemical scavenger
1,3,5-tris (2-hydroxyethyl)-1,3,5-triazinane (triazine) is atomized into the lift gas
pipeline and the mist is homogenized by flow. Then the lift gas with the scavenger
mist is continuously injected into the production line through a mandrel after
segment 8. The scavenger droplets disperse through the produced fluid substantially
homogeneously because of the natural turbulence of the fluid flow. As the pressure

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Modeling H2S Removal by Scavengers

1239

Figure 1. Flow path and flow regimes of the chemical system.

drops below the bubble point, a gas phase containing part of the H2S is formed. The
droplets of triazine injected into the gas phase decompose H2S by the nucleophilic
substitution of sulfur into the triazine ring, and the droplets encountering water
phase are rapidly hydrolyzed in a competing reaction. The reactions take place in
the multiphase flow along the flowline. The reaction products disperse in the liquid
phase. The lift gas is recovered from the oil at a separation stage and is reused.
The geometry of chemical system is shown in Table I.

Simulation of the Chemical System

The chemical system considered corresponds to an existing offshore oil well in the
Campos Basin of Brazil, which has turned sour after injection of seawater for several
years. Besides design data, the available field data are flow rates of reservoir fluids:
839 m3=day of oil, 1,300 m3=day of water, and 79,000 m3=day of free gas for a lift gas
injection rate of 171,552 m3=day. All flow rates cited in this work are in STP m3 per
day (at standard temperature and pressure of 293.15 K and 101325 Pa) per day. The
concentration of H2S in the separator reduced from 450 to 10 ppmv after injection of
2.4 STP m3=d of a commercial chemical scavenger, triazine. The system is modeled
using available data along with several physical properties measured for the purpose
of this study (Table IIA). The simulation is done in three steps: (1) multiphase simulation to determine the pressure, temperature, velocity of each phase, liquid holdup,
and flow rates of each phase, (2) estimating the phase distribution of hydrogen
sulfide from total amount or from gas phase concentration, and (3) estimating

1240

Subsea line

Subsea line

Well=column
Well=column
Well=column
Well=column
Lift gas injection
Well=column
Well=column

Well=column
Well=column

Well=column

9
10

11
12

13

5
6
7
8

Subsea line
Subsea line

Flow line

1
2

Segment
no.

194

50
53

18.4
482.6
544
250
N.A.
222.7
358

80

1200

790
150

Length [m]

4.88

3.94
4.88

3.95
4.88
4.88
4.88
4.88
4.88
4.88

4.00

6.00

6.00
6.00

Tube
diameter
[inch]

8.681

8.681
8.681

8.681
8.681
8.681
8.681
8.681
8.681
8.681

0
0

Lining
diameter
[inch]

11.5

31.6
27.3

90
90
69.6
59.2
58.8
58.8
54.2

2.3

2.3

90
2.3

Angle=
horizontal
[deg]

70.0

69.1
70.0

4.7
22.1
40.5
48.2
57.7
57.7
68.2

4.0

4.0

25.0
4.0

Ambient
temperature
[
C]

Orkiszewski (1967)
Beggs and Brill (1973);
Palmer (1975)
Beggs and Brill (1973);
Palmer (1975)

Duns and Ros (1963)

Beggs and Brill (1973);
Palmer (1975)
Beggs and Brill (1973);
Palmer (1975)
Beggs and Brill (1973);
Palmer (1975)
Orkiszewski (1967)
Orkiszewski (1967)
Orkiszewski (1967)
Orkiszewski (1967)
Orkiszewski (1967)
Orkiszewski (1967)
Orkiszewski (1967)

Correlation used

Liquid

Slug
Slug
Slug
Slug
Bubble
Bubble
Bubble=
liquid
Liquid
Liquid

Intermittent

Intermittent

Slug
Intermittent

Predicted flow
regime for
40600%
gas lift

Table I. Segments of flow path from offshore platform to subsea well, empirical correlations used for multiphase flow, predicted flow
regime in each segment for different injection rates of lift gas

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Modeling H2S Removal by Scavengers

