SPE

Society of Petroleum Engineer'S

SPE 18480

Inorganic Chemical Souring of Oil Reservoirs

by S.D. Marsland,* R.A. Dawe, * and G.H. Kelsall, Imperial College
* SPE Members

Copyright 1989, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Symposium on Oilfield Chemistry in Houston, TX, February 8-10, 1989.

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, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The
material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at
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abstract of not more than 300 words. Illustrations may not be copied. The abstract should contain conspicuous acknowledgment of where and by whom
the paper is presented. Write Publications Manager, SPE, P.O. Box 833836, Richardson, TX 75083·3836. Telex, 730989 SPEDAL.

Abstract 3) Combining the thermodynamic predictions of 2) with

Many North Sea oil production reservoirs are producing experimental work utilising 1) in a rotating-ring-disc
increasing quantities of hydrogen sulphide, perhaps as high as 30 electrode assembly to determine the mechanism and
ppm, although the oil itself is naturally sweet. This high level is kinetics of the dissolution reactions
endangering the sales of oil and gas, giving rise to enhanced This paper presents the preliminary work on this study.
corrosion effects in pipelines and production facilities as well as
causing concern for health and safety.
Introduction
The mechanism put forward in this paper for hydrogen
sulphide generation within the reservoir is via Non-oxidative At present there is no full explanation as to the mechanism by
dissolution of formation components: which hydrogen sulphide is produced within originally sweet
North Sea oil bearing reservoirs. One possible explanation put
forward as the route to ~S generation is due to microbial
activity 1-13 • Sulphate-reducing bacteria are known t~ generate llzS
(where MS. is especially components containing iron sulphide as a by-product of their respiratory cycle. Particular strains of SRB
species such as Fe 1 _xs, FeS 1 _x and FeSJ can withstand certain extreme conditions, but it is proving difficult
The acidic component in the above reactions is provided either to isolate strains which can survive the severity of all the
from the injection water on breakthrough, or degradation species conditions in a petroleum reservoir.
from injected components such as biocides and corrosion and scale As careful planning for reservoir development is becoming
inhibitors. more important, so too is an understanding of the mineral
The objectives of this continuing study are to investigate the processes occurring within the reservoir. There has been very little
kinetics and mechanisms of formation dissolution in reservoir detailed work concerned with· the interaction between what is
environments of high temperature, high pressure and high ionic injected into the reservoir and what is already present there , It is
14

