See

discussions, stats, and author profiles for this publication at: http://www.researchgate.net/publication/269929666

H2S and CO2 generation mechanisms on a

steam injection project on Petrocedeo Field,
Orinoco Belt
CONFERENCE PAPER JANUARY 2011

CITATIONS

READS

105

Available from: Violaine Lamoureux-Var

Retrieved on: 25 September 2015

WHOC11-112

H2S and CO2 generation mechanisms on a steam injection project

on Petrocedeo Field, Orinoco Belt.
D, UZCATEGUI
PDVSA, Petrocedeo

V, LAMOUREUX-VAR
IFP Energies nouvelles

E, BERGER
PDVSA Petrocedeo, seconded by TOTAL

This paper has been selected for presentation and/or publication in the proceedings for the 2011 World Heavy Oil Congress [WHOC11].
The authors of this material have been cleared by all interested companies/employers/clients to authorize dmg events (Canada) Ltd., the
congress producer, to make this material available to the attendees of WHOC11 and other relevant industry personnel.

Abstract
Petrocedeo field is located in the Junin area of Orinoco
Belt, East of Venezuela. The Oil in Place (STOIIP) volumes on
this field exceeds 30 Gbbl. However, the nature of Petrocedeo
crude (Extra Heavy Oil, 8API) results in a limited recovery
factor. An Enhanced Oil Recovery (EOR) Pilot Project is
currently being implemented in order to quantify the additional
recovery that can be expected with continuous steam injection
techniques. Results will be used to design future applications in
the Orinoco Belt. This article will briefly present what the
Petrocedeo EOR project consists in.
One of the main expected issues associated to steam
injection is H2S and CO2 in situ production. Due to the
detrimental effects of these gases and the constraints they
impose on facilities design, it is of paramount importance for
the Petrocedeo EOR Project to understand their origin, in
order to be able to predict their concentrations in production
fluids.
This paper presents the results of the laboratory
experiments that were carried out to fulfill such purpose. A
geochemical characterization study was first carried out on
several oil sand cores. Oil composition variability and sulfur
content distribution in the oil sand were assessed, along with
total and labile sulfur content of the crude oil. The matrix
mineralogical composition was also determined in order to

investigate possible chemical interactions between oil and

minerals.
Finally, the results of several aquathermolysis experiments
performed at 250C on different oil sands are also presented,
along with the H2S and CO2 produced quantities for increasing
exposure time to steam.
Keywords: H2S and CO2, thermal oil recovery,
aquathermolysis, Orinoco Belt.

Introduction
PDVSA Petrocedeo is a joint venture between the 3 oil
companies PDVSA from Venezuela (with a 60% shareholding),
Total from France (30.3%) and Statoil from Norway (9.7%).
The main purpose of this association is to exploit and develop
an 8API extra-heavy oil reservoir located in JUNIN Block of
the Orinocos Oil Belt. The field operations began in 1999,
using a production scheme based on natural depletion also
called cold production.
Taking into consideration the type of reservoir, oil
characteristics and the initial production scheme, it has been
evaluated that the maximum ultimate recovery factor which can

