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Using Geochemistry to Address H2S Production

Risk due to Steam Injection in Oil Sands
ARTICLE JUNE 2013
DOI: 10.2118/165437-MS

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SPE 165437
Using Geochemistry to Address H2S Production Risk
due to Steam Injection in Oil Sands
Violaine Lamoureux-Var and Claire Barroux, IFPEN

Copyright 2013, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Heavy Oil Conference Canada held in Calgary, Alberta, Canada, 1113 June 2013.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Steam injection for enhanced oil recovery induces chemical reactions within the reservoir, called aquathermolysis, which can
lead to in-situ H2S generation and to H2S production at the wellhead. H2S production risk is particularly acute in oil sand
reservoirs because they contain sulfur-rich bitumens. To forecast H2S production risk in these conditions, a workflow based
on geochemical investigation and reservoir simulation has been developed. It relies on (1) a quick estimate, using a dedicated
technique, of sulfur content and thermal reactivity of a large number of reservoir samples to map the H2S production risk over
the field; (2) carrying out more time-consuming aquathermolysis experiments on oil sand samples selected from step 1, to
define a kinetic model for H2S generation based on atomic sulfur thermal reactivity; (3) transforming this sulfur-based kinetic
model into a molecular SARA components-based kinetic model, usable in a compositional and thermal reservoir simulator;
(4) simulating the EOR process with the reservoir simulator to calculate H2S/oil ratio at the wellhead.
The geochemical methodology has been applied to four oil sand samples from Athabasca. The results have underlined
that sulfur content and sulfur thermal reactivity of oil sands measured with the quick estimation technique are well correlated
with the amount of H2S produced from the more lengthy aquathermolysis experiments. Moreover, it was shown that the
sulfur in the oil sand, when distributed among Saturates, Aromatics, Resins, Asphaltenes, Solid matrix and H2S, as a function
of time and temperature of aquathermolysis, can be interpreted in terms of sulfur-based kinetic model. This model can be
used for a calculation of H2S generation upon aquathermolysis at field production temperature and time scale, thus for
estimating the H2S production potential.
As detailed in another SPE paper (Barroux et al., 2013), reservoir simulation has been used to simulate a SAGD process
in a generic 2D model of an Athabasca oil sand. One main finding of this study has been that the H2S/oil ratio at the wellhead
appears to depend mainly on the stoichiometry of the kinetic model.
Introduction
Enhanced oil recovery by steam injection in oil sands induces chemical reactions within the reservoir, called
aquathermolysis, which can lead to H2S production (Hyne et al., 1984; Thimm, 2001; Chakrabarty and Smith, 2012). To
quantitatively forecast this risk, the reservoir simulation is the most comprehensive tool but also the most complex to handle.
The reservoir simulation can only be predictive if it integrates smartly the reactional mechanisms yielding to H2S production,
which depend primarily on the temperature of steam, the duration of steam/rock contact and the amount and type of sulfur in
presence (Greidanus et al., 1977; Hyne et al., 1984; Chen et al., 1991; Lamoureux-Var and Lorant, 2005a; Song et al., 2005).
The quality of the prediction depends then on the synergy developed between the reservoir simulation and the geochemistry.
Laboratory aquathermolysis experiments allow the study of the chemical mechanisms and the quantification of the H2S
source terms as a function of the key-parameters, from which a kinetic model can be derived and implemented in a reservoir
simulator.
Since the 1980s numerous aquathermolysis experiments have been performed at relevant temperatures for steam injection
processes, evidencing modifications in oil composition and H2S generation. These include in particular the works published
by Hyne et al. (1984), Attar et al. (1984), Clark et al. (1990), Chen et al. (1991), Belgrave et al. (1994), Hoffman et al.
(1995), Hongfu et al. (2002), Uzcategui et al. (2011), Lamoureux-Var et al. (2011). But only a few contributions are leading
to kinetic models describing H2S generation. Attar and coworkers (1984) have proposed a relevant kinetic model for H2S
generation due to steam exposure, based on the quantitative transformation of the main groups of organo-sulfur compounds