concentration based on: believed that the possible inorganic reactions caused by changing
the nature of the reservoir environment are the source of HzS
1) Preparing pure iron sulphides of known stoichiometry and generation. It is known that North Sea reservoir formations
homogeneity contain mineral sulphides, and in particular iron sulphides of the
2) Using generated thermodynamics diagrams to predict the form FeS, FeS 1_x and FeS 2• The reaction of these materials with
behaviour of the iron-sulphur-water system at any required acidic components coming either from the injection water on
conditions relevant to the reservoirs breakthrough, or degradation species from injected components,
such as biocides and corrosion and scale inhibitors will cause
hydrogen sulphide generation. To understand and be able to
control the above reactions it is necessary to monitor the kinetics
~~~:--;::~----;-:'~----:------=---~---::--=---------I and mechanisms of such reactions.
* References and illustrations are at the end of the paper
201
2. INORGANIC CHEMICAL SOURING OF OIL RESERVOIRS SPE 18480

This paper provides the information necessary to show that the The dissolution rate is dependant upon the concentration of
generation of hydrogen sulphide by the non-oxidative dissolution iron (II) ions in solution. The variation seen in the composition of
of iron sulphides within high temperature, high pressure and high formation waters, shows that it is important to have an
ionic concentration reservoirs is a feasible mechanism. understanding as to what role, if any, cations and anions in solution
will have upon the rate of dissolution.
v) Redox potential of solution and mineral surface potential
Within the reservoir the formation will be at a potential which
Background is sensitive to external conditions. It is therefore important to
Leaching of sulphide minerals may occur naturally, or as a unit establish the history of the change in potential of a reservoir and
process in the hydrometallurgical extraction processes from ores the effect this has upon the stability of iron sulphides.
and concentrates. It involves one of three types of reaction:
vi) Initial surface area
i) non-oxidative dissolution:
The form and distribution of the iron sulphides present in the
MS +2/J+ ~ M 2 + +H2S (1) reservoir is important, because the initial rates of dissolution are
controlled by the stoichiometry of the FeS surface.
ii) oxidative dissolution:
MS +4H20 +xO ~M 2 + +So;- +8H+ +xR (2)

Presence of Iron Sulphides

iii) reductive dissolution:
The generation of iron sulphides within the formation can be
explained in terms of the events occurring during diagenesis. The
(3)
stages of diagenesis can be separated into progressive time and
where 0 and R are some oxidised and reduced state of some burial 'zones'. Within each of these zones redox and acid
appropriate redox couple, or for electrochemical experiments, the generating reactions take place, producing solutes which then
reductant R would be electrons supplied from an external power assist in mineral dissolution.
supply, so producing no oxidised form 0.
The most recently deposited zone is where the oxidisation (by
The presence, quantity and form of the iron sulphides within species such as 02.Mn02,FeP3.NO:;) of the organic matter takes place
reservoir formations is usually unknown. In the past it has been resulting in an increase in acidity and Hco:; activity. Carbonate
assumed that the mineral sulphides have been restricted to only the dissolution results in increases in the acidity. The thickness of this
poor regions of reservoir formation material. Although the zone is usually very thin and would be thinner if it were not for the
location of iron sulphides to particular bed members is particular water circulatory activities of burrowing organisms. High levels of
for each reservoir, Table 1 indicates the distribution within a reaction products (e.g. Hco:;,Fe 2 +.Mn 2+.N2) are unlikely to be
section of the Fulmar Sands in the Northern North Sea province. maintained in this region due to the diffusion and mixing of pore
This shows that on a reservoir scale the amount of iron sulphide waters with overlying depositional waters. Reactions taking place
material is large, and not necessarily restricted to regions of poor in this zone ensure that the organic matter is destroyed.
permeability and porosity.
The second zone is where microbial sulphate reduction takes
In the study of non-oxidative dissolution of iron sulphides place. This will result in an increased acidity and Hco:; activity. In
factors which affect the reaction are represented in equation (1). this zone s 2 - precipitation as iron sulphides of the form FeS is
These factors have been investigated mainly in the context of the highly probable, with the further possible conversion to pyrite,
mineral processing industry 15 •26 and may be summarised as: FeS 2 • The continuing reduction of available Mn 4 +,Fe 3 + will also take
i) Acid type and concentration place.

