SPE-174486-MS

Experimental Evaluation of H2S Yields during Thermal Recovery Processes

Riyi Lin, China University of Petroleum and University of Regina; Duopei Song, and Xinwei Wang, China
University of Petroleum; Daoyong Yang, University of Regina and Chenglin Hi-Tech Industry Co., Ltd.

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Canada Heavy Oil Technical Conference held in Calgary, Alberta, Canada, 9 –11 June 2015.

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
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Abstract
Experimental techniques have been developed to quantitatively evaluate in-situ H2S generation as a
function of solution alkalinity, SO42⫺ concentration, and carrier gas during thermal recovery processes.
Experimentally, well-designed laboratory tests have been conducted to quantify the in-situ generation of
H2S in a surface passivation reactor. The reaction gases were analyzed by using a gas analyzer, while the
pH values were measured by using a glass electrode after adding anions or cations into the solution.
Solution alkalinity is found to restrain the formation of H2S after subtracting the amount of H2S that
neutralizes alkali in the solution. H2S production increases with increasing SO42⫺ concentrations, more
evidently at a high temperature. As temperature increases, using either carbon dioxide or nitrogen as
carrier gas increases the H2S production; carbon dioxide as a carrier gas, however, yields more H2S up
to 57.6% than nitrogen at temperature of 200-280°C. It is suggested that effect of pH of the formation
water be taken into account while predicting the produced acid gas rates.

Introduction
As for heavy oil, thermal recovery methods, including steam huff-n-puff, steam flooding, and steam
assisted gravity drainage (SAGD) processes, have been considered to be effective under certain conditions
(Wren et al., 2013). The injected steam has a temperature ranging from 180 to 350°C at 1.0-16.5 MPa.
When steam is injected into a reservoir and releases latent heat of condensation, oil viscosity is reduced
and liquidity distillation is enhanced as well (Szasz et al., 1965; Romaov et al., 2011). Meanwhile, there
exist complex chemical reactions among crude oil, condensation water, and minerals, namely aquather-
molysis, under various conditions (Hyne et al., 1984; Thimm, 2001). Such reactions lead to generation of
hydrocarbon gases, CO2, H2 and H2S with the produced oil (Clark et al., 1984a; 1990; Ibatullin et al.,
2011), among which the produced H2S is in the range of 0-261,400 ppm of bitumen produced. Not only
is the generated H2S production mingled hope and fear, but also, to some extent, shows that desulphu-
rization of the oil and others brings toxicity, corrosion and active chemistry into the recovery cycles (Wren
et al., 2013). It is of fundamental and practical importance, therefore, to evaluate H2S yields during
thermal recovery processes under various conditions.
Depending on the nature of sulfur present in a reservoir, formation of H2S under hydrothermal
conditions can be potentially explained by two main reactions, i.e., aquathermolysis and thermochemical
2 SPE-174486-MS