SPE 165437

in oil. However, this model, based on a large number of organo-sulfur components, is tough to calibrate, and appears too
complex for being used in reservoir simulation.
Belgrave and coworkers (1997) have proposed a kinetic model for aquathermolysis, describing the oil composition and
the generation of different gases including H2S. It has been derived from aquathermolysis experiments at temperatures
between 360C and 420C that are much higher than the ones prevailing in steam injection conditions. In these high
temperature conditions, chemical phenomena, other than those involved in the aquathermolysis reactions, are expected to
occur. This comprehensive model, based on the hydrothermal cracking of oil, describes the oil as the composition of three
fractions: "Asphaltenes", "heavy oil", comprising heavy Saturates+Aromatics+Resins, and "light oil" comprising light
Saturates+Aromatics+Resins. The Asphaltenes are assumed to be the only organic source of H2S. But, from observations
made by Chen and coworkers (1991) and from our own results presented here, it appears that H2S comes also significantly, maybe predominantly -, from the Resins. Resins are hosting the major part of sulfur of heavy oils and bitumen and are the
most labile oil components with the Asphaltenes.
Thimm (2008) has proposed a simple model for a first estimation of H2S production using a pseudo-zero order kinetic
reaction calibrated on production data. This model appears to fit the majority of the Athabasca SAGD projects, but does not
relate the H2S production to the oil composition. Then this approach suffers from a lack of intrinsic predictive value given
that steam processes on different fields of Alberta can produce very different quantities of H2S because of noticeable
differences in bitumen sulfur content or reactivity (Clark et al., 1990, Lamoureux-Var and Lorant, 2005a).
Lamoureux-Var and Lorant (2005b, 2007) have proposed a kinetic model for H2S generation, based on atomic sulfur
distribution among the oil SARA fractions, the solid matrix and H2S. From the model calibration step, H2S has been assumed
to come from two sulfur classes in the Resins, and two sulfur classes in the Asphaltenes, each class having a different H2S
generation potential. This 4-reaction sulfur-based kinetic model does not handle oil molecular-type components.
Consequently, for using the information delivered by this model in a compositional and thermal reservoir simulation, Barroux
and coworkers (2013) have proposed a method for traducing this experimentally derived atomic sulfur-based kinetic model
into a component-based kinetic model, which integrates the parameters of the atomic sulfur-based model. The used pseudocomponents represent the oil SARA fractions. This component-based model has been used to simulate a SAGD process using
industrial reservoir simulation software (Barroux et al., 2013).
Three other teams (Ibatullin et al., 2011, Perez-Perez et al., 2011, Kapadia et al., 2010 through 2012) have recently
published works on reservoir simulation integrating a kinetic model of H2S production, these contributions being reviewed in
Barroux and coworkers (2013).
In this paper we present the kinetic model proposed by Lamoureux-Var and Lorant (2005b, 2007), with newly published
related experimental data, and some results of reservoir simulation that have been obtained using it. We present also a new
method allowing for reducing the number of the lengthy aquathermolysis experiments needed to build the sulphur-based
kinetic model. This method is based on a technology allowing for fast characterization of sulfur hosted by sedimentary rocks
and oils (Espitali et al., 2008, 2010; Lamoureux-Var et al., 2008; Uzcategui et al., 2011). This technique, if applied
intensively on the whole field area, could allow for delimitating at low cost the areas of high H2S production risk. This new
method is presented in this paper and accompanied with results.

Geochemical investigation
Materials.
Four oil sands were studied, issued from four Canadian oil sand production projects (Table 1): Foster Creek, Christina Lake,
Surmont (Lower Manville Group, Athabasca Formation) and Orion-Hilda Lake (Upper Manville Group, Lloydminster
Formation). The samples were obtained from the Oil Sands Sample Bank of Alberta. On receipt in our laboratories, they were
mixed for homogenization and then stored in a glass bottle at 5C. Water, used for the aquathermolysis experiments, was
distilled, de-ionized and deoxygenized by nitrogen bubbling. N-pentane and dichloromethane solvents, used for oil
extraction, were obtained from Rathburn and were used as received. Standard gases, used for gas chromatography analysis,
were obtained from Air Liquide and were used as received.

Field
Fisher field
Leismer field
Resdeln field
Ethel Lake field

TABLE 1 - OIL SAND SAMPLES SELECTED FOR THIS STUDY

Project
Well name
Formation
Foster Creek
AEC Fischer 12-22-70-4
Athabasca
Christina Lake
PCP PCR Leismer 6-16-76-6
Athabasca
Surmont
Gulf Resdeln 5-24-83-7
Athabasca
Orion Hilda Lake
Norcen YBR Cold Lake OV 12-17-64-3
Lloydminster

Core number
002: 446-455m
002: 365-374m
007: 346-362m
001: 438-446m

SPE SPE 165437

Fast method for sulfur characterization of oil sands.

