Equilibrium Phase Distribution of hydrogen sulfide in

produced gas, recombined oil and formation water

Krishnaswamy Rajagopal1∗, Luis Augusto Medeiros Rutledge1, Ian Hovell1,

Alexandre Jaime Mello Viera2, Eugenio André Campagnolo2
1
Universidade Federal do Rio de Janeiro, Escola de Química, Laboratório de Termodinâmica
e Cinética Aplicada (LATCA), C.P. 68502, Ilha do Fundão, 21949-900, Rio de Janeiro, Brazil.
2
PETROBRAS, Centro de Pesquisa e Desenvolvimento (CENPES), Ilha do Fundão, Q7,
21949-900 Rio de Janeiro, Brasil.

Keywords: distribution coefficient, phase equilibrium, recombined oil, acid gas, souring

Abstract
In several petroleum reservoirs, the concentration of hydrogen sulfide (H2S) in produced
fluids has been observed to increase unexpectedly, mainly due to the action of sulfur
reducing bacteria. Due to the high toxicity and corrosion of H2S, several precautions are
necessary in design and operation of production, transport and storage equipments when the
concentration of H2S exceeds three ppmv in the gas phase of produced fluids. Towards this
end we need to measure, correlate and model the equilibrium distribution of H2S in gas, oil
and aqueous phases at pressures and temperatures similar to reservoir and production
conditions. We report an experimental methodology developed for the measurement of 3-
phase distribution coefficients at high pressures, utilizing a Ruska, model 2370, mercury free
PVT equipment [1] and a positive displacement pump. A synthetic reservoir fluid was
prepared by recombining a characterized tank oil sample from Campos Basin with little or no
H2S with ultra pure methane at reservoir conditions. A known amount of H2S was dissolved in
a weighed sample of aqueous solution containing 3.7% of sodium chloride by weight. The
saline solution and a known amount of recombined oil were introduced into a high pressure
cell with a motor driven piston and a sapphire window (pump cell) at a pressure far above the
bubble point of the recombined oil. The sample was thoroughly agitated and then maintained
at the desired temperature and pressure for sufficient time for the different phases of the
mixture to reach equilibrium and to separate into three phases. Each phase was removed in
turn into another high-pressure cell with a floating piston using the sapphire window. The gas
phase was bubbled through an absorption system for trapping H2S and its volume was
measured at standard conditions using a calibrated gasometer. The oil phase and the
aqueous phase were then flashed independently to atmospheric pressure and the volume of
liberated gases was measured after trapping H2S using a gasometer. The hydrogen sulfide
was recovered as zinc sulfide in alkaline zinc acetate, EDTA stabilized solutions and the
sulfide content of the gas phase and of the gases liberated from oil and aqueous phases
were determined by the USEPA spectrophotometric method 376.2. The sulfide concentration
in the residual oil and water was determined by a modified USEPA method 4500-S D. From
these measurements equilibrium distribution coefficients of H2S in gas, oil and aqueous
phases Kgo, Kow, and Kgw were calculated. Experiments were carried out at several pressures
between 69 and 345 Bar at 40°C and 60°C. The coefficient Kow increases with pressure and
decreases slightly above bubble point. The behavior and the values are in qualitative
agreement with those predicted by Sour gas Peng-Robinson equation of state.