be expected from the natural depletion phase would be around

8-10%.
In order to improve the recovery factor, Petrocedeo and its
shareholders launched in 2006 a project to enhance oil recovery.
After an extensive review of various technologies, EOR
mechanisms based on thermal processes were recommended
and approved by the shareholders. Petrocedeo EOR pilot
project encompasses a 30 Km2 area (Figure 1) with the
objective to evaluate recovery performances of 3 steam assisted
recovery techniques: Steam Drive (SD), Steam Assisted Gravity
Drainage (SAGD) and Horizontal Alternating Steam Drive
(HASD). First steam injection is expected to occur in 2013.
Steam and hot water assisted recovery from heavy oil
reservoirs can induce physicochemical interactions between
water, oil and rock. As a result, significant amounts of hydrogen
sulfide, together with carbon dioxide, may be generated,
increasing the risk of corrosion and health security problems
during production (Burger et al., 1985; Fassihi et al., 1990;
Thimm, 2001). For this reason, it is very important for the
Petrocedeo EOR project to understand their origin, in order to
be able to predict their concentration in produced fluids.
Depending on the nature of sulfur present in reservoirs,
three main types of reactions can potentially explain the
formation of H2S under hydrothermal conditions.
Thermochemical reduction of sulfates (TSR) is one possible
process. TSR corresponds to the thermally-activated reduction
of sulfates into free sulfur that rapidly reacts with hydrocarbons
to form, among other products, large amounts of hydrogen
sulfide (Hoffmann and Steinfatt, 1993; Worden and Smalley,
1996). Pyrite that commonly occurs in reservoir rocks is also a
potential source of H2S. In contact with hot water or steam, this
mineral can indeed be oxidized, generating sulfuric acid and
sulfate ions that can promote TSR (Hutcheon, 1996). Finally,
aquathermolysis of sulfur-rich heavy oils is a third process for
the generation of H2S in reservoirs. Aquathermolysis is defined
as chemical reactions between heavy oil and steam (Hyne et al.,
1984).
This paper presents the results of the laboratory experiments
that were carried out to fulfill such purpose. In the first time, a
geochemical and mineralogical characterization study was
carried out on several oil sand cores from the EOR pilot area.
Then, aquathermolysis experiments were carried out in IFPEn
laboratories to reproduce in situ contact between reservoir
rocksand steam.

well (the upper well) and forms what is known as a steam

chamber (a zone above the injector well with a high saturation
of steam). The oil will be heated by the steam, will flow easier,
and will be drained by gravity along the steam/oil interface back
to the producer well. For such a chamber to develop, relatively
thick (50 ft+) and permeable sands are needed. (Figure 2).
HASD (Horizontal Alternating Steam Drive)
The HASD (Horizontal Alternating Steam Drive) process
combines the advantages of steam injection processes like
Steam Drive, SAGD and cyclic steam stimulation.
The HASD configuration selected consists of 3 horizontal
parallel wells drilled at the lower part of the reservoir sands.
The central well is a permanent producer. The steam injection
starts in one flank well and the production in the others. After a
certain period the injection well is switched to a producer and
the other flank producer is converted to an injector (Figure 3).
The cycle time is a parameter that requires optimization for
each reservoir (preliminary simulations indicate periods of 3 to
6 months for Petrocedeo). The HASD process involves three
important aspects, (1) a high amount of steam being injected,
(2) the alternating characteristic of cyclic steam soak and (3) the
well known gravity drainage typical of SAGD. HASD is
expected to be efficient in thinner sandy layers (30ft+) than
SAGD, although it may target thick sands as well.
SD (Steam Drive)
Steam Drive, known as well as steam flooding, is a thermal
recovery process that comprises continuous steam injection into
the reservoir through vertical injection wells. The mechanism
involves 3 main concepts; (1) the steam will push the oil to the
producer well; (2) the steam injection will generate higher
pressure and temperature, the latter lowering the viscosity of the
heavy oil; and (3) the gravity effect will cause the steam to go
up and the oil to drain down to the horizontal producers
(Figure 4). Steam Drive may be envisaged in layers of less than
30ft, although applicable in sandy layers of 30ft+, but with a
lower recovery factor than HASD.
A southwestern area (around 30 km2) of the Petrocedeo
field was selected to implement the pilot, taking into account
the actual geological knowledge regarding sand thickness and
main sedimentological axes. This area was also known as
having a limited cold development plan, hence limited
interferences between the Pilot Project and the existing wells.
This zone was further delineated with 42 wells, drilled in 2
steps, in order to get a much more precise description of sand
channels organization in space (vertically and laterally), and to
optimize the final location of the EOR pilot. The first
delineation campaign consisted of 30 vertical wells, drilled
following a grid of more or less 1km, and with the most
complete
acquisition
program
(conventional
and
unconventional logging, coring (around 2000ft), production
tests, vsp, minifrac). The second step consisted of 12 deviated
wells drilled following a grid of 500m, and where full combo
LWD (GR, resistivities, neutron/density) was acquired.