sulfate reduction (Liu et al., 2004; Zhu et al., 2010). Since temperature is usually higher than 180°C in
the reservoir during thermal recovery processes, H2S is mainly resulted from the interactions between
aquathermolysis of heavy oil and thermochemical sulfate reduction of sulfate under high temperatures
(Lin et al., 2014). Sulfate ion in the formation water also affects the production of H2S, demonstrating by
the decreased amount of sulfate ion in the piloted area swept by steam (Zhu et al., 2010). This is mainly
attributed to the fact that the organosulphur compounds react with water, implying that such chemical
reactions are sensitive to the pH of the system (Clark et al., 1984a; Hoffmann et al., 1995; Cross et al.,
2004).
Numerous experimental efforts have been limited to quantify the in-situ generation of H2S as a function
of temperature and reaction time. In general, the production of H2S by chemical reactions during thermal
recovery processes depends on the sulfur content of the oil and minerals (Hyne et al., 1984; Ritchie, 1985;
Chen et al., 1991; Lamoureux-Var and Lorant, 2005; Marcano et al., 2013). H2S generation is found to
sharply increase with an increase in either temperature or pressure (Lamoureux-Var and Lorant, 2005; Lin
et al., 2014). Heavy components of heavy oil and bitumen were prone to hydrolysis, showing various
desulfurization performance in metal salt solutions (Clark et al., 1984b; 1987a; b). Although no efforts
have been made to examine the effects ofSO42⫺, extensive focus has been directed to qualitatively
evaluate impact of pH on the reactivity of the reactants and H2S formation during the aquathermolysis
processes (Clark et al., 1987a; Hoffmann et al., 1995). Also, detailed experimental measurements on how
alkaline affects the performance of H2S generation have not been made available. In general, CO2 is
resulted from the water-gas-shift-reaction, accompanied by H2S formation, during the aquathermolysis
reactions (Ibatullin et al., 2011; Kapadia et al., 2012; 2013).
In this paper, experimental techniques have been developed to quantitatively evaluate in-situ H2S
generation as a function of solution alkalinity, SO42⫺ concentration, and carrier gas during thermal
recovery processes. More specifically, the multi-element analysis has been performed to determine the
low sulfur content from the collected heavy oil by using the X-Ray Fluorescence Spectrometer, X-Ray
Diffractometer and CHSN/O elemental analyzer. Hydrous pyrolysis was then carried out in a quartz glass
cylinder installed in stainless steel autoclave with crude oil, ground sand and demineralized water at high
temperature. Subsequently, the reacted gas products were analyzed as a function of pH value, SO42⫺
concentration, and type of carrier gas by employing gas chromatography, respectively.

Experimental

Materials
Three core samples in the Wa-38 Fault Block, Liaohe Oilfield, PetroChina, were collected from the
exploratory wells that are now under thermal recovery production (see Table 1). Prior to each experiment,
the three core samples were homogenized by crushing and cleaning, while their element and mineral
contents were quantified by using an X-Ray Fluorescence Spectrometer (Model: Axios-Petro, PANalyti-
cal B.V., Netherlands) and X-Ray Diffractometer (Model: X‘Pert Pro, PANalytical B.V., Netherlands),
respectively. The physical properties of all the samples were tabulated in Table 1 and Table 2,
respectively. Sodium hydroxide (NaOH) with purity of 98.5% was manufactured by the Xilong Company
Ltd., China. In addition, CO2 and N2 with purity of 99.999% were purchased from the Huachen High
Pressure Container Company in China and used in the experiments as the carrier gas.
SPE-174486-MS 3

Table 1—The element analysis results of the core samples

Table 2—The mineral contents distribution of the core samples

Well Name Wa-38-J1 Wa-38-J1 Wa-38-34-27

Depth, m 1322.5-1328.0 1279.0-1283.2 1358.5-1363.5

Formation Shasan Dongsan Shasan
Quartz, wt% 46 51 29
Potassium feldspar, wt% 19 14 21
Plagioclase, wt% 29 24 43
Calcite, wt% - 1 -
Ankerite, wt% 3 2 3
Pyrite, wt% 1 - 1
Clay minerals, wt% 2 8 3

Since the targeted formation has been under production for many years, it has failed to obtain the crude
oil samples at the early stage of the production. Consequently, the oil extracted from the core samples by
using the Soxhlet extractor (Model: SXT-02, Hongji, China) as the experimental sample. Due to the
limited amount of such extracted oil, five extra oil samples were collected for comparison from the
existing wells under thermal recovery processes (i.e., steam flooding or steam huff-and-puff) in the Liaohe
Oilfield. Prior to the experiments, not only were all five oil samples dewatered, but also their element
contents were quantified by using a CHSN/O elemental analyzer (Model: Vario EL III, elementary,
Germany). The physical properties of all the five samples were shown in Table 3.
4 SPE-174486-MS

Table 3—The physical properties of the oil samples

Element, wt%

Well Name Recovery Method Geologic Formation N H C Sulfur, wt%

1712C Steam flooding Dongsan 0.63 11.17 85.71 0.77

1713C Steam flooding Dongsan 0.63 10.84 82.52 0.61
1914 Steam flooding Dongsan 0.64 10.99 84.47 0.45
33G41 Steam huff and puff Dongsan 0.63 11.07 85.53 0.52
38432 Steam flooding Shasan 0.60 11.04 84.78 0.44

