PETROLEUM EXPLORATION AND DEVELOPMENT

Volume 35, Issue 3, June 2008

Online English edition of the Chinese language journal

Cite this article as: PETROL. EXPLOR. DEVELOP., 2008, 35(3): 349–354. RESEARCH PAPER

Generation mechanism and control measures for H2S in oil

wells, Liaohe Oilfield
WANG Qian*
Drilling & Production Technology Research Institute, Liaohe Oilfield Company, PetroChina, Panjin 124010, China

Abstract: H2S may be generated by the reactions of sulphur-alcohol and sulfoether in the crude oil or by the sulfur-bearing minerals in
the formation at high temperatures. Sulphate can also be reduced to H2S by the sulphate-reducing bacteria in formation water at formation
conditions. Experiments show that temperature is the key external factor affecting the formation of H2S. When the temperature is over
100 ć, the content of H2S increases by about 0.03% for every 20 ć increase in temperature. The content of H2S increases rapidly with
the temperature ranging between 160 ć and 180 ć. When the temperature is higher than 180 ć, the speed of H2S generation decreases
obviously. With the addition of surfactants and mixed additives, the release of H2S can be prohibited. With the addition of acid chemicals,
the content of H2S will increase. H2S in oil wells can be basically eliminated in some time with self-developed H2S remover added.

Key words: oil well; H2S; mechanism; control; Liaohe Oilfield

Introduction content higher than the criterion, even a maximum H2S

Steam flooding is a primary means for thermal recovery of
heavy oil. Under the action of high temperature steam, the
sulfide in reservoirs is extremely prone to generating
hydrogen sulfide through combination reaction. Also,
hydrogen sulfide will flow with crude from bottom hole to
surface and will be released from the crude eventually. At
present, H2S gas has been found in some oil wells in the
associated oil production units in Liaohe Oilfield. In some oil
wells, the maximum H2S concentration has exceeded 20 000
mg/m3, far greater than the threshold value of H2S in the air,
10mg/m3. To prevent H2S associated accidents during
operations such as casing pressure release at wellhead, choke
installation, sampling, valve replacement, and oil measuring in
storage tanks, it is imperative to study the mechanism of H2S
generation and the control measures. In combination with the
production practice of heavy oil in Wa-38 Oilfield, this article
conducts a study on the H2S generation mechanism, the
affecting factors, and the control measures, providing a good
instruction to the solution of H2S problems in the thermal
recovery of sulfur bearing oilfields.
1 Investigation of H2S content
In 2006, a general survey on H2S content was carried out in
some oil wells in 7 oil production plants of Liaohe Oilfield,
with totally 41 021 tests involved in 6635 wells, including
3169 producers with H2S content and 2056 wells with H2S
content up to 10 000 mg/m3 found in a particular well. Table 1
shows the statistics of H2S contents in some producers.
2 Mechanism of H2S generation
The research has revealed that the H2S gas produced in
Liaohe Oilfield was genetic both organically and
inorganically.
2.1 Mechanism of inorganic H2S origin
The inorganically genetic H2S is produced primarily by the
thermochemical reduction of sulfate and the chemical
decomposition of pyrite [1], following the reaction equations
below:
2CaSO4 + 4C + 2H2O == 4CO2Ĺ+ Ca(OH)2 + Ca(SH)2
Ca(SH)2 + CO2 ĺ CaCO3 + H2SĹ
CaSO4 + 4H2 == Ca(OH)2 + H2SĹ+ 2H2O
FeS2 + HCl ĺ FeCl3 + H2SĹ
2.2 Mechanism of organic H2S origin
2.2.1 Generation through mercaptan
Mercaptan is an alcohol like compound and can be regarded
as a derivative of a hydrogen sulfide molecule (H2S) with one
of its hydrogen atom replaced by an alkyl radical, or as a
derivative of a hydrocarbon molecule with one of its hydrogen
atom replaced by a sulfur radical (-SH). It has a general
expression as RSH, where, R represents an alkyl, naphthenic,

Received date: 06 September 2007; Revised date: 23 January 2008.