1241

Table IIA. Measured properties of the fluids

Reservoir fluids

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Property
Density of
formation
gas
Density
of lift gas
Density of
produced
gas
Gas-oil ratio

Scavenger solution

Value

Surface
Temperature Viscosity Density Temperature tension




C
cP
g=cm3
C
mN=m

0.710
(air 1.0)

10

160.88

1.0319

0.640
(air 1.0)
0.660
(air 1.0)

20

86.23

1.0246

19.9

30.04

30

49.41

1.0172

30.4

29.12

40

30.03

1.0097

40.8

28.34

50

19.25

1.0021

50.0

27.9

60

12.93

0.9943

60.5

27.05

70

9.03

0.9864

80

6.51

0.9782

90

4.82

0.9698

86.0
(m3=m3)
0.935
(water 1.0)
218.70 (cP)

Density
of oil
Viscosity
of oil
at 30
C
Viscosity
69.36 (cP)
of oil
at 50
C
Wax appearance 20.0 (
C)
temperature
Density of
1.030
formation
(water 1.0)
water

scavenging reaction rates and gas phase concentration of hydrogen sulfide along the
flow path. The proposed methodology is described below for each of the steps.
Multiphase Flow Simulation
The flow in the production tubes was simulated using in-house software. The following three components of pressure drop along a flow path were considered: hydrostatic head, velocity head, and frictional loss. Frictional loss occurs both between
the fluid and the pipe and between the phases. The flow rates and properties of
the phases determine the physical arrangement of the fluid, and this arrangement
determines the pressure drop. The conceptual model was developed according to
the data available and the basic assumptions on multiphase fluid hydrodynamics
outlined above. All the main features of the production line were represented in
the simulator environment in order to perform the calculations. The simulation
model was applied to predict the flow regime and pressure drop along the production
line from the reservoir up to the platform.

1242

K. Rajagopal et al.

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For the purpose of simulation, the flowline from surface to reservoir was divided
into 13 segments based on the inclination and location, whether the line is located
under the seabed or not. Suitable empirical correlations were used to determine
the flow regime and pressure drop along the tubes. The pressure drop due to fittings
and valves was included by manufacturers specifications. Each segment was divided
in to sub-segments for calculating pressure drop and heat transfer more precisely.
Table I also shows the empirical multiphase correlation used and the predicted flow
regime in different segments for a range of injected lift gases. Figure 1 shows the evolution of the flow regimes along the line. Between the reservoir and the point of the
gas lift injection the flow regime goes from liquid phase to bubbling flow, and after
the gas lift injection up to the platform the flow regime is slug. The heavier water
phase flows generally as an annulus near the wall. The temperature, pressure, and
flow rates of oil, water, and gas phases were determined along the flow path by this
simulation for different gas lift rates, ranging from 40% to 600% of field flow rate.
Estimation of Phase Distribution of H2S
From the available literature data (Eden et al., 1993) we developed a correlation to
estimate the equilibrium constant of hydrogen sulfide between oil and water phases
(K oil=water) from temperature, pressure, and gas-oil ratio. The equilibrium Henrys
constant KH2S for the gas=oil phases and for gas=water phases was correlated with
temperature at low pressures. The correlation is shown in Figure 2. In this condition,
the equilibrium constants are independent of composition and pressure and the
distribution coefficient K oil=water is calculated at each temperature (Figure 3).
The salt concentration of the particular case under study was similar to that in the
literature data used. If the compositions of the phases are very different from the
literature case, it is advisable to determine the equilibrium constant by experiment.
The thermodynamic equilibrium of oil, water, and gas phases was calculated using
the Sour Peng-Robinson (Sour PR) model. This model combines the Peng-Robinson
equation of state and Wilsons API-Sour Model for handling sour water systems and
can be applied to sour water processes containing hydrocarbons, acid gases, and
H2O. The method uses Wilsons model to account for the ionization of the H2S,

Figure 2. Linear correlations for equilibrium constants of oil and formation water.