As can be seen in Table 3, in general, sulfur element with concentration of 0.4-0.8 wt% was contained
in the crude oil from the Wa-38 Fault Block. Although such concentration is higher than the average sulfur
element content found in other formations in the Liaohe Oilfield (Huang et al., 2008), it is lower than those
in many other areas that have high H2S production (Zhang et al., 2007).
Experimental setup
As depicted in Figure 1, the experimental setup mainly consists of the heating subsystem, reaction
subsystem, and detection subsystem. For the reaction subsystem, the stainless steel autoclaves (Model:
HKY, Haian, China), with an internal volume 100 mL, had been designed for a maximum operating
temperature of 600°C and pressure of 20 MPa. The quartz class cylinder with a volume of 50 mL was set
in stainless steel autoclaves, which were placed in an electrically tubular furnace (Model: Guanshi,
Longkou-Xianke, China) with a temperature controller, permitting the vessel to be heated from temper-
ature to 1000°C. The apparatus was equipped with a pressure gauge of 4 MPa. The stainless steel valves
with maximum operating pressure of 16 MPa were installed at the outlet of the stainless steel autoclaves,
the inlet of the drying cylinder, and gas sampling bag, respectively. The minimum detectable concentra-
tion for the H2S detector (Model: PN-2000-H2S, Penglei, China) is 1 ppm, which has upper limit of 10000
ppm.

Figure 1—Schematic of experimental setup.

SPE-174486-MS 5

Experimental procedure
To avoid reactions between metal and catalysts, experiments were conducted in a quartz glass cylinder
which is encapsulated in a stainless steel autoclave. Prior to each experiment, a core plug was weighed
and placed in a quartz glass cylinder with heavy oil and demineralized water. Then, nitrogen was
continuously injected in the stainless steel autoclave to pressurize the system at 0.35 MPa for removing
any residuals in the stainless steel autoclave.
As for each experiment, the temperature in the stainless steel autoclave was constantly maintained by
using the tubular-furnace calefaction. In general, experimental samples were heated in the stainless steel
autoclave for 20 h under a constant temperature. Once the reaction is completed, the autoclave was cooled
to 70°C, opening the valve, and then to ensure gases to be discharged from the stainless steel autoclave.
After the reacted gas products flow through the drying cylinder, they are first checked by using a H2S
detector and then collected by the gas sampling bag to be analyzed by using a Gas Chromatography
(Model: 7890A, Agilent, USA).
Prior to each experiment, sodium hydroxide (NaOH) was dissolved in the demineralized water to
obtain the alkaline solution with different pH values. The alkaline solution is prepared by continuously
adding the accurately weighed NaOH into 1 L demineralized water until its pH value reached the
pre-specified value and measured by using the pH-Meter (Model: PHBJ-260, REX, China). The physical
properties of such prepared alkaline solution are tabulated in Table 4.

Table 4 —pH value corresponding with the amount of sodium hydroxide

pH 9 10 11 12 13

OH- Molarity, mol/L 0.00001 0.0001 0.001 0.01 0.1

Concentration of NaOH, g/L 0.00040 0.0040 0.040 0.40 40

Results and Discussion

Thermal cracking and aquathermolysis

Both thermolysis and aquathermolysis occurred during thermal recovery processes since viscosity of
heavy oil is decreased, converting macromolecules of heavy oil to the micromolecules gradually (Liu et
al., 2004). On average, the heavy oil produced from the Wa-38 Fault Block contains 0.4-0.8 wt% of sulfur
element. To identify mechanisms underlying in-situ generation of secondary-H2S during steam injection,
thermolysis and aquathermolysis reaction experiments were firstly conducted. During experiments, only
5 g crude oil from Well 19-14 were prepared for thermolysis and then mixed with 10 g demineralized
water in aquathermolysis. After 20 hours, concentration of H2S in thermolysis and aquathermolysis was
measured to be 215 ppm and 466 ppm, respectively.
Since the amount of H2S is not too high, other components of the generated gas were analyzed by using
the Gas Chromatography (GC) analysis (see Table 5). As shown in Table 4, at a high temperature, the
thermolysis and aquathermolysis reaction generated organic gases, among which light hydrocarbon gases
(C1-C3) were less than the heavy hydrocarbon gases (C4-C6). Consequently, H2S is generated during
heavy oil thermolysis and aquathermolysis.
6 SPE-174486-MS