Petrocedeo thermal EOR pilot

The PETROCEDEO field, located in the core of the
Venezuelan Orinoco Belt, hosts an Enhanced Oil Recovery
(EOR) pilot project whose main objective is to demonstrate the
possibility of increasing the recovery factor and extension of
production plateau by testing different types of EOR
techniques. After an extensive review of various technologies,
the 3 steam injection based techniques - SAGD (Steam Assisted
Gravity Drainage), HASD (Horizontal Alternating Steam Drive)
and SD (Steam Drive) - were selected. A brief description of
these techniques is given below.

Additionally, an intensive program of special laboratory studies

was launched (Thermal PVT, geomechanics, aquathermolysis,
and relative permeability). All of these studies were performed
under high temperature conditions. The aquathermolysis study
was required in order to assess the risk of H2S and CO2
generation upon steam injection and evaluate its effect on oil
and gas composition. Outside of the safety and environmental

SAGD (Steam Assisted Gravity Drainage)

SAGD is a continuous steam injection technology that
consists of two parallel horizontal wells, one injector and one
producer, drilled with a vertical offset of 5 to 10 meters. The
steam injected into the reservoir moves up from the injector

aspects, which are the most important, the results will also
provide key information regarding the rate of corrosion to be
expected for surface equipment. Five preserved core samples
(full diameter) from the EOR area were sent to IFP Energies
nouvelles (France) in order to perform this analysis.

Results and Discussion

The characterization of cores showed that the cores 2, 3 and 4
have homogeneous properties. On the contrary, there is
geochemical heterogeneity in the reservoir at a scale lower than
30cm as seen in the cores 1 and 5. The core 1 showed a gradient
of heavy oil content (from 15wt% to 19wt%, over 30cm),
accompanied by a gradient of porosity and a gradient of sulfur
content (from 4.0 to 4.8wt% in heavy oil, over 30 cm): at its top
the core 1 is more porous, contains more oil and the oil is richer
in sulfur. Consequently, it was decided to evaluate the effect of
this gradient on gas production. Hence the upper part and the
lower part of this core were selected to undergo
aquathermolysis experiments separately. The core 6 appeared to
be a green clay containing oil<1wt%. It was left apart from the
study. For this reason 5 cores were selected for the study: 2, 3, 4
and 1 (top and base).
Oil sand samples dedicated to aquathermolysis experiments
It was relevant to study geochemical properties of the
samples dedicated to the aquathermolysis experiments. Two
points were considered: the oil composition and the
mineralogical composition of the matrix.

Oil sand cores

6 cores issued from Petrocedeo Field, were
provided by Petrocedeo Company for this study (Table 1).
They were all cored during the delineation campaign in the
target reservoirs of the EOR project.

Experimental protocols
To ensure reproducible aquathermolysis experiments, one of
the required conditions was that the oil sand samples were
homogeneous. So the oil sand samples were mixed with a spoon
or a spatula to homogenize them.

Table 1: Origin and sedimentary environment of the cores (data

from Petrocedeo)

For each oil sand sample, the C14+ oil was extracted with nC5
and then with CH2Cl2, at reflux. The nC5 extracts were
fractionated into Saturates, Aromatics and Resins by liquid
chromatography MPLC. The asphaltenes were separated by nheptane precipitation. Hence the SARA (Saturates, Aromatics,
Resins, Asphaltenes) composition of C14+ oil was deduced.
For each SARA fraction, elemental oxygen and sulfur contents

Core well Reservoir type

fluvial

fluvial

fluvial

seal

The sulfur content in oil was quantified by analyzing oil

sands with the Rock-Eval designed for sulfur analysis. The
organic compounds were analyzed as well, with an FID and an
IR spectrometer.

Oil sands geochemistry

fluvial

Deltaic

Experimental protocols
In order to quantify the heavy oil content (C14+) in the oil
sands, the oil was extracted from rock with dichloromethane
CH2Cl2. Then the obtained C14+ oil was dissolved in a mix of
nC5 and CH2Cl2 and separated by liquid chromatography on
Florisil into 2 fractions: the NSO and the maltenes C14+, which
proportion was quantified. The maltenes C14+ are constituted
by the Saturates C14+, the Aromatics C14+ and the light
Resins. The mass of NSO was deduced.