* Corresponding author. E-mail: wangqian@petrochina.com.cn
Copyright © 2008, Research Institute of Petroleum Exploration and Development, PetroChina. Published by Elsevier BV. All rights reserved.
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354

Table 1 Survey result of H2S contents in some producers, Liaohe Oilfield, in 2006
Percentage of wells Percentage of wells
Max. H2S content
Wells with H2S content with H2S higher with H2S higher
Unit Tested wells Wells with H2S in individual wells
higher than criterion than criterion than criterion
(mg/m3)
in producers in tested wells
Huanxiling Prod. Plant 1 151 587 561 1 500.0 32.02 48.74
Jinzhou Prod. Plant 1 481 391 315 302.0 18.83 21.27
Shuguang Prod. Plant 1 653 917 677 264.0 40.96 40.96
Gaosheng Prod. Plant 499 147 55 1 500.0 4.05 11.02
Jinma Company 427 78 51 10 000.0 11.94 11.94
Teyou Company 741 444 247 250.5 24.50 33.33
Lengjia Company 683 605 150 > 200 21.96 21.96
Total 6 635 3 169 2 056

or aryl. than that of homolysis to produce free radicals, a molecule has

Mercaptan has a special odor, and is prone to reacting with
other substances to generate H2S since it has sulfur radical
(-SH), for example:
2CuCl2 + 4RSH == RSSR + 2RSCu + 4HCl
FeS + 2HCl == FeCl2 + H2SĹ
The energy of the C-S bond in mercaptan is low
(327kJ/mol). As a result, C-S bond will break first when a
particle with certain energy impacts the sulfur compound. The
primary and secondary mercaptans are prone to thermal
decomposition while the tertiary mercaptan may be
decomposed into hydrogen sulfide and associated olefin under
low temperatures:
RCH2CH2SH ĺ H2SĹ+ RCH==CH2
In some cases, especially under low temperatures,
mercaptan can provide high recovery of H2S and will be
cracked more easily when catalyst is present. When hydrogen
and catalyst (for example, Co—Mo—Al2O3) are present,
mercaptan can react and produce alkane and hydrogen
sulfide[2].
2.2.2 Generation through thioether
A compound called thioether is produced when the oxygen
atom in an ether molecule is replaced by a sulfur atom, having
generally a structural formula of R-S- Rƍ. The following types
of thioether are present in petroleum: alkyl thioether (R-S-Rƍ),
aryl thioether (Ar-S-Ar), alkyl-aryl thioether (R-S-Ar), and
heterocyclic thioether, as well as other hybrid thioethers with
various alkyl structures. Based on the research of the
structures of various petroleum molecules, the following
distribution of thioether can be found in petroleum if thioether
is divided into two types - chain and cyclic: cyclic thioether
exists primarily in naphthenic petroleum, namely,