The sulfur content and the sulfur thermal reactivity of the four initial oil sand samples were quantified. The four initial oil
sands were extracted with dichloromethane, giving four bitumen samples and four solid samples, insoluble in the
dichloromethane. XRD and Rock-Eval 6 screening indicated that the solids were mainly composed by sand but also by some
clay minerals and traces of organic compounds. Sulfur content of the solid samples was analyzed by direct elemental analysis
using coulometry detection. Sulfur content and sulfur thermal reactivity of the initial bitumens were analyzed with a RockEval-based technology, dedicated to the characterization of organic matter of sedimentary rocks (Lafargue et al., 1998),
which was extended to sulfur analysis (Espitali et al., 2008 and 2010). Sulfur characterization is relying on two successive
stages: an open pyrolysis under nitrogen flow of a small aliquot of bitumen (~5mg) followed by an open oxidation under air
flow of the residual bitumen after pyrolysis. During this thermal treatment using specific temperature programs, the sulfur
contained in the bitumens is progressively released by cracking and converted into SO2, which is monitored continuously.
The amount of sulfur released at each stage is deduced, from a calibration with a sulfured reference sample, two sulfur
contents being calculated: the pyrolyzable sulfur content, for the pyrolysis stage, and the residual sulfur content, for the
oxidation stage. The total sulfur content of the sample is the sum of pyrolyzable sulfur content and residual sulfur content.
The pyrolizable sulfur being assumed to be more labile to thermal treatment than the residual sulfur, this sulfur content split
can be used as an indicator of two levels of thermal reactivity of sulfur.
This new technology has been improved from the one proposed by Lorant and coworkers (2005) since the pyrolyzable
sulfur content is now measured directly (instead of being deduced from the residual sulfur content and the total sulfur content
measurements as in the original methodology). Consequently, data of pyrolyzable sulfur content presented hereafter can be
considered as more accurate than the ones previously published by Lamoureux-Var and Lorant (2005a).
Aquathermolysis experiments for quantifying H2S generation.
Experiments.
The four oil sands were submitted to aquathermolysis experiments, at different times and temperatures. An aquathermolysis
experiment consists in heating an oil sand aliquot, together with pure water and nitrogen, in a closed and static gold tube,
under fixed and constant temperature and pressure. The oil sand aliquot and water were precisely weighed (accuracy 0.5
mg) and settled in the gold tube in a glove box under nitrogen atmosphere (%O2<50 ppm; P~1 bar). The mass of the oil sand
aliquot was between 0.5g and 5g according to the heating conditions; the mass of added water was determined to get a
water/oil volume ratio close to 1. Once filled with the reactants, the gold tube was sealed in the glove box by ultrasound
welding to prevent any oxygen pollution and any vaporization of the reactants. So the composition and the mass of the
reactants were precisely controlled ( 1 mg). Each gold tube was then placed in an autoclave equipped with a thermocouple
set in contact with the tube, a gas line with a pressure gauge allowing for applying a fixed isotropic pressure around the gold
tube. As gold is a ductile material, and as the walls of the tube are thin enough, the pressure outside the gold tube is almost
entirely transmitted to the reactants inside. For each of the four oil sands, several experiments were carried out under 100bar,
at different temperatures in the range from 240C to 320C, during 203 hours. For the oil sand from Foster Creek, additional
experiments were performed during 24 hours in the same range of temperatures.
Gas analysis.
At the end of each run, the gold tube is rapidly cooled down to room temperature and then depressurized down to 10-5 bar at
about 70C on a vacuum line. Then it is pierced and the whole gas is recovered using cryogenic traps at approximately
-180C. Due to these pressure and temperature conditions, dissolved gas in oil and water, and adsorbed gas on solids are
expected to be respectiveley exsolved and desorbed, then recovered and quantified together with the free gas. At this stage,
the C5-C13 oil cut and water are lost in the vacuum line. The gas pressure is measured in a calibrated volume and its molar
amount is deduced using the ideal gas law, the conditions of ideality being practically met. The gas sample is then stored in
an ampule and transferred onto a gas chromatograph to analyze its molecular composition. By combining all experimental
data, the absolute yield of H2S, H2, CH4, CO2, C2H6, C3H8, iC4H10 and nC4H10 per gramm of initial oil sand is estimated rather
accurately, even the available quantities are small.
Bitumen analysis.
After gas analysis, the gold tube is removed from the vacuum line and opened. The feed is extracted with n-pentane (nC5) and
then with dichloromethane (CH2Cl2) to recover the C14+ oil cut and to separate it from the sand. The n-pentane solution is
separated by a preparative medium pressure liquid chromatography into three fractions: C14+ Saturates (SAT), C14+ Aromatics
(ARO) and Resins (RES), which are weighed after solvent evaporation. The dichloromethane solution, corresponding to the
Asphaltenes insoluble in n-pentane (ASP), is also weighed after solvent evaporation. From all these data, the C14+ oil SARA
composition of oil is calculated. The atomic sulfur, carbon and hydrogen mass contents of each SARA fraction are quantified
by direct elemental analysis, i.e. by coulometry for S and by thermal conductivity for C and H.
Solid analysis.
The residue, insoluble in dichloromethane, is recovered and weighed. This residue is composed of the mineral phase (mainly
sand) and potentially of a pyrobitumen, an organic material resulting from thermal alteration of bitumen. This pyrobitumen
behaving as a solid in in-situ conditions due to its high density and viscosity, the set of mineral and pyrobitumen is named
"Solid" (SLD). It is analyzed by direct elemental analysis, to quantify its carbon and sulfur elemental contents, and by RockEval 6, to quantify its organic elemental carbon content and to estimate its proportion of pyrobitumen.

SPE 165437

Mass balance and estimation of C5-C13 oil cut.

The total mass of the following fractions: C1 to C4, CO2, H2, H2S, C14+Saturates (SAT), C14+Aromatics (ARO), Resins (RES),
Asphaltenes/nC5 (ASP) and Solid (SLD), is calculated; rt, the recovery ratio at time t of aquathermolysis, is defined by:
mt Gas + mt C14+Saturates + mt C14+Aromatics + mt Resins + mt Asphaltenes + mt Solid
(1)
rt =
mi oil sand
where mioil sand is the initial mass of the oil sand used in the aquathermolysis run.
rt is used as an indicator for the quality of the experimental results: a too low value of rt reveals an excessive loss of
products during their recovery; in this case experimental data are considered unusable.
The global mass balance equation should take into account the C5-C13 oil cut and the water content, both being not
measured:
(2)
mi oil sand + mi water = mt Gas + mt C14+Saturates + mt C14+Aromatics + mt Resins + mt Asphaltenes + mt Solid + mt C5-C13 oil + mt water
Rearranging equations (1) and (2), it comes:
mt C5-C13 oil = mi oil sand (1 rt) + mi water mt water
(3)
Considering that the net water balance is negative i.e. mt water < mi water, the mass of C5-C13 oil cut is in the range given by
the following inequalities:
mi oil sand (1 rt) < mt C5-C13 oil < mi oil sand (1 rt) + mi water
(4)
This is the way used for quantifying the upper limit of C5-C13 oil cut in the results of aquathermolysis experiments
reported hereafter.
Sulfur mass balance.
The sulfur mass balance is calculated on the following fractions: H2S, C14+ aromatics, resins, asphaltenes and solid. The
C14+ saturates are not taken into account as they are assumed not to contain significantly sulfur.
Experimental results and Discussion
Sulfur and sulfur thermal reactivity of the initial oil sands.
The initial sandy solids and the initial bitumens, obtained from solvent extraction of the initial oil sands, were analyzed
separately for sulfur characterization. The initial sandy solids have been found not to contain any significant sulfur:
S< 0.0001 [g S]/[g Solid] (Table 2). Consequently it has been considered that the initial sands can be practically excluded
from potential sources of H2S during steam treatment. The analytical results showed that the initial bitumens contained
between 0.0488 and 0.0566 [g S]/[g Bitumen] of total sulfur (Table 2). This sulfur is organic, meaning that it is linked to the
hydrocarbon chains that compose the bitumens, and can be split into pyrolyzable sulfur and residual sulfur, as explained
above. The Figure 1 emphasizes that the pyrolyzable sulfur content of the four initial bitumens increases with their total
sulfur content.
H2S generation and sulfur thermal reactivity.
The experimental results of aquathermolysis on the four oil sand samples show that the H2S yield varies significantly from
one sample to another (Table 3, Figure 2). This variability has been already noticed by different authors (Hyne et al., 1984;
Clark et al., 1990) and depends on the amount sulfur in bitumen and its type (disulfides, sulfides, thiols, benzothiophenes,
dibenzothiophenes, etc...) (Katritzky et al., 1990 through 1992; Song et al., 2005). By plotting the H2S yield versus the
pyrolyzable sulfur content of the initial bitumens, we can see that both are well correlated (Figure 3). Such correlation has
been also found for heavy oils from Petrocedeo field in the Orinoco belt in Venezuela (Uzcategui et al., 2011). This
confirms that the pyrolyzable sulfur content could be a relevant indicator of the sulfur thermal reactivity, whatever there is
steam or not. This suggests also that the pyrolyzable sulfur content could be used as proxy for identifying oil sands likely to
generate H2S under steam treatment, and the level of H2S production risk.
TABLE 2 SULFUR CONTENTS OF THE INITIAL OIL SANDS
S
FOSTER CREEK
CHRISTINA LAKE
ORION HILDA LAKE
SURMONT