It is apparent that the rate of dissolution is dependant upon the The third zone is where microbial fermentation can take place.
hydrogen ion concentration, however, it is important to know the Here organic matter is broken down, methane being one of the
order of the reaction with respect to [H+]. products, with an increase in acidity and Hco:; activity. Continuing
reduction of available Fe20 3 will produce iron carbonate minerals.
ii) Partial pressure of H 2S
In the fourth zone excess iron (Fe 20 3 ) is reduced and excess
If the dissolution is chemically controlled then the rate is carboxylates eventually undergo dissolution to carbonates.
retarded due to the promotion of the reverse reaction in equation 1,
or due to the possible adsorption of ~S on the mineral surface. The final zone is where liquid hydrocarbon generation takes
place. Here there is the possibility of increased acidity due to C02
iii) Temperature
generation from organic matter. The residual pore waters will
An estimate of the effect of temperature on the rate of reaction probably be maintained at an acidic pH.
can be obtained from the Arrhenius equation.
The presence of iron sulphides within the formation is iikely to
iv) Anions and cations in solution occur as small nodules (of the order of a few tens of micrometres

202
SPE 18480 S.D. MARSLAND, R.A. DAWE, G.H. KELSALL 3.

in dimension) associated with residual organic matter, clay flasers,

Troilite, Fe1_0S1.0 Synthesis
splayed micas and early kaolinitic clays, or as a pore-lining. Less
commonly, extensive multicrystal iron sulphide aggregates occur Naturally occurring pyrrhotites are a combination of either
in the form of a highly corrosive cement phase. This latter type of sulphur rich, iron rich or iron oxide containing minerals. To
iron sulphide cementation is found particularly in marine and interpret and simplify the mechanism of non-oxidative dissolution
marginal marine type reservoir sands. it is necessary to initially work with 1:1 stoichiometric iron
sulphide, troilite, Fe~. 0 S~, 0 •
At present in the North Sea the maximum limit of H2S which
can be transported along a pipeline is 30 ppm (mg per m-3). With a Should the material be sulphur rich (Fe1_xS) then the dissolution
well producing at 10,000 bbls per day, then over a period of 3 is preceded by an induction period during which it is predicted the
months the amount of H2S produced would be 4.293 kg. The surface of the pyrrhotite is reduced to an exact stoichiometry:
dissolution reaction, equation 1, is a 1 kmol to 1 kmol conversion,
and so the amount of FeS required is 11.11 kg. The density of
pyrrhotite is 4,760 kgm- 3 • Assuming that pyrrhotite occupies
0.75% by volume of the rock formation and the porosity of the With iron rich iron sulphides (FeS 1) no induction period is
formation material is 30%, the amount of mineral needed to be observed due to the_ oxidative (anodic) dissolution of iron.
contacted would be 0.405 m-3. If the perforated interval in the In natural pyrrhotite with an iron oxide content, non-oxidative
well were to be 1Om, then the depth into the formation which dissolution is preceded by an induction period during which the
would contain this amount of pyrrhotite would be 11 em. It is oxide undergoes preferential dissolution:
more probable that the pyrrhotite exist as small nodules spread at a
Fe 30 4 +8HCl-7FeCl2 +2FeCl3 +4H20 (7)·
much greater distance around the wellbore. This elementary
calculation shows that only very small quantities of FeS are The iron (III) chloride is then reduced by either traces of
required to generate high levels of H2S. hydrogen sulphide:

(8)

or the pyrrhotite surface:

Thermodynamics of the Iron-Sulphur-Water System
0
Fe7 S 8 + 14FeCl3 --7 21FeCl2 + 8S (9)
The extent to which a reaction can occur depends to an extent
upon the pH of the solution, the redox potential and the activities
The produced sulphur formed on the pyrrhotite surface inhibits
of the reacting materials.
the dissolution so giving rise to the induction period.
The standard free energy for a reaction, !J.Gi, is related to the Troilite (Fe 1_0 S1.0) has been synthesised from a method similar
equilibrium constant for a reaction, k, by:
to that used by Dutrizac29 by sealing iron bars (Johnson Matthey
0
D.G = -RTlnk (4) Specpure, 15ppm metal impurities, 5mm diameter and 150mm
where R is the gas constant and T is the absolute temperature. The length) and sulphur lumps (Johnson Matthey Specpure, 10ppm
Gibb's free energy value is also related to the potential of a total impurities, maximum lump size 10mm) in an evacuated silica
reaction, which depends upon the relative activities of the species ampoule. The ampoule was gradually heated to 550°C where it
involved. This potential is known as the 'electrode potential', and was held for 190 hours prior to cooling. The resulting iron
sulphide was homogenised at 900°C for 48 hours. The mother
if the system is in thermodynamic equilibrium, as the 'reversible