thio-heterocyclic alkane; the content of chain thioether tends
to increase as the alkane content in petroleum rises. In
petroleum without mercaptan, there is very little chain
thioether, if any, it accounts for 3% of the total thioether at
most; in sulfur contained petroleum, thioether has mainly a
structure of open chain R-S-R and occupies a percentage of
25% of the total sulfur compounds.
By heating, the S-C bond in thioether will crack under a
typical mechanism of free radial reaction. Since the S-C bond
produces ions at a speed of heterolysis considerably slower
considerably fewer opportunities to decompose and produce
ions than to produce free radicals. The reaction products
depend mainly on the reaction approaches of free radicals; the
thermal stability of thioether is less than that of hydrocarbon
with similar boiling point. Therefore, thioether in petroleum
usually tends to decompose and convert into hydrogen sulfide.
As proved by research, mercaptan, hydrogen sulfide, and
olefin are the primary products in the thermal decomposition
of thioether. For example:
C9H19SC9H19 ĺ C9H19SH + C9H18
C9H19SH ĺ H2SĹ+ C9H18
C2H5SC2H5 ĺ H2SĹ+ CH3CH3
C2H5SC2H5 ĺ C2H5SH + C2H4
C2H5SH ĺ H2SĹ+ C2H4
Almost no mercaptan is produced by the catalytic
conversion of single ring thioether and the entire product is
hydrogen sulfide. Under the condition of the presence of
hydrogen and the catalysis of Al—Co—Mo, thioether is
normally hydrogenolyzed to produce mercaptan initially at a
maximum content, and then at less content. The reaction
proceeds continuously [3]:
RSRƍ + H2 ĺ RSH + Rƍ H
RSH + H2 ĺ RH + H2SĹ
3 Experimental study on factors affecting H2S
content in oil wells
3.1 Experiment method
Taking some oil wells in Wa-38 block, Xiaowa Oilfield as
an example, the impacts of temperature, surfactants, and acid
substances on the H2S contents in oil wells have been
researched. In Wa-38 block, there are 51 wells with H2S
content higher than the criterion, accounting for 18.21% of the
total wells tested in the block. The maximum H2S content in
individual wells reaches up to 11 894 mg/m3.
10.00g crude sample and other reactants (core 10g and
formation water 10g) were put into a conical flask. Then, the
flask was placed in an enclosed vessel filled with 50.00 ml of
cadmium hydroxide suspension. The enclosed vessel was
located in a high pressure tank filled with 50.00 ml pure water
for absorption of the small volume of H2S that escaped from
the enclosed vessel. Then, the high pressure tank was put into
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354