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Modeling H2S Removal by Scavengers

1243

CO2, and NH3 in the aqueous water phase. The fugacities of the vapor and liquid
hydrocarbon phases as well as the enthalpy for all three phases were calculated using
this equation of state. The K-values for the aqueous phase were calculated using
Wilsons API-Sour method (American Petroleum Institute, 1978).
The Pressure-Volume-Temperature (PVT) tests were done to determine the
reservoir fluid composition and physical properties like dissolved gas content and
residual oil density. The liberated gas and residual oil compositions were obtained
by gas chromatography. The H2S concentration was determined by spectroscopy.
The oil phase is considered as a semi-continuous mixture with components and
fractions based on normal boiling point. The fractions and the residue are considered
as pseudo-components. The binary interaction parameters are obtained by tuning
with PVT tests. Table IIB shows the reservoir fluid composition and physical properties obtained from the PVT analysis.
The pressure variation along the tube was calculated using the Peng-Robinson
equation of state, considering the composition of the fluids without hydrogen
sulfide.
Estimation of Reaction Rates
Buhaug (2002) reported the kinetics of triazine liquid reacting with gaseous hydrogen
sulfide and buffered water solution. In the scavenging reaction, the concentration
variation of triazine in contact with hydrogen sulfide gas was determined by isotopic
nuclear magnetic resonance (NMR) studies and the rate was determined to be first
order in hydrogen sulfide concentration:
dT=dt ka THHS

for pH > 10

with ka 9.1  107 Ka [mol 2 * s] where Ka is the acid constant of triazine in

solution. The author has also concluded that the reaction will be first order and fast
for pH < 10. The reported kinetic constants may, however, have large errors,
Table IIB. Reservoir fluid composition
Component
H 2S
Methane
CO2
Nitrogen
Ethane
Propane
i-Butane
n-Butane
i-Pentane
n-Pentane

Mole fraction

Pseudo-component

Mole fraction

70 ppm
0.449
0.000
0.003
0.031
0.018
0.005
0.025
0.004
0.005

C6 fraction
C7 fraction
C8 fraction
C9 fraction
C10 fraction
C11 fraction
C12 fraction
C13 fraction
C14 fraction
C15 fraction
C16 fraction
C17 fraction
C18 fraction
C19 residue

0.015
0.022
0.041
0.043
0.040
0.039
0.037
0.045
0.038
0.040
0.031
0.027
0.025
0.018

1244

K. Rajagopal et al.

especially if extrapolated to low pH values. The triazine is rapidly hydrolyzed on

contact with water with reported kinetics of

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dT=dt kH TH for pH < 10

with kH 1.42  106 s1 at 22
C and 3.40  108 s1 at 60
C. The hydrolysis will be
almost instantaneous for pH values of 5 or below.
We model the kinetics of hydrogen sulfide removal by triazine injection with the
following considerations. The triazine solution is atomized into gas stream in nearly
uniform droplets about 10 mm diameter. The smaller and larger droplets have small
survival times. A computational fluid dynamics (CFD) simulation of the flow supports this consideration. The highly reactive triazine in the droplets will be destroyed
almost instantly on contact with water phase flowing near the wall. The rate of
removal of hydrogen sulfide is limited by the rate of mass transfer of H2S from
the gas phase to scavenger solution droplets. The oil, water, and gas phases are in
thermodynamic equilibrium along the flow path.
The rate of removal of H2S is estimated using a model that combines mass transfer resistance and reaction. Fisher et al. (2003) have used this model for natural gas
treatment. The amount transferred is estimated using the rate equation:
dyH2 S KG aPyH2 S

dz
G

where yH2S is mole fraction of H2S in the gas phase; G is molar gas velocity, mol=m2s;
Z is tube length, m; KG is overall mass transfer coefficient, mol=m2 s bar; a is
interfacial area, m2=m3; and P is pressure, bar.
The pressure and molar gas velocity will vary along the path. We have estimated
the rate constant (KGa) using the field data of H2S concentration with and without
injection of scavenger solution for same rate of lift gas injection and flow rates in the

Figure 3. Equilibrium constant K oil=water for hydrogen sulfide at low pressures (unassociated hydrogen sulfide and formation water with pH 5).