∗
Corresponding author. Tel + 55 21 2562 7654. E-mail: raja@eq.ufrj.br
1. Introduction
The souring of oil wells occurs in several reservoirs where the concentration of hydrogen
sulfide (H2S) increases unexpectedly with time and the produced fluids turn acidic exhibiting
a pH equal to or less than 5. This process may be occurring due to a number of factors, such
as, biodegradation due to the action of sulfur reducing bacteria or dissolution mechanisms of
sulfide minerals. It is particularly present in the offshore petroleum reservoirs where seawater
is injected into the well to improve reservoir fluid production and to maintain well pressure. [2]
When the concentration of H2S exceeds 3 ppmv, measured at 20ºC and 1 bar absolute
pressure, in the gas phase in contact with oil phase and with an aqueous phase, precautions
are necessary in design and operation of production, transport and storage equipments due
to H2S toxicity, corrosion, plugging of reservoir formations and increased sulfur content of
produced oil [3].
H2S is highly corrosive and its presence in oil reservoirs, pipelines, up stream operations,
and even well samples collected for PVT is undesirable. Pipelines, valves and equipment
have to be replaced with expensive H2S resistant materials increasing the operational cost
and expensive scavengers have to be employed to inhibit the liberation of this acid gas,
Therefore it is necessary to determine the concentrations of acid gases found in the wells
and its distribution within the various phases. The solubility of H2S is dependant on
temperature, pressure, composition and pH, making exhaustive experimental measurements
nearly impossible. Using minimum of amount of experimental data, we need to select and
tune a suitable equation of state to estimate the distribution of H2S under different flow
conditions.
To this effect we have developed an experimental methodology and measured the H2S
content across VLL equilibriums at a range of pressures either side of the bubble point
pressure, P(bubble) of a methane recombined oil for three temperatures. The data were
analyzed with the Sour Peng-Robinson equation of state [4].
2. Experimental Procedure
The procedure developed to obtain the distribution coefficient of hydrogen sulfide between
the gas, aqueous and oil phases can be described using various stages starting from the
preparation of the live oil to the collection of the data.
The first stage of this experimental process begins with the preparation of a sample of live
oil. To this end a known mass, 800g, of well characterized tank oil is placed into a
recombination cylinder of a known volume, 1400 cm3. The cylinder is closed and evacuated.
A known quantity of ultra pure methane gas is injected on top of the dead oil. The cylinder
was pressurized to 345 Bar isolated and agitated at 40 °C for 36 hours in order to solubilize
the methane gas producing a single-phase live oil. The pressure was monitored and kept at
345 Bar to compensate the pressure loss due to the solubility of the methane in the oil. After
three days the pressure had stabilized and the sample was deemed to be in a single phase.
15 cm3 of this live oil was transferred under isobaric conditions into the PVT cell for the
determination of the P(bubble), for this oil. The P(bubble) was determined experimentally,
using the method described by Rutledge, [5] by measuring the volume of the cell with
successive decreases in pressure. The pressure volume data produces a graph with an
inflexion point, P(bubble) value, showing a change in the behavior of the material in the cell
at the P(bubble) value. The point of inflexion may be found by solving simultaneously the
equations of the best line fits above and below the point at which the first gas bubble was
observed.
The next stage consisted of the preparation of the acidic aqueous phase. The recombination
cell was prepared with a minimum amount of mineral oil sufficient to record the pressure
within the cylinder. In this way the volume of the cylinder was at its maximum value of 1400
cm3. The cylinder was closed and evacuated and subsequently filled with a standard H2S
methane mixture, 10/90 w/w, at a rate of 0.3 L/min at a pressure of 3.5 Bar for 2 minutes.
Afterwards 150 cm3 of a sodium chloride solution, 3.7% m/v of NaCl, was injected and the
cylinder was pressurized to the pressure of the live oil. A known volume, measured by the
displacement of mineral oil, of live oil was transferred to the recombination cylinder
containing the acidic aqueous phase. The recombination cylinder was now agitated for 24
hours at the predetermined pressure and temperature after which the cylinder was placed in
the vertical position for 24 hours, with the sample side uppermost where the two phases
were allowed to separate. The sample was then transferred under isobaric and isothermal
conditions into the PVT cell and again the phases were allowed to separate for 18 hours. The
sub P(bubble) experiments had three phases, gas, oil and aqueous.
Each phase in turn was isolated from the equilibrium system using the float cell and viewing
window. The equilibrium conditions were maintained throughout the phase separation
process. The pressure of the isolated phase was first reduced to 20 Bar in order to safely
release the phase through the gas wash bottle system. and finally into the gasometer. In the
cylinder no measurable liquid drop out was noticed and the volume of washed gases was
measured by a gasometer. All the sulfur present is transferred to the wash bottle solutions.
The two liquid phases were released from the PVT pump cell and the gas phase, when
present, from the float cell. The gas caps produced from the two liquid phases on reducing
the pressure of the PVT cell to 20 Bar were released followed by the dead phase. These
dead phases were expelled by reducing the size of the PVT pump cell to its minimum and
collecting the phase into a dry and weighed glass trap. The gas wash bottle system was
connected to the exit side of the glass trap to recover any H2S in the system. Any remaining
H2S in the dead phase in the trap was now extracted using a N2 stream. The H2S was
recovered in the gas wash bottle system. Figure 1 shows the five streams found in a sub
P(bubble) equilibrium sample when all the three phases are separately flashed to ambient
conditions.

Figure 1 – The five streams separated from a Sub P(bubble) sample.

The hydrogen sulfide, was detected and quantified using the procedure described by
Rajagopal et al [6] reacting the H2S in the gas streams with the alkaline zinc acetate EDTA
solution producing a zinc sulfide precipitate held in suspension by the chelating agent, EDTA,
in the dreschel bottles. The dreschel bottle system was renewed for each separate liberation.
The contents of the dreschel bottles, after each liberation, were immediately analyzed for
H2S by spectrophotometry using a DR4000 Hach spectrophotometer, which is capable of
measuring concentrations of hydrogen sulfide in the range of 8 to 880 ppb. Throughout this
work the amount of zinc acetate employed in each wash bottle is recorded and from this and
the H2S concentration result it is possible to calculate the amount of H2S present in each
phase from which the equilibrium constant can be calculated and is defined as:
Mass fraction of H 2 S in phase A
K A/ B
=
Mass fraction of H 2 S in phase B
In order to achieve experiments that cover both two and three phase systems the equilibrium
system of gas, oil and water contaminated with H2S was modeled using a chemical process
simulator; Unisim Design R370.1 configured using the Sour Peng-Robinson property
Package, [7]. The program incorporates the better-known chemical process engine, Hysys.
The P(bubble) found experimentally measured at 40°C was used in the simulation of the
equilibriums at 40 and 60 °C and for a range of pressures between 68.9 to 275.8 Bar for
each temperature.
2.1. Apparatus
The present work uses a Ruska PVT, model 2370 equipment, fitted with two cells; one
mechanically driven, denominated as the PVT cell, and a second cell, called the float cell,
which is pressurized using mineral oil acting on a floating piston. A Ruska gas meter was
used to collect the insoluble gases liberated from the various gas oil water phases. The two
vertical cells are controlled independently of each other and the volumes and pressures of
each cell were monitored using a computer connected to the PVT. The mechanically driven
PVT cell was fitted with a glass window at the highest part of the cell. The various phases
were separated using this window. The two cells were fitted with electromagnetic stirrers that
permitted the agitation of pressurized fluids. The two interconnected cells are shown in
Figure 2.