a thermostat box for reaction under constant temperature for 4 Table 2 H2S content in crude-formation water-core system
hours after being capped and filled with 3MPa nitrogen. At the
Experimental Experimental
same time, the released H2S was absorbed by the caustic Well No. H2S content/%
Temperature/ć pressure/MPa
cadmium hydroxide suspension in the enclosed vessel. The 38-34-27 0.302 3
liquid outside and inside the vessel were put together to form 38-29-49 0.311 6
180 3.0
38-38-37 0.309 3
the cadmium sulfide precipitation. The addition of polyvinyl 38-k032 0.312 7
alcohol triammonium phosphate into the absorption is helpful
to reducing the photo-decomposition of cadmium sulfide. Table 3 H2S contents in crude system at different temperatures
Finally, by the reaction between hydrogen sulfide and Experimental Experimental
Well No. H2S content/%
p-amino-methyl toluidine solution and iron trichloride, temperature/ć pressure/MPa
methylthionine chloride was produced, which was analyzed 100 0.122 4
120 0.161 7
colorimetrically. 140 0.196 7
By the above mentioned method, an experiment was carried 38-k032 160 3.0 0.238 1
out using cores, crude, and formation water taken from 4 oil 180 0.284 6
200 0.291 6
wells (Table 2). It can be seen from Table 2 that very high H2S
220 0.295 6
content was measured in the crude-formation water-core
system under the above experimental condition. The reason is Table 4 H2S contents in crude-formation water system at
possibly that at high temperature, crude, cores, and water were different temperatures
involved in the reaction, resulting in more H2S being produced. Experimental Experimental
Well No. H2S contents/%
temperature/ć pressure/MPa
3.2 Impact of temperature on H2S content in crude
100 0.131 5
By the above experiment method, the crude samples were 120 0.177 5
140 0.214 9
studied in the experiment. See Table 3 for the results. 38-k032 3.0
160 0.258 2
It can be seen from Table 3 that the H2S content increased 180 0.294 9
from 0.1224% to 0.2956% when all other conditions were 200 0.301 5
unchanged but the temperature rose from 100ć to 220ć. It is
Table 5 H2S contents in crude-formation water–core mixture
thus indicated that the higher the temperature, the more H2S
system at different temperatures
produced in the crude system.
Experimental Experimental
3.3 Impact of temperature on H2S contents in Well No. H2S content/%
temperature/ć pressure/MPa
crude-formation water mixture system 100 0.145 0
120 0.189 7
By the above experiment method, the H2S contents in the 140 0.228 7
38-k032 3.0
crude-formation water mixture system were studied in the 160 0.275 1
180 0.312 7
experiment. See Table 4 for the results. 200 0.321 4
It can be seen from Table 4 that the H2S content increased
from 0.1315% to 0.3015% when all other conditions were 3.5 Impacts of temperature and mud acid on H2S content
unchanged but temperature rose from 100ć to 200ć. It is in crude
seen that more H2S is released from the oil-water mixture By the above experiment method, an experiment study was
system than that from the pure oil system. The reason lies in conducted using mud acid and crude. See Table 6 for the
the fact that more H2S is carried into the gas phase by bubbles results.
generated from water under high temperatures. Additionally, It can be seen from Table 6 that the H2S content in the
in the process of extensive mixing of oil and water, a mixing crude-mud acid system increased from 0.1862% to 0.3074%
equilibrium is reached and H2S in crude is dissolved partially when all other conditions were unchanged but temperature
in formation water. As the temperature increases, the H2S in rose from 100 ć to 200 ć. The mechanism can be explained
the water tends to escape, leading to higher H2S content. as follows: mud acid is an acidic substance, which can
3.4 Impact of temperature on H2S contents in promote the release of H2S from crude, leading to a reduction
crude-formation water-core mixture system of H2S gas dissolution in crude and more H2S in gas phase [4,5].
It is found from the comparison with the data in Table 3 that
By the above experiment method, the H2S contents in the
the H2S content released from the crude-mud acid mixture
crude-formation water-core mixture system were studied in
system is higher that that from the pure oil system at identical
the experiment, using crude, formation water, and core
temperatures, indicating that the presence of mud acid
powder (Table 5). It can be seen from Table 5 that the H2S
promoted the H2S generation and release.
content increased from 0.1450% to 0.3214% when all other
conditions were unchanged but temperature rose from 100ć 3.6 Impacts of temperature and surfactant on H2S
to 200ć. contents in crude-formation water mixture system
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354