5.13
5.23
4.88
5.66

BITUMEN
S Pyrolyzable
S Residual after pyrolysis
gS/gBitumen *100
4.15
0.98
4.28
0.95
3.81
1.07
4.73
0.93

SAND
S
gS/gSand *100
<0.1
<0.1
<0.1
<0.1

SPE SPE 165437

Pyrolyzable and Residual

Sulfur
g S / g bitumen *100

Orion
Hilda Lake

Foster Christina
Creek Lake

Surmont

5
S Pyrolyzable

4
3

S Residual after
pyrolysis

2
1
0
4.8

5.0

5.2

5.4

5.6

5.8

Total sulfur
g S/ g bitum en *100
Figure 1: Sulfur content in initial bitumens.

Surmont

mg H2S / g initial bitumen

14

16

Surmont
Christina Lake
Foster Creek
Orion Hilda Lake

12
10
8
6
4

320C

Christina
Lake

14
mg H2S / g initial bitumen

16

12
Foster
Creek

10
8
Orion
Hilda Lake

300C

280C

2
0
220

240

260

280

300

320

340

260C
240C

0
3.6

3.8

4.0

4.2

4.4

4.6

4.8

Aquatherm olysis tem perature, C

Pyrolyzable Sulfur in initial bitum ens,

g S / g bitum en *100

Figure 2: H2S yield from aquathermolysis experiments

(t=203h)

Figure 3: H2S yield from aquathermolysis experiments

(t= 203h), compared to pyrolyzable sulfur content in
bitumens. Each dotted line is associated to a specific
temperature of aquathermolysis run.

Evolution of bitumen composition.

The SARA composition of the Foster Creek bitumen was quantified after 24 hours and 203 hours of aquathermolysis. The
results show that with increasing aquathermolysis severity (increasing duration or temperature):
- C14+ bitumen proportion in oil sand decreases, this being well correlated with an increase of light oil and gases (Table 4 and
Figure 4).
- Resins and asphaltenes, representing more than 60 wt% of the initial bitumen, decrease significantly, lose hydrogen and
sulfur (Figs. 5 through 7, Table 4).
- C14+ aromatics increase significantly, lose hydrogen and are enriched in sulfur compared to their mass and to their carbon
content (Figs. 5 through 7, Table 4).
- Simultaneously, a sulfured solid is generated, whatever organic and/or mineral as seen in Figure 7. According to RockEval6 analyses, the carbon in the solid matrix after aquathermolysis is mainly organic: the organic carbon content in solid
varies from 0.4 to 0.8 wt%, whereas the mineral carbon content in solid varies from 0.02 to 0.06 wt%. If this organic carbon
content increases effectively with increasing aquathermolysis severity as it seems on Figure 8, despite very low values, then
this suggests that the aquathermolysis reactions are inducing the formation of small quantities of pyrobitumen.

SPE 165437

- Simultaneouly, H2S generation increases as seen in Table 3, showing a kinetic phenomenon.

TABLE 3 H2S YIELD
Aquathermolysis Aquathermolysis
FOSTER CREEK
CHRISTINA LAKE ORION HILDA LAKE
SURMONT
temperature,
duration,
C
hours

320
203
416
882
328
1169
374.5
2241
300
203
1362
244
684
532
790
13
280
203
996
101
753
362
2244
0
589
399
260
203
1808
9
1179
223
240
203
2527
2
320
24
3804
413
300
24
4808
151
280
24
5710
18
260
24
7677
9
240
24
8028
4
: mg of Initial oil sand in aquathermolysis runs; : g H2S / g initial oil sand from the aquathermolysis runs.
TABLE 4 COMPOSITION OF THE BITUMEN - FOSTER CREEK

AquaAquathermolysis thermolysis
duration
temperature
C
h
320
203
300
203
280
203
260
203
240
203
320
24
300
24
280
24
260
24
240
24
/
/

Initial
oil sand
mg
416.1
1361.8
995.6
1807.7
2526.6
3803.5
4807.5
5710.1
7677.0
8027.6
2554.3