electrode potential'. The value of the potential, E, is given by the material was ground under a nitrogen atmosphere to produce a fine
Nernst equation: grain powder. Samples of this material were sealed in 7mm
diameter silica glass ampoules for casting into ingots for use in the
E =Eo_ RT In {Reduced state} rotating ring disc assembly.
(5)
zF { Oxidisedstate}
where, z is the number of electron-s transferred, F is Faraday's
constant and Eo is the standard electrode potential corresponding to
the value of E when the activities of the reduced and oxidised Ion-Selective Electrode Calibration
states are unity.
Monitoring of. the sulphide ion concentration in solution was
The most useful representation of the thermodynamic stability achieved using a Philips IS 550-Sz. ion-selective electrode (I.S.E.).
data of aqueous chemical systems is in the form of potential In use, the electrode may be represented as:
(Eh)-pH diagrams. Figure 1 indicates the thermodynamic areas of
2
stability of iron-sulphur-water compounds considering Fe20 3 as the [Ag:AgCl(s) I Aq+(O.lM) I Ag S] I test sample I reference electrode
stable iron (III) oxide. species. The diagram was constructed using where [] denotes the I.S.E .. The electrode potential of the cell, E,
thermodynamic data contained in Bard27 and Pourbaix2B, is given by the Nernstian equation:

203
4. INORGANIC CHEMICAL SOURING OF OIL RESERVOIRS SPE 18480

Conclusions
(10)
1. Hydrogen sulphide souring of originally sweet oil can be by
where aA,+ is the activity of the silver ions. This may be related to inorganic chemical means.
the sulphide ion activity by the solubility product of silver
2. The most probable method of inorganic chemical souring of
sulphide, K., =a:,•.a5 a-. as:
North Sea oil reservoirs is by the non-oxidative dissolution of
reservoir formation iron sulphides, FeS, Fe1_xS and FeS 1.x·
(11)
3. The technique of using a R.R.D.E. with the disc fabricated from
The constant E"" includes a term for the solubility product KIP. synthesised iron sulphides of known stoichiometry is the most
The concentration of an ion is related to its activity by: suitable method for determining the mechanism and kinetics of
non-oxidative dissolution of iron sulphides.
(12)

Providing the concentrations are low, less than 1 x 10·3 M then

·the activity coefficient, y, can be taken as unity and the activity is
equivalent to the concentration. Acknowledgements
In the rotating ring disc electrode, R.R.D.E., the sulphide ·We are grateful to Shell Expro UK Ltd and Occidental
sensor is a sulphidised silver ring. As this differs from a Petroleum (Caledonia) Ltd for their support. We thank Steve
commercial sulphide I.S.E. calibration work has been carried out Bieshaar and Sam Dalziel for their continued interest.
on a sulphidised silver wire for comparison purposes.
Figure 2 shows the results of the calibration for the two
electrodes. The lower limit of the near-Nernstian response for both
the I.S.E. and the sulphidised silver wire was 10·5 kmol/m-3
sulphide ion. These results are in reasonable agreement with those
found by other workers3o-3s.

Rotating Ring Disc Electrode Work References

Figure 3 illustrates a cross-section of the rotating ring "disc 1. Brown R.A. and Norris R.D., "Hydrogen Peroxide Reduces
assembly. When the R.R.D.E. is rotated in a large vblume of Sulfide Corrosion", Oil and Gas J., (1982) Sept 6.
solution a well defined flow pattern distribution is establish, in
2. Cord-Ruwisch R., Kleinitz W. and Widdel F.,
which the solution is pulled vertically upwards towards the disc
"Sulphate-Reducing Bacteria and their Activities in Oil
and then thrown outwards. In this regime any intermediates ~Production", J.Petrol.Technol., 39(1) (1987) 97-106.
formed at the disc (where the synthesised FeS is undergoing
non-oxidative dissolution) are swept out towards the ring. The 3. Herbert B.N., Gilbert P.D., Stockdale H. and Watkinson
ring acts as a downstream monitor (a silver ring which prior to R.J., "Factors Controlling the Activity of SRB in Reservoirs
experimentation is sulphidised and so acts as a Ag/Ag2S ion During Water Injection", SPE Paper N!. 13978 (1985).
selective electrode) and can provide information about the 4. Maxwell S., "Assesment of Sulfide Corrosion Risks in
solution-free intermediates formed by any reaction at the disc. The Offshore Systems by Biological Monitoring", I. Production
electrical contacts to the ring and disc are made separately Engng., , (1986), .
allowing the ring and disc to be potentiostatted independently of
each other. S. Moses V. and Springham D.G., "Bacteria and the
Enhancement of Oil Recovery", Applied Science Publishers,
Initial experimentation involves the disc being held at a (1982).
constant potential where the non-oxidative dissolution takes place
(as can be determined from Figure 1 ) and the ring recording a 6. Pankhurst E.S., "Significance of Sulphate-Reducing Bacteria
decrease in potential as the concentration of sulphide builds up. to the Gas Industry: A Review", J.Appl.Bacteriology, 31(2)