Table 5—The GC analysis results of thermolysis and aquather-

molysis
Organic gas component content, wt%

Gas composition Thermolysis Aquathermolysis

Methane 8.72 -
Ethane 3.68 -
Ethylene 1.92 -
Propane 11.04 3.14
Propylene 10.21 6.02
Iso-Butane 1.68 16.89
N-Butane 2.91 6.42
Cyclopropane - 5.27
Trans-2-Butene - 7.57
1-Butylene 2.12 7.90
Iso-Butene 2.68 3.98
Cis-2-Butene 4.69 26.31
Iso-Pentane 4.40 2.61
N-Pentane 2.66 -
Trans-2-Pentene - 2.64
Cis-2-Pentene - 2.19
2-Methyl-1-Butene 1.81 -
2-Methyl-2-Butene 1.30 1.48
C6⫹ 40.18 7.58

Effect of sulfate ion concentration

Thermochemical sulfate reduction (TSR) was referred to the redox reaction between hydrocarbons and
sulfate ion in the formation water and/or sulfate minerals in a carbonate reservoir at high pressures and
elevated temperatures. Physically, sulfate ions or sulfate minerals were easily converted into H2S. During
the thermal recovery processes, temperature of the injected steam is higher than that of the carbonate
reservoir, TSR reaction can be initiated easily if sufficient sulfate ions/minerals are made in contact with
hydrocarbons. Thermal recovery of H2S during TSR reaction is complex due to interactions between
organic and inorganic substances. So far, there has been no clear understanding on the TSR mechanisms
and their dominant factors.
To examine effects of SO42⫺ concentration on H2S generation, deionized water with a concentration
of 1.0, 2.0, 3.0, 4.0, and 5.0 g/L sulfate ion has been used in the experiments. Sulfate solution was prepared
with content of 99.99% sodium sulfate (AR). 10 g of the prepared sulfate solution is used to mix with 5
g heavy oil from Well 19-14 and 5 g ground sand from Well Wa-38-34-27. After 20 hours, the generated
H2S concentration is plotted as a function of concentration of sulfate ion (see Figure 2).
SPE-174486-MS 7

Figure 2—Measured H2S concentration as a function of concentration of sulfate ion.

As shown in Figure 2, H2S concentration generated in these experiments was far more than those
produced during the thermolysis and aquathermolysis. Since the ground sand from Well Wa-38-34-27 was
added to the experiments, this means that H2S was mainly originated from the ground sand and that H2S
was mainly formed by interactions between aquathermolysis of heavy oil and thermochemical sulfate
reduction of sulfate under a high temperature (Lin et al., 2014). In addition, thermochemical sulfate
reduction reaction imposes a dominant impact on the formation of H2S.
As can also be seen from Figure 2, H2S concentration is increased significantly with an increase in the
concentration of SO42⫺ and peaked at 3.0 g/L. When using the demineralized water, firstly, pyrite in the
ground sand was oxidized into sulfate ion. Then, the sulfate ion was further converted into H2S by
thermochemical sulfate reduction. When the sulfate ion was dissolved in the demineralized water, the
activation energy of the entire reaction system has been directly reduced. Since sulfate ions are involved
with TSR, H2S generation is reduced accordingly.
As the concentration of sulfate ions is increased to 4.0 g/L, concentration of the generated H2S has been
decreased slightly. Since the aqueous solution contains more SO42⫺ and Na⫹ ions, both sodium ions and
hydroxyl ions react with the quartz of the ground sand, consuming hydroxyl ions in the aqueous solution
and breaking the hydrolytic equilibrium as well. The remaining sulfate ion is then reacted with hydrogen
ions to form sulfuric acid, allowing for transformation into SO2 (see Equation 1).
[1]