C14+
Gas

Saturates

5.1
2.2
1
0.8
0.6
2.1
1.1
0.6
0.4
0.3
0

24.5
25.4
24.9
24.2
23.8
24.7
24.4
23.9
23.8
23.6
22.5

C14+
AsphalAromatics
Resins
tenes
mg/g initial oil sand
32.6
30.8
15.9
31.7
39.3
20.0
31.3
42.8
22.5
30.6
44.5
23.7
28.4
44.9
25.0
31.9
40.5
22.6
30.6
42.3
25.7
29.9
42.9
26.7
29.2
43.7
27.1
28.1
44.0
29.5
25.2
46.5
28.7

Total

859
862
865
870
872
869
870
871
872
875
882

968
981
988
994
995
991
994
995
996
1001
1005

32
19
12
6
5
9
6
5
4
0
0

Upper
Recove
limit of
ry
C5-C13
factor
oil cut in
rt
oil
Eq.(1)
Eq. (4)
wt.%
97%
24%
98%
14%
99%
9%
99%
5%
99%
4%
99%
7%
99%
5%
99%
4%
100%
3%
100%
0%
100%
0%

0.40

C14+ oil composition

(g/g)

C14+ oil / initial oil sand, g/g*100

14%

Solid

Upper
limit of
C5-C13
oil cut in
oil sand
Eq.(3)

13%

12%

11%

203 h

Resins

0.35

Asphaltenes
0.30

Aromatics C14+
Saturates C14+

0.25
0.20
0.15

24 h
10%
220

0.10
240

260

280

300

320

340

Aquatherm olysis tem perature, C

Figure 4: C14+ oil proportion in oil sand after

aquathermolysis of Foster Creek oil sand (t=24h, 203h)

20

60

100 140 180 220 260 300 340

Aquatherm olysis tem perature (C)

Figure 5: C14+ oil SARA composition after

aquathermolysis of Foster Creek oil sand (t=203h)

SPE SPE 165437

Asphaltenes
C14+ Aromatics

1.5

H/C, mol/mol

1.4
1.3
1.2
1.1
1.0
1

Sulfur in fractions, g S/ g fraction*100

Resins
1.6

8
7
Resins
6
Asphaltenes
5
C14+
Aromatics
Solid

4
3
2
1
0

20 60 100 140 180 220 260 300 340

S/C*100, m ol/m ol

Aquatherm olysis tem perature, C

Figure 6: Atomic composition of the fractions after

aquathermolysis of Foster Creek oil sand (t=203h). The
arrows indicate the increasing aquathermolysis
temperature.

Figure 7: Sulfur content in the SARA fractions after

aquathermolysis of Foster Creek oil sand (t=203h)

0.8
0.76

TOC in solid, wt%

0.72
0.68
0.64
0.6
0.56

203 h

0.52

24 h

0.48
0.44
0.4
220

240

260

280

300

320

340

Tem perature of aquatherm olysis, C

Figure 8: Total organic carbon content in the solid matrix after

aquathermolysis of Foster Creek oil sand (t=24h, 203h), measured by
Rock-Eval 6.
From these data the sulfur distribution among the C14+ aromatics, resins, asphaltenes, solid and H2S, was deduced (Table 5).
It appears clearly in Figure 9 that a part of sulfur initially present in resins and asphaltenes has been redistributed into C14+
aromatic sulfur, H2S and the solid sulfur. The simplest interpretation of these results is that resins and asphaltenes are
progressively cracked during aquathermolysis, generating sulfured C14+ aromatics, H2S and a sulfured solid, probably a
sulfured pyrobitumen and possibly sulfur bearing minerals, whatever they are formed directly or indirectly.

SPE 165437

TABLE 5 ELEMENTAL SULFUR DISTRIBUTION AMONG THE FRACTIONS FOSTER CREEK

Aquathermolysis
temperature

Aquathermolysis
duration

Gaseous S
(H2S)

Aromatic S

C
320
300
280
260
240
320
300
280
260
240
/

h
203
203
203
203
203
24
24
24
24
24
0

0.14
0.04
0.02
0.01
0.00
0.06
0.02
0.00
0.00
0.00
0.00

0.26
0.23
0.21
0.19
0.20
0.19
0.18
0.21
0.20
0.18
0.18

Resinic S

Asphaltenic S

Normalized mass of Sulfur

0.25
0.34
0.38
0.40
0.46
0.32
0.34
0.43
0.44
0.43
0.44

0.15
0.21
0.25
0.27
0.34
0.23
0.27
0.36
0.36
0.39
0.38

Solid S
0.20
0.19
0.15
0.13
0.00
0.20
0.18
0.00
0.00
0.00
0.00

SPE SPE 165437

b
0.5

0.45
0.4
S in Asphaltenes / S, g/g

S in Resins / S, g/g

0.45
0.4
0.35
0.3

203h
24h

0.25
0.2
220

0.35
0.3
0.25
0.2
0.15
0.1
203h

0.05

240
260
280
300
320
340
Aquatherm olysis tem perature, C

24h

0
220

240

260

280

300

320

340

Aquathermolysis tem perature, C

d
0.16

0.3
0.25

S in Solid/ S, g/g

S in H2S / S, g/g

0.12

0.08

0.04
203h

240

260

280

300

320

0.15
0.1
203h
0.05

24h
0
220

0.2

340

0
220

Aquatherm olysis tem perature, C

24h

240
260
280
300
320
Aquatherm olysis tem perature, C

340

f
203h aquathermolysis
50%

0.29
0.27
0.25
0.23
0.21
203h

0.19

24h

0.17
0.15
220

S in fractions/ S, g/g

S in Aromatics C14+/ S, g/g

0.31

40%

30%
20%
Resinic S
Asphaltenic S
Aromatic S
Solid S
Gaseous S

10%
0%

240

260

280

300

320

Aquatherm olysis tem perature, C

340

20

60

100 140 180 220

260 300 340

Aquatherm olysis tem perature, C

Figure 9: Sulfur distribution among the SARA fractions (a,b,e), H2S (c) and the Solid (d) vs Foster Creek oil sand
aquathermolysis temperature (t=24h, 203h). Fig. (f) synthesizes the data at 203h.