A complete corrosion study was as well performed for

surface facilities. Corrosion allowance and / or suitable
materials were selected for process equipments and piping
where corrosion problems were detected. Moreover, connection
points for corrosion inhibitor injection and corrosion coupons
were added in the design. A comprehensive monitoring of fluids
H2S content will be as well performed with sampling points in
various parts of the surface facilities, and with a H2S liquid
analyzer located at the export point towards the main station. At
last, a stripper will bring the emulsion H2S concentration down
to the 12 ppm required for the export to the main station. The
gas produced by the EOR pilot will be used as fuel gas for the
boilers, along with natural gas coming from the main station.
The expected high concentration of H2S in burnt gas will result
in a significant amount of SO2 in exhaust gas, which will be
mitigated through adequate chimney height.

Prior to aquathermolysis experiment; it was very important

to measure some properties of the cores, to get an idea of the
variability of some relevant properties at the core scale (40cm to
90cm length). Aliquots were taken in different places on each
core. For each aliquot, the heavy oil content (C14+), the NSO
content (NSO = heavy organic molecules of oil containing
Nitrogen, Sulfur and Oxygen) and the sulfur content were
quantified. These properties were chosen because they are the
most relevant with regard to the issue of H2S production.

A possibly significant amount of H2S in the production

stream had to be taken into account for the EOR pilot surface
installations and wells design.
As for EOR wells design, corrosion studies evidenced a
significant risk of corrosion, mostly due to H2S and CO2
presence along with condensed water. After an exhaustive
evaluation of different steel grades for tubings, liners, casings
and wellheads, and balancing risks and costs, the use of carbon
steel L80 was recommended for tubings and casings, due to the
performance of this steel grade when it is exposed to a
constrained thermal expansion and its reliability in sour
environment. Blanket gas will be injected in the casing-tubing
annulus as another way of corrosion protection for the
production casing (single barrier). Same carbon steel concept
recommendation was given for wellheads and X-Mas trees
using EE class material for the equipment and parts in direct
contact with the production flow and using a surface double
mechanical barrier.

were measured by direct coulometry, whereas elemental

hydrogen and carbon contents were measured by direct thermal
conductivity.
The total and pyrolyzable sulfur contents in oil were
quantified by the Rock Eval designed for sulfur analysis. This
analysis enables discriminating labile sulfur from refractory
sulfur: (Pyrolyzable sulfur = sulfur released by oil sand during
Rock-Eval pyrolysis; Refractory sulfur = sulfur released by oil
sand after Rock-Eval pyrolysis, during Rock-Eval oxidation).

Finally, the sulfur contentin oil could be split into pyrolyzable

sulfur and residual refractory sulfur, as presented in the Table
4.

Table 4: Rock-Eval "pyrolyzable" sulfur and refractory sulfur

Sample

Sulfur

Pyrolyzable

Refractory Sulfur

(Wt % in oil)

Sulfur

(Wt % in oil)

(Wt % in oil)

The Matrix mineralogical composition was also evaluated

by X-Ray Difractometry (XRD), Fourier Transform Infrared
Spectrometry (FTIR), and direct elemental analysis by X-Ray
Fluorescence Spectrometry (XRF).
Results and Discussion
The geochemical study showed that the 5 oil sand samples
have close geochemical properties. They contain 14 to 16 wt%
of C14+ oil C14+, they have almost identical SARA
composition (Table 3), and the elementary composition of the
SARA fractions is very similar (Table 2).