By the above experiment method, an experiment study was Table 6 H2S contents in crude-mud acid system at different
conducted using surfactants, crude, and formation water. See temperatures
Table 7 for the results. Experimental Experimental
Well No. H2S content/%
It can be seen from Table 7 that the H2S content in the temperature/ć pressure/MPa
100 0.186 2
crude-formation water- surfactant mixture system increased
120 0.204 8
from 0.0115% to 0.0246% when all other conditions were 140 0.239 1
38-k032 3.0
unchanged but temperature rose from 100ć to 200ć. The 160 0.255 9
mechanism can be explained as follows: the surfactant 180 0.282 7
200 0.307 4
emulsifies H2S, crude, and formation water into a
Note: In the mixture system, the mass of crude sample is 10g and that
homogeneous phase, making H2S release difficult. By
of mud acid is 1g.
comparison with the data in Table 4, it is found the value of
H2S content in Table 7 is less than that in Table 4 under the Table 7 H2S contents in crude-formation water-surfactant
same temperature, indicating that the surfactant presence mixture system at different temperatures
reduced the value of H2S content, i.e., the surfactant has an Experimental Experimental
Well No. H2S content/%
inhibition to H2S generation. temperature/ć pressure/MPa
100 0.011 5
3.7 Impacts of temperature and additive mixture on H2S 120 0.014 1
140 0.017 4
contents in crude-formation water-core mixture system 38-k032 3.0
160 0.020 3
By the above experiment method, an experiment study was 180 0.022 8
200 0.024 6
conducted using additive mixture, crude, formation water, and
Note: In the mixture system, the mass of crude sample is 10g, that of
cores. See Table 8 for the results. It can be seen from Table 8
formation water is 10g, and that of surfactant is 0.1g.
that the H2S content in the crude-formation
water-core-additive mixture system increased from 0.0753% Table 8 H2S contents in crude-formation water-core-additive
to 0.1738% when all other conditions were unchanged but the mixture system at different temperatures
temperature rose from 100ć to 200ć. By comparison with Experimental Experimental
Well No. H2S content/%
temperature/ć pressure/MPa
the data in Table 5, it is found that the value of H2S content in
100 0.075 3
Table 8 is less than that in Table 5 at the same temperature, 120 0.087 5
indicating that the presence of additive mixture also has an 140 0.107 9
38-k032 3.0
inhibition to H2S generation. 160 0.134 5
180 0.158 3
In summary, the following understandings are concluded: 200 0.173 8
(1) Temperature rise is the primary external factor for H2S
Note: In the mixture system, the mass of crude sample is 10g, that of
generation. At a temperature above 100ć, every rise of 20ć core is 10g, that of formation water is 10g, and that of additive
will cause an average increase of H2S content of about 0.03%; mixture is 2g.
at a temperature range of 160 – 180ć, and it will cause a
Table 9 Statistics for H2S content and removing rate before and
maximum increase of H2S content; when the temperature is
after chemical addition at various dosing concentrations
higher than 180ć, the increase of H2S content will become
less remarkably. Remover
H2S content H2S content
Removing
(2) The addition of chemicals with surfactant functions can before after
concentration/% rate/%
addition/% addition/%
inhibit H2S release, thus reducing H2S content [6]. 0.050 0.3 0.008 1 97.3
(3) The addition of acid chemicals will promote the increase 0.125 0.3 0.004 5 98.5
of H2S content. 0.200 0.3 0.001 99.7
0.250 0.3 0 100
4 Control measures against H2S over a period of time. The application dosage can be calculated
4.1 Study on H2S remover as follows:
Drop dosing: when the H2S content in crude is less than
As a result of the experimental study, an H2S remover
0.3%, a dosing concentration of 0.25% can completely remove
effective for application has been developed, i.e., LH-XCJ-1.
H2S; when the H2S content is higher than 0.3%, the dosage
From the research, it was seen that the H2S content in
must be increased proportionally.
crude-formation water-core-additive mixture system was
Squeezing in H2S remover completely in a single dosing: the
measured as 0.0081% at an LH-XCJ-1 dosing concentration
dosage for every 10m pay zone is about 2t, and the dosage has
0.05%; as 0.0045% at an LH-XCJ-1 concentration 0.125%,
to be calculated specifically based on H2S content in an oil
and as zero at an LH-XCJ-1 concentration 0.25%. Table 9
well and the pay zone thickness [7].
shows the statistics for H2S content and removing rate before
and after chemical addition at various dosing concentrations. 4.2 H2S removing methods
As a liquid H2S remover, it can completely eliminate H2S For a producer with high H 2 S content, treatment is
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354