10

SPE 165437

Geochemical kinetic model

On the basis of the observations and statements presented above, a sulfur-based kinetic model for H2S yield has been derived
and calibrated from the sulfur distribution data among resins, asphaltenes, C14+ aromatics, solid and H2S (TABLE 5)
(Lamoureux-Var and Lorant, 2005a, 2007). It is assumed that sulfur in resins and sulfur in asphaltenes are the only reactants.
Sulfur in C14+ aromatics has not been considered as a reactant, as a first approximation. The sulfur species are:
RES
S , the resinic sulfur , i.e. the fraction of atomic sulfur contained in the resins.
ASP
S , the asphaltenic sulfur , i.e. the fraction of atomic sulfur contained in the asphaltenes.
ARO
S
, the aromatic sulfur , i.e. the fraction of atomic sulfur contained in the C14+ aromatics.
H2S
S , the gaseous sulfur , i.e. the fraction of atomic sulfur contained in hydrogen sulfide.
SLD
S , the solid sulfur , i.e. the fraction of atomic sulfur contained in the solid matrix.
The kinetic system has the following form:
SRES a1 SH2S + a2 SARO + a3 SSLD
(5)
SASP b1 SH2S + b2 SARO + b3 SSLD
RES
ASP
S
and S
are each the single reactant for at least one first-order kinetic reaction, the reaction rate being directly
proportional to the concentration of the reactant:
d[SRES]/dt = -KrRES [SRES]
and
d[SASP]/dt = -KrAsp [SASP],
(6)
The constant rates Kr are functions of temperature, following the Arrhenius law:
(7)
EAr
Kr = Ar exp
R T
where EAr (kJ.mol-1 or kcal.mol-1) is the activation energy; Ar (s-1) is the frequency factor. R is the universal gas constant
(R=8,314 J.mol-1.K-1), and T is the temperature (K). For fulfilling the elemental sulfur mass balance, the sum of
stoichiometric coefficients per reaction r is equal to unity.
The reactions, two for the resins and two for the asphaltenes, and the activation energies are presented hereafter:
EARES1 = 48.8 kcal/mol
SRES1 0.22 SH2S + 0.38 SARO + 0.40 SSLD
RES2
H2S
EARES2 = 55.2 kcal/mol
S
S
(8)
ASP1
SLD
EAASP1 = 48.5 kcal/mol
S
S
ASP2
H2S
ARO
SLD
ASP2
0.07 S + 0.60 S
+ 0.33 S
S
EA
= 54.6 kcal/mol
As the number of constraining experimental data was limited, the value of the frequency factor Ar was set to 1014 s-1=8.64 1018day-1,
this order of magnitude being considered as relevant for oil cracking (Behar et al., 2008; Freitag and Exelby, 2006).
We can see two types of sulfured resins in this set of reactions: the first one is labile (EARes1 is low =48.8 kcal/mol) and
generates H2S, sulfured aromatics and pyrobitumen, whereas the other one is more refractory to aquathermolysis (EARES2 >
EARES1) and generates only H2S. In the same way, two types of sulfured asphaltenes are considered: the first one is labile
(EAASP1 is low =48.5 kcal/mol) and generates only pyrobitumen, whereas the other one is more refractory (EAASP2 > EAASP1)
and generates mainly sulfured aromatics and pyrobitumen.
This kinetic model has been used for simulating, using GeoKin software, the H2S generation at various temperature
conditions: 220C, the bottom hole temperature in Foster Creek project, and lower temperatures, on a year time scale (Figure
10). The obtained values represent the H2S production potential, which appears to be drastically influenced by the
temperature between 170C and 220C at the production time scale.
1100