%C

%H

%S

%O

%Total

1 Upper

83.6

10.6

4.3

1.3

99.7

1 lower

83.2

10.4

4.4

1.5

99.5

83.3

10.3

4.5

1.4

99.4

83.7

10.4

4.6

1.5

100.3

83.4

10.3

4.5

1.3

99.5

4.27

3.65

0.62

1 lower

4.46

3.95

0.51

4.41

3.81

0.60

4.52

4.00

0.52

4.42

3.90

0.52

The residual sulfur content in the heavy oil varies between

0.51wt% and 0.62wt%, whereas the pyrolyzable sulfur content
is much higher and varies on a wider range: between 3.65wt%
and 4.00wt%. It is interesting to note that the pyrolyzable sulfur
content increases with the total sulfur content (Figure 5).
This result suggests that only 11% of the total sulfur in the oil is
refractory to thermal treatment. This induces that the other 89%
of the total sulfur in the oil might be a source of H2S upon
steam treatment.
The characterization of the matrix by X-Ray Diffraction
investigation relieved that the 5 sand matrices contain quartz at
approximately 90wt% and potassium feldspar at less than
10wt%. They also contain few percents of kaolinite and
carbonates: calcite and possibly siderite and dolomite that can
act as a CO2 source. Infra-Red spectrometry investigation
allowed quantifying the relative carbonates content, showing
different values according to the sample (Table 5).

Table 2: Elementary composition of the C14+ oils, from direct

elemental analysis
Sample

1 Upper

The mass balance of the elementary composition reaches more

than 99%, indicating that the heavy oils were almost exclusively
composed by C, H, S and O, N and heavy metals (Ni, V)
representing less than 1wt%. Additionally, it can be noticed that
the sulfur content is very high.

Table 5: Carbonates relative content in the matrices, measured by

Infra Red Spectrometry
Sample

1 Upper

Normaliced
carbonates
content
1

1 lower

0.24

0.26

0.44

0.28

Table 3: SARA composition of the 5 heavy oil samples.

Sample Saturates Aromatics Resins Asphaltenes
C14+
C14+
nC7
1Upper

14%

25%

52%

8%

1 lower

14%

25%

52%

10%

13%

25%

52%

9%

13%

24%

55%

8%

13%

24%

52%

11%

The metallic elements in presence are aluminum (0.85 to 1.52

wt%), potassium (0.02 to 1.14 wt%), calcium (0.08 to 0.17wt%)
and iron (0.06 to 0.18wt%). They might catalyze the
aquathermolysis process.

It can be seen from Table 3 that the resins are the main fraction
of C14+ oil, which is a typical property of the heavy oils.
Moreover, the elementary composition of the SARA fractions
showed that the resins were the main carrier of sulfur in the oil:
they carry 65 to 69wt% of sulfur in the oil, whereas the
aromatics carry 20 to 24wt% and the asphaltenes carry only 10
to 13wt% of sulfur in the oil.

The matrices contain a very small amount of sulfured coke,

with a sulfur content of 1wt% of the matrix. As a contrary,
mineral sulfur was bellow the quantification limit (<0.1%). So it
was deduced that the matrices didn't contain any sulfate, pyrite
or sulfide. This was an important point, which indicates that
during steam treatment H2S originates from sulfur in bitumen
only and there cannot be any thermochemical sulfate reduction
(TSR), which is a major process for H2S production. It also
indicates that no pyrite played any role in H2S production.
4

steaming. However, such correlations suggest that carbonates

and especially calcite in the sand matrix, even in very small
quantities, induce significant CO2 generation under steam
treatment at 250C. Besides this mineral origin, an organic
origin of CO2 exists. As a matter of fact, CO2 generation was
observed from aquathermolysis experiments on the oil extract
only. Moreover, similar aquathermolysis experiments
performed at 300C on thiolane and thiophene showed CO2
generation as well (Clark et al., 1983).

H2S and CO2 production from

aquathermolysis laboratory experiments
The aquathermolysis study was conducted aiming at
assessing the capacity of the oil sands to generate gas, and
especially H2S and CO2, upon steam treatment. For that,
aquathermolysis experiments were designed to simulate in
laboratory the chemical reactions occurring in the reservoir
during steam injection.

H2S PRODUCTION
The experimental results showed that H2S production varies,
according to the sample, from 0.08 to 0.12 [g H2S]/[kg oil sand]
after 56 days of aquathermolysis (Figure 10).