In order to further explore the impact potential associated with the sulfate ion, concentration of
methane, ethane, and propane generated during these reactions were depicted as a function of concen-
tration of sulfate ions in Figure 3. As can be seen, methane concentration is increased with an increase in
concentrations of SO42⫺. Compared with Figures 2 and 3, concentration of H2S is found to increase as
concentrations of the generated ethane and propane increase. Since activation energy of TSR varies with
temperature and hydrocarbons, the Gibbs free energy decreases with an increase in temperature, facili-
8 SPE-174486-MS

tating TSR reaction (Zhu et al., 2005). Since hydrocarbons with larger molecules have more Gibbs free
energy, methane is least likely to react and keeps increasing as concentration of is SO42⫺ increased.

Figure 3—Organic gases distribution under the influence concentration of sulfate ion.

As can also be seen, ethane and propane concentrations are increased at a lower concentration of SO42⫺
and then decreased at a higher concentration. As for ethane, other heavy compounds may need to be
consumed during the reaction in the range of 1.0-3.0 g/L concentration of sulfate ion. Once concentration
of sulfate ion is higher than 3.0 g/L, both ethane and propane contribute to the TSR. This means that all
the hydrocarbons gases can be selectively consumed by TSR, while the heavier hydrocarbon gases were
prone to TSR. Also, it is demonstrated that the higher concentration of sulfate ion in water is, the higher
concentration of H2S generated by TSR will be. The TSR mainly affects the formation of H2S instead of
thermolysis and aquathermolysis.
Effect of pH
In the process of steam injection, a vast amount of bicarbonate was usually contained in the boiled
condensate water. Because the bicarbonate was thermal-decomposed in a boiler at a high temperature, the
boiled condensate water has strong alkalinity with pH value as high as 12 (Shi et al., 1998). According
to the Surin taxonomy, connate formation water from Well Wa-38 was analyzed to be NaHCO3 type, an
alkaline aqueous solution. Meanwhile, either sulfide or H2S was strongly pH-dependent. As a conse-
quence, pH shall have imposed a significant impact on H2S generation.
After mixing the sodium hydroxide solution of different pH values with 5 g heavy oil from Well 19-14
and 5 g ground sand from Well Wa-38-34-27 for 20 hours, concentration of H2S was measured and listed
in Table 6. As can be seen, the concentration of H2S is decreased with an increase in pH value. Since the
generated H2S may be neutralized by the NaOH solution to lower the concentration of H2S, it is necessary
to examine effects of neutralization reactions between NaOH solution and H2S.
SPE-174486-MS 9

Table 6 —The influence of sodium hydroxide on the generation of hydrogen sulfide

Experimental sample pH Temperature (°C) Concentration of H2S (ppm)

Oil ⫹ sand ⫹ sodium hydroxide solution 7 280 3927

9 280 3398
11 280 2575
13 280 624

Assuming that all the added NaOH was used to neutralize H2S, the neutralized mass of H2S (see Table
7) can be theoretically calculated according to the following chemical reaction.
[2]

Table 7—The theoretical results for acid-alkali neutralization

reactions
OH- Molarity Mass of Mass of neutralized
pH (mol/L) NaOH (mg) H2S (mg)

9 0.00001 0.004 0.0017

11 0.00100 0.400 0.1700
13 0.10000 40.000 17.0000

Compared with Table 6, the reduced mass of H2S between experimental measurements and theoretical
calculations are calculated and tabulated in Table 8. It is worthwhile noting that the generated concen-
tration of H2S was 3927 ppm under the neutral conditions (i.e., pH value of 7). At pH ⬍ 11, the
theoretically calculated mass for H2S was less than the experimentally measured value. This means that
the mass of H2S neutralized by NaOH was much less than the total generated amount. In this case, there
exists an inhibition effect on the formation of H2S. At pH ⬎11, the opposite trend is observed, though it
is impossible to determine whether there exists an inhibition or absorption effect only by comparing the
reduced mass of H2S.