220C

LH2S / m3 initial bitumen

1000
900
800
700

200C

600
500
400

190C

300
200

180C

100

170C

0
0

10

11

12

13

14

Tim e, year

Figure 10: H2S production potential computed with the kinetic sulfur-based model

15

SPE SPE 165437

11

Reservoir simulation
As is, the 4-reaction sulfur-based kinetic model is not usable in a compositional, thermal and reactive reservoir simulation,
given that any reservoir simulation software is not handling atoms, but molecular-type components. Barroux and coworkers
(2013) have proposed a methodology for traducing the sulfur-based kinetic model proposed here above in reactions where
reactants and products are the components (or pseudo components) used for the fluid thermodynamic modeling. They have
then applied this methodology to get a SARA components-based kinetic model. A first step has consisted in validating this
model by the reservoir simulation of the aquathermolysis experiments. The reaction model has been then input in a 2D
reservoir model built using generic properties for an Athabasca oil sand. The results of SAGD reservoir simulations in terms
of H2S/oil ratio at well head versus time are found to depend strongly on the stoichiometry of the reactions. A hypothesis of
H2S adsorption on solid species produced by the reactions is formulated for explaining the observed differences in H2S
production between the laboratory results and the field measurements. Such an adsorption phenomenon could be partly taken
into account by modifying the reactions stoichiometry. As stated by the authors, there are a number of subjacent hypotheses,
of simplifications, to be further checked and validated. In particular:
the stoichiometry of the reactions is related not only to the sulfur-based kinetic model presented here, but also to the
attribution of given molecular weights to the SARA-type pseudo-components. No experimental measurement of the
molecular weight of the SARA fractions has been available for this work, this letting the reaction model for
reservoir simulation unconstrained concerning the component molecular weights;
the unique solid product of reactions, considered in the reservoir simulations, has not been well defined;
an adsorption phenomenon on a solid is very sensitive to the solid specific area.
What will be considered in a next future are the improvements in the experimental protocol which could contribute to
reduce the number of experimentally unconstrained parameters: measuring the molecular weight of the SARA-type pseudocomponents; characterizing the sulfur compounds in the solid matrix, using XRD, SEM and Rock-Eval+Sulfur, for
discriminating the mineral sulfur from the organic sulfur; quantifying the light oil C5-C13; designing experiments to address
the hypothesis of gas adsorption on the solid matrix.
Conclusions
For predicting, at reservoir scale during a steam-based EOR process, the H2S/oil production ratios, a 4-stage methodology is
proposed: (1) screening sulfur properties of a large number of reservoir samples to rapidly delimitate the areas over the field
where a risk of H2S production exists; (2) quantifying the H2S source terms using aquathermolysis experiments on some
relevant reservoir samples selected from (1), and then deriving a sulfur-based kinetic model. This model, as is, provides an
estimation of the maximum potential of H2S production; (3) traducing the sulfur-based kinetic model into a SARA
component-based kinetic model with consistent component thermodynamic properties, usable in a compositional, thermal
and reactive reservoir simulator; then simulating aquathermolysis experiments for validating the component-based kinetic
model; (4) simulating the production process using the reservoir simulation software.
Aknowledgments
The authors would like to acknowledge Dr. Eric Delamaide from IFP Technologies (Canada) Inc. for numerous valuable
discussions and suggestions, and for identifying and providing relevant oil sand samples used in this work. The authors
would like to acknowledge Dr. Pauline Michel for reviewing and for valuable comments.
Nomenclature
Ar
Frequency factor of reaction r
stoichiometric coefficient of sulfur species k in reaction r
ar, br
EAr
activation energy of reaction r
Kr
constant rate of reaction r
R
ideal gas constant
T
temperature
References
Al Darouich, T., Behar, F., Largeau, C. 2006. Thermal cracking of the light aromatic fraction of Safaniya crude oil - experimental study
and compositional modelling of molecular classes. Organic Geochemistry, 37 (9),1130-1154.
Attar, A., Villoria, R. A., Verona D. F. et al. 1984. Sulfur Functional Groups in Heavy Oils and their Transformations in Steam Injected
Enhanced Oil Recovery, paper presented at the Symposium on the Chemistry of Enhanced Oil Recovery - Division of Petroleum
Chemistry- American Chemical Society, 29(4), 1212-1222.
Barroux, C., Lamoureux-Var, V., Flauraud, E. 2013. Forecastingof H2S Production due to Aquathermolysis Reactions, Paper SPE 164317,
presented at the SPE Middle East Oil and Gas Show and Conference, Manam, Bahrain.
Behar, F., Lorant, F., Mazeas, L. 2008, Elaboration of a new compositional kinetic schema for oil cracking, Organic Geochemistry, (39)6,
764-782
Belgrave, J.D.M., Moor, R.G., Ursenbach, R.G. 1994. Gas evolution from the aquathermolysis of heavy oils, Canadian Journal of
Chemical Engineering, 72(3), 511-516.