Experimental Protocols
The aquathermolysis experiments consisted in heating few
grams of oil sand with added distilled and free-oxygen water
(1/1,(v/v)) in a closed gold tube, under inert gas and under
external isotropic pressure. The temperature was isothermal at
250C. The external pressure was maintained at 80 bar, which
allowed water to be in the liquid phase. The experiments were
carried out respectively for 14, 28 and 56 days.
At the end of each experiment, the total gas was recovered and
the produced CO2, H2S, H2, CH4, C2H6, C3H8, iC4H10 and
nC4H10 were quantified in absolute amounts. The gas produced
within each gold tube was recovered in a vacuum line equipped
with a Tpler pump. The amount of gas was quantified by
pressure measurement in a calibrated volume. Then the
molecular composition was determined by gas chromatography
analysis (GC), using a calibrated thermal conductivity detector
and a flame ionization detector. Knowing the total amount of
the bulk gas, the percentage of each individual gas species was
converted into absolute yield. Nitrogen and Oxygen where
removed at the end of the calculation as the former was in
excess in the experiments and the latter came from atmospheric
pollution during the analysis, though it was in negligible
quantity.

It was seen from the geochemical characterization that,

whatever the oil sand sample studied, they do not contain any
mineral sulfur. As a consequence, it can be asserted that H2S
generation is derived from sulfur occurring in oil. H2S
production could be correlated to the sulfur content of C14+ oils
(Figure 11), and even more clearly to the "Rock-Eval
pyrolyzable sulfur" content (Figure 12). It is important to note
that a difference of sulfur content in heavy oil by 0.1wt% only
induces an augmentation of H2S production by 0.04 [g H2S]/[kg
oil sand] after 56 days of aquathermolysis, which represents
approximately 30% to 200% of the total H2S production. This
shows that if we intend to foresee properly H2S production and
its concentration, then a precise quantification of sulfur in oil is
required (S absolute uncertainty <0.1wt%).
The elements Al, Fe and K, which were found in the matrices,
are known to promote catalysis oxidation, decarboxylation and
hydrogenation of organic compounds. In this respect, it is
possible that they played a catalytic role on gas production such
as H2S and CO2 during aquathermolysis.
SPATIAL VARIABILTIY OF GAS PRODUCTION
Another important point to note is that the maximum and
the minimum of gas production generated by the 5 different oil
sand samples are associated with two samples collected from
the same core and separated by only 20cm. The top of the core
produced approximately 50% more gas than the bottom. The
other samples from other wells produced intermediate quantities
of gas. This leads to underline that laboratory results should be
interpreted keeping in mind that the heterogeneity in the
reservoir can exist at a very small scale (20cm here) and may
have significant effects. Hence this confirms that a small scale
screening study is appropriate to estimate the spatial variability
of the steam treatment impact. For example, a simple screening
study could be directed only on sulfur and carbonates
quantification, since these characteristics seem to be key points
for gas production in these EOR and geological contexts.
Accordingly the Rock-Eval appears as a good tool for this
purpose, with a rapid time of analysis and with a level of
precision for sulfur and mineral carbon quantification which is
probably sufficient to screen the spatial relative risk of CO2 and
H2S production.

Results and Discussion

Whatever the oil sand sample, the experimental results
showed that the produced gas was composed mainly by CO2,
amounting 70 to 90mol%. The produced H2S was in significant
concentration, from 3 to 11mol%. H2 production reached 2 to
7mol%, and CH4 production reached 4 to 7 mol%. Hydrocarbon
gases, C2 to C4, reached around 1mol% each, indicating a slight
hydrocracking of the oil.
CO2 PRODUCTION
The experimental results showed that the gas production
continuously increased as aquathermolysis occurred. Although
having similar compositions, the 5 oil sand samples produced
significantly different quantities of gas upon aquathermolysis:
gas production varies from 1100 to 1800 [g gas]/[g oil sand]
after 56 days of aquathermolysis, according to the sample. This
variability comes mainly from the variability of CO2
production, varying from 900 to 1600 [g CO2]/[g oil sand]
according to the sample (Figure 6).
CO2 production could be correlated to the mineral carbon
content (Figure 7), to the relative carbonates content (Figure 8)
and to the calcium content (Figure 9) in the sand matrix. This
result is surprising, because the carbonates contents and calcium
contents are very small -around 0.1wt% of calcium in the
matrices- and, until now, carbonates were thought as a whole to
have a negligible role in CO2 production during oil sand