Fig. 1 Elimination of H2S effect by continuous drop dosing from casing

Fig. 2 Elimination of H2S effect by continuous squeezing of additives from tubing into formation

Fig. 3 Elimination of H2S effect by under-balanced swabbing-neutralization treatment

necessary prior to operation, to reduce the H2S content in
conformity with the environment standard. The following are
the treatment methods and equipment:
(1) Continuous drop dosing from casing (Fig.1). This
method is applicable to oil wells with low H2S content. The
dosage has to be determined based on the H2S content in the
production from the oil wells.
(2) Squeezing in additives into formation from tubing
(Fig.2). It is suitable for application in oil wells with high H2S
content prior to operation. The H2S remover is squeezed
completely from tubing into the formation in a single
treatment. The dosage has to be determined based on the H2S
content in the production from an oil well, the pay zone
thickness, the treatment radius, and the reservoir porosity [8].
(3) Under-balanced swabbing - neutralization treatment
(Fig.3). This is suitable for such cases – prior to operation or
during operation in an oil well. The casing gas must be
swabbed into the treatment pit for H2S neutralization [9].
(4) Simplified treatment equipment for H2S removing at
wellhead (Fig.4). This method needs less investment and is
easy for installation; it is suitable for producers with low H2S
content.
(5) Central treatment of casing gas in stations (Fig.5).
Although it requires a large lump-sum investment initially, but
repeated and sporadic investments are eliminated, and the
treatment result is good, facilitating ongoing improvement and
perfecting of the treatment method; it is suitable for oil wells
with high H2S content [10].
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354
Fig. 4 Simplified treatment equipment for H2S removal at wellhead
Fig. 5 Central treatment of casing gas in station
5 Conclusions
The primary causes for H2S generation in oil wells are:
organic sulfide compounds such as mercaptan and thioether in
crude react at high temperatures to produce hydrogen sulfide;
the sulfur contained minerals in the formations react at high
temperatures to produce hydrogen sulfide; sulfate is reduced
into hydrogen sulfide by sulfate reducing bacteria in formation
water under reservoir conditions.
From the experiments, it can be proven that H2S content
tends to increase as temperature rises. The addition of additive
mixture, including surfactants, flow agents, emulsion breakers,
and viscosity reducers has obvious inhibition to H2S
generation, thus reducing H2S release. The application of acid
liquid will increase H2S release, particularly in the cases of
frequent acidizing jobs and many wells being acidized and
more H2S will be generated.
Preventive measures will be taken predominately against
the hazards caused by H2S produced from oil wells while
removing as the supplementary measure. The preventive
measures to be taken mainly include: formulation of a proper
management system and associated personal training,
availability of portable H2S detectors, simplified rescue
facility equipped at key posts, clear identification of H2S
containing wells (red, yellow, and blue signs depending on
H2S content), protective equipment available for persons at
well sites in H2S containing wells, hazard alert line set up at
well sites, etc.
References
[1] DAI Jin-xing. A discussion on distribution feature,
classification and origin of H2S bearing natural gas in China.
Acta Sedimentologica Sinica, 1985, 3(4): 109-120.
[2] ZHONG Tai-xian, YUAN Shi-yi, ZHOU Long-ping, et al.
Phase behavior and flow of sour gas under reservoir conditions.
Petroleum Exploration and Development, 2004, 31(5):
109-111.
[3] GU Ming-xing, LI Qun, CHEN Wei-dong, et al.
Thermo-dynamic model for solid sulfur dissolution (II) in
supercritical/pseudocritical acidic fluid. Journal of Chemical
Industry and Engineering (China), 1993, 44(3): 321-327.
[4] LI Shi-lun. Natural gas engineering. Beijing: Petroleum
Industry Press, 2000.
[5] SHEDID A S, ZEKRI A Y. Formation damage due to sulfur
deposition in porous media. SPE 73721, 2002.
[6] LEPPIN D. New, lower-cost acid gas removal and sulfur
recovery technology for Permian basin natural gas production
operations. SPE 59712, 2000.
[7] KENNEDY H T, WIELAND D R. Equilibrium in the
methane-carbon dioxide-hydrogen sulfide-sulfur system. AIME,
1960, 219: 166-169.
[8] SWIFT S C, MANNING F S, THOMPSON R E.
Sulfur-bearing capacity of hydrogen sulfide gas. SPE Journal,
1976, 16(2): 57-64.
[9] ROBERTS B E. The effect of sulfur deposition on gas well
 WANG Qian / Petroleum Exploration and Development, 2008, 35(3): 349–354

inflow performance. SPE Reservoir Engineering, 1997, 12(2): of sulfur plugging in carbonate reservoirs. Journal of Petroleum
118-123. Science and Engineering, 2000, 26(1-4): 91-103.
[10] ABOU-KASSEM J H. Experimental and numerical modeling