12

SPE 165437

Belgrave, J.D.M., Moor, R.G., Ursenbach, R.G. 1997. Comprehensive kinetic models for the aquathermolysis of heavy oils, J. of Can. Pet.
Tech., 36(4), 38-44.
Chakrabarty, T., Smith, R.J. 2012. Identification of SSC (Sulfide Stress Cracking)-Susceptible Wells and Risk Prediction, paper SPE
160489 presented at the SPE Heavy Oil Conference Canada, Calgary, Alberta, Canada, 12-14 June.
Chen, H.H., Mojelsky, T.W., Payzant, J.D., Lown, E.M., et al. 1991. Chemical changes in Alberta Oil Sands During Steam Treatment,
AOSTRA Journal of Research, 7(1), 17-35.
Clark, P. D., Clarke, R. A., Hyne, J. B., Lesage, K.L. 1990. Studies on the Chemical Reactions of Heavy Oils under Steam Stimulation
Conditions. AOSTRA Journal of Research, 6, 29-39.
Espitali, J., Antonas R., Lamoureux-Var, V., Letort, G., et al., 2008, Mthode et dispositilf pour caractrisation et la quantification rapides
de soufre dans les roches sdimentaires et dans les produits ptroliers, French Patent No.FR2937737.
Espitali, J., Antonas R., Lamoureux-Var, V., Letort, G., et al., 2010, Method and device for rapidly characterizing and quantifying sulphur
in sedimentary rocks a,d petroleum products, International (PCT) Patent WO2010/049609 A1.
Freitag, N.P., Exelby, D.R. 2006. A SARA-Based Model for Simulating the Pyrolysis Reactions That Occur in High-Temperature EOR
Processes. J. Can. Pet. Tech., March, 45 (3), 38-44.
Greidanus, J.W., MacDonald, D.D., Hyne J.B., 1977. Hydrothermal (Water) Reactions of Athabasca Bitumen Organosulphur Model
compounds and Asphaltene, Oil Sands, 162-167.
Hoffman, G.G., Steinfatt, I., Strohschien, A. 1995. Thermal recovery processes and hydrogen sulfide formation. Paper SPE-29016-MS
presented at the SPE International Symposium on Oilfield Chemistry, San Antonio, Texas, February 14-17.
Hongfu, F., Yongjian, L., Liying, Z., et al. 2002. The study on composition changes of heavy oils during steal stimulation processes. Fuel,
81, 1733-1738.
Hyne, J.B., Greidanus, J.W., Tyrer, J.D., et al. 1984. Aquathermolysis of Heavy Oils. 2nd Int. Conf. on the Future of Heavy Crude and Tar
Sands, Mcgraw Hill, New York, 45, 404-411.
Ibatullin, T.R., Yang, T., Petersen, E.B., et al. 2011. Simulation of Hydrogen Sulfide and Carbon Dioxide Production during Thermal
Recovery of Bitumens, paper SPE 147934 presented at the SPE Reservoir Characterisation and Simulation Conference and
Exhibition, 911 October, Abu Dhabi.
Kapadia, P. R., Kallos, M. S. and Gates, I. D. 2010. A Comprehensive Kinetic Theory to Model Thermolysis, Aquathermolysis,
Gasification, Combustion, and Oxidation of Athabasca Bitumens. paper SPE 129660 presented at the SPE Improved Oil Recovery
Symposium, 24-28 April, Tulsa, Oklahoma, USA.
Kapadia, P. R., Wang, J., Kallos, M. S. et al. 2011. Reactive Thermal Reservoir Simulation: Hydrogen Sulphide Production in SAGD.
Paper SPE 149448 presented at the Canadian Unconventional Resources Conference, 15-17 November 2011, Alberta, Canada.
Kapadia, P. R., Wang, J., Kallos, M. S. et al. 2012. New Thermal-Reactive Reservoir Engineering Model Predicts Hydrogen Sulfide
Generation in Steam Assisted Gravity Drainage. Journal of Petroleum Science and Engineering, 94-95,100111.
Katritzky, A. R., Lapucha, A. R., Luxem, F. J., Greenhill, J. V., Siskin M. 1990. Aqueous High-Temperature Chemistry of Carbo- and
Heterocycles. 14.' Mercaptans and Sulfonic Acids, Energy & Fuels, (4), 572-577
Katritzky, A.R., Murugan, R., Balasubramanian, M., Greenhill, J.V., et al. 1991, Aqueous High-Temperature Chemistry of Carbo- and
Hydrogen Sulfide Generation Heterocycles. 16.' Model Sulfur Compounds: A Study of Hydrogen Sulfide Generation, Energy &
Fuels, (5), 823-834.
Katritzky, A.R., Balasubramanian, M., Siskin, M. 1992. Aqueous High-Temperature Chemistry of Carbo- and Heterocycles. 17.'
Thiophene, Tetrahydrothiophene, 2-Methylthiophene, 2,5 -Dimethylthiophene, Benzo[ b ]thiophene, and Dibenzothiophene, Energy
& Fuels ( 6), 431-438.
Lafarge, E., Marquis, F., Pillot, D. 1998, Rock-eval 6 applications in hydrocarbon exploration, production, and soil contamination studies,
Revue de lInstitut Franais du Ptrole, 53-4, 421-437.
Lamoureux-Var, V. and Lorant, F. 2005a. Experimental evaluation of H2S yields in reservoir rocks submitted to steam injection. Paper D08
presented at the 13th European Symposium on Improved Oil Recovery, EAGE, Budapest, Hungary, 25 - 27 April.
Lamoureux-Var, V., Lorant, F. 2005b. H2S Artificial Formation as a Result of Steam Injection for EOR: a Compositional Kinetic
Approach. SPE 97810, SPE/PS-CIM/CHOA International Thermal Operations and Heavy Oil Symposium, 1-3 November, Calgary,
Alberta, Canada.
Lamoureux-Var, V. and Lorant, F. 2007. Method for constructing a kinetic model allowing the mass of hydrogen sulfide produced by
aquathermolysis to be estimated. US Patent No. 2007/0100594 A1.
Lamoureux-Var, V., Kohler, E., Huc, A.-Y., et al. 2011. Laboratory simulation of H2S and CO2 generation in steamed oil sands, Orinoco
Belt, Venezuela. In Natural Gas Geochemistry: Recent Developments, Applications, and Technologies: Proceedings of the AAPG
Hedberg Research Conference, 9-12 May 2011, Beijing, China.
Lorant, F., Antonas, R., Espitali, J. 2005. Characterization of sulfur in reservoir rocks by Rock-Eval analysis, Paper D06 presented at the
13th European Symposium on Improved Oil Recovery, EAGE, Budapest, Hungary, 25 - 27 April.
Perez-Perez A., A.M. Kamp, A.M., Soleimani, H. et al. 2011. Numerical Simulation of H2S and CO2 Generation during SAGD. Paper
WHOC11-303 presented at the In World Heavy Oil Congress [WHOC11], Edmonton, Alberta, Canada, March 14-17.
PumaFlow Release 5.0 Reference Manual. 2012. Reservoir Simulation Software, Beicip-Franlab.
Song, Z., Wang, M., Batts, B.D., Xiao, X. 2005. Hydrous pyrolysis transformation of organic sulfur compounds: Part 1. Reactivity and
chemical changes, Organic Geochemistry, 36(2005) 15231532.
Thimm H.F. 2001. Hydrogen sulphide measurements in SAGD operations. J. of Can. Pet. Tech., 40 (1), 51-53.
Thimm, H.F. 2008, Prediction of Hydrogen Sulphide Production in SAGD Projects, J. of Can. Pet. Tech., 47(1),7-9.
Uzcategui, D., Lamoureux-Var, V. and Berger, E. 2011. H2S and CO2 generation mechanisms on a steam injection project on Petrocedeo
Field, Orinoco Belt. Paper WHOC11-112 presented at the World Heavy Oil Congress [WHOC11], Edmonton, Alberta, Canada,
March 14-17.