Discussion of results and way forward

These aquathermolysis experiments evidenced the heavy oil
as the main source for H2S generation, and possibly the matrix
as the main source for CO2 generation although some doubts
remain about the respective contribution of matrix carbonates
5

and heavy oil (all the experiments having been performed on

oily sands, and not yet on oil and sands separately). The
remaining issues are the effect of temperature on the H2S and
CO2 generation, the search for H2S and CO2 plateau, and to
confirm the origin of H2S and CO2 by performing experiments
on heavy oil and cleaned matrix alone separately. Moreover, the
scope of future experiments had to be adapted to account with
the experimental dispersion observed during this first phase. At
last, the need to integrate later on the experimental results in
thermal dynamic simulation models had to be accounted for, in
particular the need for preliminary kinetics for H2S and CO2
generation equations in these models.
Hence, it was decided to perform new aquathermolysis
experiments on at least three different samples of oily sands, at
different temperatures (250, 275 and if possible 300C), and
with three time steps (1, 2 and 3 months, this last one being the
maximum duration possible with current equipments). Two
experiments of one month duration, at 250C were added, in
order to investigate the behavior of matrix and heavy oil
separately.
Lately, it was decided to drop the 300C experiment, both
for budgetary constraints and because it was feared that new
reactions might take place when reaching such temperatures.

Acknowledgement
The authors want to express their gratitude to PDVSA
Petrocedeo and its shareholders TOTAL, and STATOIL, as
well as to IFP Energies nouvelles for allowing the publication
of this work. The authors also want to express their gratitude to
the laboratory staff that performed the experimental work.

REFERENCES
1.

BURGER J., SOURIEAU P., COMBARNOUS M.,

Thermal methods of oil recovery, Ed. Technip,
Paris, France pp 430, 1985.

2.

FASSIHI M.R., MEYERS K.O.,WELSBROD K.R.,

Thermal Alteration of Viscous Crude Oils, SPE
14225, 1990.

3.

THIMM H.F., Hydrogen sulfide measurements in

SAGD operations, Journal of Canadian Petroleum
Technology, Vol.40 N1, pp.51-53, 2001.

4.

HOFFMANN
G.G.,
STEINFATT
I.,
Thermochemical sulfate reduction at steam flooding
processes - a chemical approach. ,ACSPetroleum
ChemistryDivision, Vol. 38,N1, pp181-184,1993.

5.

WORDEN R. H. AND SMALLEY P.C.,H2S

producing reactions in deep carbonate gas reservoirs:
Khff Formation AbuDhabi, Chem.Geol., Vol.
133,pp. 157-171, 1996.

6.

HUTCHEON I., The potential role of pyrite

Conclusion
.

Steam injection for EOR can lead to H2S and CO2 generation, in
oil sand reservoirs at temperatures from 200C, resulting from
physicochemical transformations of sulfur compounds. Aiming
at deciphering H2S and CO2 generation mechanisms,
aquathermolysis laboratory experiments were carried out on
various oil sand samples issued from Petrocedeo field of the
Orinoco Belt in Venezuela.
The results showed a significant production of H2S and
CO2, along with the production of H2, CH4, C2, C3, C4.
CO2 might be generated by organic and/or mineral source.
The experimental results suggest that the matrix is a probable
source. However, CO2 generation from the crude oil is possible
as well. In order to verify this issue complementary work is in
progress.
Like CO2, H2S might be generated by organic and/or
mineral source. As the oil sand samples studied don't contain
any mineral sulfur, it was deduced that H2S is generated from
the sulfur in the crude oil. Consequently, the possibility of any
thermochemical sulfate reduction (TSR), which is a major
process for H2S production and induces high contents in H2S,
was excluded. It also indicates that pyrite cannot be involved in
the reaction and in the H2S fate. However, the catalytic effect of
the minerals found in the matrix might also contribute to the
generation of H2S.
Finally, H2S generation could be correlated to "pyrolyzable
sulfur content" in oil, suggesting that only a labile part of sulfur
in oil participates to H2S generation. Assuming that our
experiments are representative of the aquathermolysis occurring
in oil sands reservoirs during steam injection, the determination
of the labile sulfur distribution within a reservoir would provide
useful information for the evaluation of sour gas production risk
during steam-assisted recovery projects.