Table 8 —Comparison for the reduced mass of H2S between

experimental measurements and theoretical calculations
Mass of absorbed H2S (mg)
Concentration
pH of H2S (ppm) Calculated Measured

9 3398 0.0017 0.0748

11 2575 0.1700 0.1912
13 624 17.0000 0.4670

After experiments, the three collected sample gases were analyzed by using the GC to further evaluate
the impact potential associated with adding sodium hydroxide (see Table 9). Through the GC analysis, not
only is the concentration of H2S found to decrease dramatically, but also the content of heavy hydrocarbon
gases of aquathermolysis is declined after sodium hydroxide is added. Since only methane, ethane, and
propane were detected by performing GC analysis, concentration of heavier hydrocarbon gases (i.e., C3⫹)
10 SPE-174486-MS

was reduced after sodium hydroxide is added. Consequently, the thermochemical sulfate reduction was
inhibited so that the generated concentration of H2S is reduced.

Table 9 —Measured gas concentration during sodium hydroxide

thermal simulation experiments
pH 9 11 13

Organic gas component Methane 61.55 62.12 97.07

content, wt% Ethane 27.22 37.88 2.93
Propane 11.23 - -

Effect of carrier gas

During the experiments, 10 g of the demineralized water is used to mix with 5 g heavy oil from Well 19-14
and 5 g ground sand from Well Wa-38-34-27. After 20 hours, concentration of H2S was measured and
showed in Figure 4 for both CO2 and N2 as the carrier gas at 130-280°C. As temperature increases, using
either CO2 or N2 as carrier gas increases the H2S production. Compared to nitrogen, presence of CO2in
gas phase leads to more generated H2S up to 57.6%, implying that CO2 probably serves as a catalyst. This
may be primarily ascribed to the fact that CO2 dissolves in the demineralized water to make the solution
weakly acid, stimulating the production of H2S.

Figure 4 —Measured H2S concentration as a function of carrier gas of CO2 and N2 at different temperatures.

Conclusions
Experimental techniques have been developed to quantitatively evaluate in-situ H2S generation as a
function of solution alkalinity, SO42⫺ concentration, and carrier gas during thermal recovery processes.
At a high temperature, the thermolysis and aquathermolysis reaction generated organic gases and H2S,
though light hydrocarbon gases (C1-C3) are found to be less than the heavy hydrocarbon gases (C4-C6) and
SPE-174486-MS 11

the amount of H2S is not too high. After the ground sand is added to the experiments, H2S concentration
generated in these experiments is far more than those produced during the thermolysis and aquather-
molysis, indicating that H2S is mainly originated from the ground sand. When deionized water with a
concentration of 1.0, 2.0, 3.0, 4.0, and 5.0 g/L sulfate ion has been used in the experiments, H2S
concentration is found to increase significantly with an increase in the concentration of sulfate ion. Since
the activation energy of the entire reaction system has been directly reduced by adding sulfate ion, H2S
concentration is larger than those generated from the aforementioned experiments. Also, the heavier
hydrocarbon gases are prone to the TSR since the heavy hydrocarbon contents are declined with an
increase in concentration of sulfate ion. The concentration of H2S is found to decrease with an increase
in pH value, while heavy hydrocarbon gases of aquathermolysis are declined after sodium hydroxide is
added. The thermochemical sulfate reduction is inhibited for the fewer heavy hydrocarbon gases so that
the generated concentration of H2S is reduced. Compared to nitrogen as a carrier gas, the presence of
CO2in gas phase leads to generating more H2S up to 57.6%, implying that CO2 probably serves as a
catalyst.

Acknowledgements
The authors would like to acknowledge the financial support provided by the Jinma Oilfield Company,
Liaohe Oilfield Company, PetroChina and the Instrumental Analysis Center at the China University of
Petroleum for analyzing the experimental samples.

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