Figure 2 - The inside view of the PVT showing the two cells
2.2. Materials
Ultrapure methane gas obtained from Linde gas, Barros Filho - Rio de Janeiro, was used to
produce the recombined oil. H2S / Methane 10/90% mol/mol standard mixture was obtained
from White Martins, Osasco, São Paulo. The reagents used in the analysis of the zinc sulfide
solutions were obtained from Hexis, Jundiaí, São Paulo. All the reagents used were
analytical grade and their solutions were prepared using twice distilled water. The 0.5% w/v
zinc acetate solution was prepared using hydrated zinc acetate crystals obtained from Vetec
Química Fina Ltda., Duque de Caxias, Rio de Janeiro/RJ, 0.5% w/v disodium
ethylenediaminetetraacetic acid, EDTA, obtained from Merck Kmbh, Darmstadt, Germany
and 0.8% w/v sodium hydroxide from Vetec Química Fina Ltda., Duque de Caxias, Rio de
Janeiro/RJ
3. Results and Conclusions
The experimentally determined bubble point for this recombined oil measured at 40°C was
194 Bar and 164 bar at 60°C and gas–oil ratio (GOR) of the recombined oil considering only
methane as gas is 87.2 m3std/m3std. These states are in the retrograde condensation region.
The results of the experimentally determined distribution coefficients together with the
modeled coefficients are shown in Table 1. It can be seen that the Kow experimental values
around bubble point pressures were considerably different from the respective modeled
values. Partly this may be due to an error in the concentration of H2S in the gas phase
because loss of gas as small amount of liquid drop-out during depressurization to
atmospheric pressure. The pressure is near the bubble point and the volume of liberated gas
is small and even minute quantity of liquid drop out will amplify the error in the concentration
of H2S as Kgo is different from 1. It can be seen that for both temperatures the modeled Kow
distribution coefficients are not greatly affected with increasing pressures the average values
being 2.62 and 2.12 respectively for 40 and 60 °C. The experimental values however
presented largest Kow distribution coefficients value at 206.8 and 137.9 Bar at 40 and 60 °C
respectively. Excluding the values near the bubble point, the average absolute deviation
between these sets of data is 8.3%. The model used may not be adequate for the retrograde
condensation region.
Table 1. Comparison between Experimental and Modeled Equilibrium Coefficients

GOR GOR Kgo Kgo Kow Kow Kgw Kgw

Oil Model*
Equilibrium
3
Pressure, (m std/ (m3std/
3
bar m std) m3std) Expt. Modeled Expt. Modeled Expt. Modeled

Equilibrium system at 40°C

68.9 88.16 92.5 0.40 0.48 2.36 2.54 0.94 1.21

137.9 88.18 92.5 0.15 0.34 2.94 2.66 0.43 0.89

206.8 88.20 92.5 5.05 2.69

275.8 88.18 92.5 2.31 2.63

344.7 88.18 92.5 2.50 2.57

Equilibrium system at 60°C

68.9 88.04 76.4 1.88 0.77 2.41 2.02 4.54 1.55

137.9 88.18 76.4 6.30 0.51 5.44 2.13 34.24 1.08

206.8 88.20 76.4 0.43 3.12 2.18 0.95

275.8 88.20 76.4 2.17 2.13

344.7 88.20 76.4 2.17 2.08

* adjusted GOR so that calculated bubble point pressure matches experimental value
4. Conclusions
The coefficient constants for H2S have been found experimentally and modeled using the
Sour Peng-Robinson state of equations for synthetic live oil - formation water equilibrium for
pressures above and below its bubble point pressures at two temperatures, 40 and 60°C.
The Kow coefficient produced the closest comparison with the experimental data, particularly
at the lower temperature, 40 °C with the exception of the values close to the system
P(bubble) value. Both experimental and modeled Kow data presented the same trend with
increasing pressure showing a larger value around the bubble point of the system.
Acknowledgements
We thank MCT/FINEP/CTPETRO/PETROBRAS for financial support under the contract
number 01.06.1036.00 entitled, “Distribuição do Gás Sulfídrico entre Óleos Pesados, Gás
Liberado e a Água de Formação nas Condições de Reservatório”. 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. We thank Mr. Jorge
Pereira dos Santos for assistance in experimental measurements.
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Petroleum Engineers, Bahrain, 2003.
[4] Peng, DY, and Robinson, DB (1976), Industrial and Engineering Chemistry:
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