th

oxidation in corrosion and reservoir souring., 47

Annual
CIM
PETROLSOCTECH
MTG
(Calgary,Canada,6/10-12/96) Proc. Vol 2, paper
NCIM 96-95, 1996.
7.

HYNE J.B., GREIDANUS J.W., TYRER J.D.,

VERONA D., RIZEK C., CLARK P.D., CLARKE
R.A., KOO J.,"Aquathermolysis Of Heavy Oils.", 2nd
Int. Conf. The Future Of Heavy Crude And Tar Sands,
McGraw Hill, New York, Chapter 45, pp. 404-411,
1984.

8.

LAMOUREUX-VAR, V. and LORANT, F;

Experimental Evaluation of H2S Yields in Reservoir
Rocks submitted to steam Injection. 13th
European Symposium on Improved Oil Recovery,
EAGE, Budapest, Hungary, D08, 25-27 April 2005.

9.

LORANT F., ANTONAS R., ESPITALI J,

Characterization of sulfur in reservoir rocks by
th

Rock-Eval analysis, 13 European Symposium on

Improved Oil Recovery, EAGE, Budapest, Hungary,
25 -27, April 2005.
10. CLARK P.D., HYNE J. B., TYRER J. D.,
"Chemistry of organosulfur
compounds types
occurring in heavy oil sands - 1. High temperature
hydrolysis and thermolysis of tetrahydrothiophene in
relation to steam stimulation process", Fuel, Vol. 62,
pp. 959-962, 1983.

Figures

Figure 1: EOR area location in the Petrocedeo block

Step n
:
inject in left produce in right

Step
n+1:
inject in right produce in left

Step
n+2:
inject in left produce in right

Figure 2: SAGD (Steam Assisted Gravity Drainage): a concept

requiring about 50 ft thick sands. Heated oil drains towards the
lower producer by gravity along the steam/oil boundary (green
area).

Figure 3: HASD 3 (Horizontal Alternating Steam Drive), with

a permanent central producer, and two alternating
producers/injectors.

STEAM

HEAT LOSS ES

PROD
UC ER
ZO NE

STEA M ZONE

CO NDENSAT ED STEAM
STEAM+HO T W AT ERCOL
D
OIL
INJECT OR

GRAVITY
HOT
OIL

OIL +W ATER

PRODUCER

Figure 4: SD (Steam Drive): Steam will be injected through

vertical wells. In Petrocedeo EOR Pilot Project horizontal
wells will be used as producers.

Figure 5: Pyrolyzable sulfur content and residual refractory

sulfur content vs total sulfur content, for the five oil sand
samples

Figure 6: CO2 production upon aquathermolysis experiments at

250C and 80 bar of external pressure, vs duration.

Figure 7: CO2 production upon aquathermolysis at 250C vs

mineral carbon content.

Figure 8: CO2 production upon aquathermolysis at 250C vs

relative carbonates content

Figure 9: CO2 production upon aquathermolysis at 250C vs

Calcium content

10

Figure 10: H2S production upon aquathermolysis experiments

at 250C and 80 bar of external pressure, vs duration.

Figure 11: H2S production upon aquathermolysis experiments

at 250C, vs total sulfur content in oil measured by Rock-Eval
in original oil sands.

11

Figure 12: H2S production upon aquathermolysis experiments

at 250C, versus "pyrolyzable sulfur" content in oil measured
by Rock-Eval in original oil sands.

12