Modeling H2S Removal by Scavengers

1245

offshore oil well under study. The H2S concentration at the entrance was obtained by
mass balance at steady-state operation of the well without injecting triazine. KGa
was determined from the measured operational concentration of H2S while injecting
a known rate of triazine solution with known lift gas rate.

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Results and Conclusions

The chemical system was simulated using the above methodology for different lift
gas injection rates with and without scavenger solution. For the case of normal
gas lift operation injecting 171,552 STP m3=day (100% gas lift) without scavenger
solution, the temperature and pressure profiles are shown in Figure 4. The flow rates
of different phases are shown in Figure 5. The flow regimes were found to be generally slug flow or intermittent flow. The amounts and concentration of hydrogen
sulfide are shown in Figures 6 and 7. The simulated value of 448 ppmv compares well
with the measured value of 450 ppmv in the separator.
The hydrogen sulfide concentration profile for the case of production without
lift gas and without scavenger solution is shown in Figure 8. The simulated concentration is 1635 ppmv. The production was shut down in the field when the concentration exceeded 1000 ppmv. Figure 8 also shows the hydrogen sulfide
concentration profile for the case of injection of 1 million STP m3=day (582.9%
gas lift). The simulated value is 108 ppmv in the separator compared to the expected
value of about 100 ppmv.
The normal gas lift operation (100% gas lift) with injection of 2.4 m3=day
of liquid triazine was simulated. The hydrogen sulfide concentration profile is shown
in Figure 8. The methodology effectively correlates the measured concentration of 10
ppmv at the separator. The rate constants were re-estimated considering that the rate

Figure 4. Pressure and temperature profile along the flow path (gas lift of 171,552 STP
m3=day without scavenger solution).

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1246

K. Rajagopal et al.

Figure 5. Flow rates of gas, oil, and water phases (gas lift of 171,552 STP m3=day without
scavenger solution).

constant proportionately varies with the square root of absolute temperature. The
effect on the profile was negligible.
In all cases studied, the proposed model and methodology of simulation were
found to be effective in simulating the chemical system. The simulation studies
indicate the need for better atomization so that the gas phase concentration of

Figure 6. Distribution of hydrogen sulfide among the three phases (gas lift of 171,552 STP
m3=day without scavenger solution).

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Modeling H2S Removal by Scavengers

1247

Figure 7. Concentration of hydrogen sulfide in the three phases (gas lift of 171,552 STP
m3=day without scavenger solution).

H2S can be reduced to acceptable levels immediately after the Christmas tree, as the
pipelines were of less noble material with little resistance to corrosion by H2S. The
proposed methodology can be readily used for evaluating any scavenger with known
kinetics. The accuracy of simulation can be improved by using measured distribution
coefficients of H2S between the oil, water, and gas phases.

Figure 8. Comparison of concentration of hydrogen sulfide in the gas phase with and without
injection of scavenger solution. Case 1, without injection of lift gas and scavenger solution, ~;
case 2, with injection of lift gas of 171,552 STP m3=day without scavenger solution, ; case 3,
with injection of lift gas of 1,000,000 STP m3=day without scavenger solution, ; case 4, with
injection of lift gas of 171,552 STP m3=day and 2.4 m3=day of triazine, .

1248

K. Rajagopal et al.

Acknowledgments
The authors acknowledge the financial support of CENPES-PETROBRAS and of
MCT=FINEP=CTPETRO=PETROBRAS under the project number: FBR 2528-06,
gua
leos Pesados, Gas Liberado e a A
entitled, Distribuicao do G
as Sulfdrico entre O
de Formacao nas Condicoes de Reservat
orio. The authors thank CNPq for the
scholarship Bolsa de produtividade to Krishnaswamy Rajagopal and FINEP=
CNPq for DTI scholarships to Ian Hovell and Luis Augusto Medeiros Rutledge for
making several experimental property measurements.

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Norwegian University of Science and Technology, Faculty of Natural Sciences and
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Duns, H. and Ros, N. C. J. (1963). Vertical flow of gas and liquid mixtures from boreholes,
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Orkiszewski, J. (1967). Predicting two-phase flow pressure drops in vertical pipes, J. Pet.
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