From computer aided data acquisition, analysis of all stages of the (1968) 179.
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Gas Underground", J.Appl.Bacteriology, 31 (1968) 311-322.
8. Postgate J.R., "Recent Advances in the Study of Sulphate
Reducing Bacteria", Bacterial. Rev., 29 (1965) 425.

204
SPE 18480 S.D. MARSLAND, R.A. DAWE, G.H. KELSALL 5.

9. Postgate J.R., "The Sulphate-Reducing Bacteria", Cambridge 23. Romankov L.T. and de Bruyn P.L., "Kinetics of Dissolution
University Press, (1979). of Zinc Sulfide in Aqueous Sulfuric Acid", Unit Operations in
10. Society of Petroleum Engineers, "Produced Water Hydrometallurgy, Gordon and Breach, 1965, pp.45.
Problems", Continuing Education Seminar, Aberdeen Section, 24. Majima H., Awakura Y. and Misaki N., "A Kinetic Study on
14th May 1987. Nonoxidative Dissolution of Sphalerite in Aqueous
11. Stott J .F .D. and King R.A., "Petroleum Reservoir Souring in Hydrochloric Acid Solutions", Met.Trans., 12B (1981)
the North Sea", Capcis, UMIST. 645-649.
25. Nicol M.J., "The Non-Oxidative Leaching of Oxides and
12. Surinach P.P., "A New Concept of Treating Surfaces Sulphides: An Electrochemical Approach", Council for
Exposed to Oilfield Water Systems", SPE Paper N!-16262. Mineral Technology, Randburg, 2125, South Africa.
13. Cochrane, W.J., Jones; P.S. Sanders, Holt, D.M. and 26. Nicol M.J, and Scott P.D., "The Kinetics and Mechanism of
Moseley, M.J., "Studies on the Thermophilic' the Non-Oxidative Dissolution of some Iron Sulphides in
Sulfate-Reducing Bacteria from a Souring North Sea Oil Aqueous Acidic Solutions", J.South African Inst.Min.Met., 79
Field", SPE Paper N!!.18368, 1988. (1979) 298-305.
14. Bourgeois J.P., Aupaix N., Bloise R. and Millet J.L.,
"Proposition D'Explication de la Formation d'Hydrogene 27. Pourbaix M., "Atlas of Electrochemical Equilibria in
Sulfure dans les Stockages Souterrains de Gaz Nature! par Aqueous Solutions", Pergamon Press Ltd., (1966).
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29. Dutrizac, J.E. and MacDonald, R.J.C., "The Synthesis of
15. Vaughan D.J. and Craig J.R., "Mineral Chemistry of Metal some Copper Sulides and Copper Sulfosalts in 500-700 Gram
Sulphides", Cambridge University Press, (1978), pp.390-392. Quantities", Mat.Res.Bull., 8 (1973) 961-972.
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of II-VI Semiconductor Compounds in Nonoxidising Acids", "Observations on the Calibration of Solid-State Silver
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(1976) 1844-1848. Sulfide-Selective Electrode to Sulfide, Iodide and Cyanide",
18. Jibicki K., "Acid Decomposition Reactions on Compounds Anal. Chim. Acta, 93 (1977) 139-144.
and Minerals in the Fe-Ni-Sulphide System", Ph.D. Thesis, 32. Vesely, J,, Jensen, O.J. and Nicolaisen, B., "Ion-Selective
University of British Columbia, 1974. Electrodes Based on Silver Sulphide",t Anal. Chim. Acta, 62
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Pyrrhotite with Hydrochloric Acid", Can.Met. Quarterly, 11(2) 33. Harsanyi, E.G., Toth, K. and Pungor, E., "The Behaviour of
(1972) 407-411. the Silver sulphide Precipitate-Based Ion-Selective Electrode
20. Subramanian K.N., Stratigakos E.S. and Jennings P.H., in the Low. Concentration Range", Anal. Chim. Acta, 161
"Hydrometallurgical Processing of Pyrrhotite", (1984) 333-341.
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21. Van Weert G., Mah K. and Piret N.L., "Hydrochloric Acid Sulfide Ion-Selective Membrane Electrode in Alkaline
Leaching of Nickeliferous Pyrrhotites from the Sudbury Solution", Anal. Chern., 40(7) (1968) 1054-1060.
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Solution", Met.Trans., 11B (1980) 377-381.

205
 Table 1. Iron Sulphide Content from a Section of the Fulmar Sands -0.70
• Philips IS 550-S• l.S.E.
Iron Sulphide Content Reservoir Production Potential Bed thickness -0.72
~ Af!/Ag,S Wire Electrode
%bv ft
0-1.5 Very Good 100 u.i
-0.74 ~

~··-
(k = 1-10 D, <11 = 25- 35%) <..)

.. .
-0.76 ~
0.2-3.5 Poor 200 u)
(k = 1-500 mD, <II= 5- 33%) -0.78 ~
ui
0- L5 Good 200 >
> -0.80
0.5-6
(k = 30-4000 mD, <11 = 20- 30%)
Moderate - Good
(k = 2-1000 mD, ~ = 15- 25%)
100
..._
~ -0.82
.
~

.
EQ) ~
2-4 Very Poor 200 -0.84
(k=0.1-2mD.~= 13-18%) 0
D....
-0.86

-0.88
l ..
-0.90
-6 -4 -2
I Jog [ HS· ],""'"red
I
1.0 t" t I i I Fig. 2-Callbration plot for Philips IS sso-s 2 - I.S.E. and Ag/Ag 2 S wire electron.
I Fe(OH) 3 : Fe(OH)~
I

o.8 r--L~---~
\
i \
\
0.6
>
-
\

so42- \
\
~ 0.4 \
Fe293 (s) ~ Brass
...
N \

=
Q
\

00 \
\
D Epoxy Resin
tt3 0.2 \
\ • Iron Sulphide
> \
] \
111!11 Silver/Silver Sulphide
...... 0
cQJ
......
0
~ -0.2
QJ
"0
0
;...
...... -0.4
~

!
QJ

~ -0.6

-0.8
Fe
•~
-1.0
0 2 4 6

Rg. 1-Eh-pH diagram for the Iron-sulfur-water syatem-temperature = 298 K; pressure= 1 atmoaphere;
{[FE(II))+(Fe(lll)]} =1o-• M; [total dleaolved sulfui')=10-• M.
8 10 12 14

Rg. 3-Representatlon of the rotating ring disc electrode and cell.

..
(X)
.c--
(X)