Reservoir Souring Mechanisms and Prevention

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RESERVOIR SOURING: MECHANISMS

AND PREVENTION
Ian Vance and David R. Thrasher

7
Reservoir souring is an example of a process of injected water at the producing wells. Dual-
that is initiated at the microbiological level, yet porosity reservoir systems could potentially
exerts an effect over an entire reservoir and its result in breakthrough of H2S at production
produced fluids within the production lifetime wells prior to injection water breakthrough,
of a field. The overall economic impact of although this is not commonly reported. Later
microbial reservoir souring can be very sig- sections of this chapter show that the appear-
nificant, yet there are few technologies aimed ance of H2S at production wells is, in fact, the
at preventing the initiation of reservoir sour- last in a chain of events that may take several
ing, and these have shown limited success. years to complete. During the production life-
Treating the symptoms of souring by shutting time of a field, changes in the gas/oil ratio
in the wells most affected or by sweetening the (GOR) and water rate/total liquid rate ratio
sour gas has been the standard industry re- (water cut) may result in apparent souring. In
sponse. Attempts to prevent the initiation of these cases, no additional H2S is formed, but
souring have relied mainly upon treating in- changes in the relative masses of produced
jected water with biocidal agents. Recently, water (in which most of the H2S is dissolved)
technologies based upon principles of micro- and the production gas (into which most of
bial ecology have been applied with apparent the H2S partitions) result in a higher con-
success. centration appearing in the gas phase, as
shown in Fig. 1. Concentrations of gas-phase
SYMPTOMS OF SOURING H2S as high as several thousand parts per
Reservoir souring is characterized by an in- million per volume (ppmv) have been re-
creasing concentration of hydrogen sulfide corded in individual wells in reservoirs that are
(H2S) in production gas, typically after the actively souring and in those where existing
initiation of secondary recovery by water in- H2S is merely being redistributed between
jection and some time after the breakthrough phases. Across a souring field, significant
masses of H2S can be generated. The Skjøld
field in the Danish sector of the North Sea, for
Ian Vance, Centromere Limited, The Hollies, Dungells Ln., example, produced 1.15 tonnes of H2S per
Yateley, Hampshire GU46 6EY, United Kingdom. David R.
Thrasher, BP plc, Chertsey Rd., Sunbury on Thames, day with maximum wellhead concentrations
Middlesex TW16 7LN, United Kingdom. of 1,000 ppmv (Larsen, 2002). Maximum
Petroleum Microbiology, Edited by Bernard Ollivier and Michel Magot,
# 2005 ASM Press, Washington, D.C.

123
124 & VANCE AND THRASHER

FIGURE 1 Example of apparent souring of sweet reservoir oil and associated gas as a result of increasing
cut of sour water containing 16.6 ppmw H2S and a constant GOR of 220 scf/stb. No additional H2S has
been generated; only the relative proportions of sour water, sweet gas, and sweet oil have changed.

concentrations of H2S in gas as high as 40,000 cost in the region of $20 million at the outset
ppmv have been recorded in the Huntington of the project but up to $200 million if ret-
Beach field in California (Khatib and Salani- rofitted after initial design and construction
tro, 1997). had commenced. Khatib and Salanitro (1997)
estimate that using sour service materials could
ECONOMIC IMPACT add hundreds of thousands of dollars to the
Sour service metallurgy should be used to cost of each well, resulting in millions of
protect against sulfide stress-cracking corro- dollars of added costs to an entire project.
sion in facilities where the partial pressure of Similarly, it is common for oil and gas ex-
H2S exceeds certain threshold levels, as de- port lines to have a maximum allowable con-
fined by the guidelines of NACE Interna- centration of H2S that is calculated to maintain
tional standards under MR0175/ISO-15156. structural integrity. If the H2S concentration
From a survey of 12 reservoirs (Khatib and cannot be controlled below this critical con-
Salanitro, 1997), it was concluded that in all centration, the export of fluids would be
cases where the injection water contained sul- curtailed with subsequent loss of revenue.
fate, souring to some degree resulted; there- A characteristic of reservoir souring is that
fore, all new seawater flood projects should be not all production wells show the same in-
designed for sour service. There is a cost pre- creases in H2S concentration at the same time.
mium, estimated to be 2% of the total project If the aim is to lower the concentration of field
cost, for sour service metallurgy (Al-Rasheedi gas H2S to below a critical value, it may be
et al., 1999) that could become up to an order possible to accomplish this by selectively
of magnitude more significant and expensive, shutting in the wells producing the greatest
should retrofitting become necessary. On a $1 mass of H2S (Al-Rasheedi et al., 1999). This
billion project, metallurgy upgrades would obviously incurs a cost in terms of lost or
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 125

deferred production, although in practice, corrosion control, steps are taken to remove
these wells tend to have high water cuts, which oxygen from injected water and this provides
limit the financial penalty. an environment conducive to the growth of
Sour facilities entail additional costs in the obligately anaerobic SRB. In addition,
preventing operator exposure to toxic H2S; production chemicals, such as antifoams, scale
control of oil-wet, iron sulfide pads that re- inhibitors, and chemical oxygen scavengers,
duce separator performance; management of are dosed into the injection water; these
iron sulfide solids that interfere with produced may add to the nutrient pool of nitrogen,
water cleanup; and accumulation of iron- carbon, and phosphorus available for SRB
sulfide-based solids that may promote under- growth (Sunde et al., 1990).
deposit corrosion and foul equipment such as Flocculants such as aluminium or ferric
pump strainers. Chemical scavenger treat- sulfate can also introduce sulfate into pre-
ments that remove H2S from the production viously sulfate-free systems by the injection of
gas may also impose significant financial costs; fluids such as river water. Although steps are
owing to the volumes that must be transported taken to minimize the activity of bacteria in
and stored offshore, these treatments may have water injection systems, typically by con-
significant logistical implications. Similarly, tinuous chlorination and batch dosing with
batch biocide treatments of water injection organic biocides, the efficacy is variable. For
systems designed to control reservoir souring these reasons, it is common for viable plank-
require frequent, high-dose applications with tonic SRB population densities approaching
cost implications (Larsen et al., 2000). 1 ml1 to be present in injected seawater, de-
Continuous treatment of injected seawater spite the fact that incoming seawater may have
with a nitrate salt, a relatively recent technique population densities 3 orders of magnitude
in the oil industry, costs around $0.76 to $1.19 lower (Maxwell et al., 2002). It is inevitable,
per kg of sulfide removed ( Jenneman et al., therefore, that viable SRB will be injected
1997). Additional facilities such as nanofiltra- into water-flooded reservoirs, and in the case
tion units, proposed to control souring by re- of seawater flooding, in the presence of ap-
moval of sulfate from injected seawater (Rizk proximately 2,700 mg of available electron
et al., 1998), have a significant capital cost. acceptor liter1 in the form of dissolved sul-
fate. Once inside the reservoir, the high spe-
MECHANISMS cific area of reservoir rock, typically 0.93 to
There have been several biotic and abiotic 5.5 m2 g1 (Lake, 1989), provides a huge sur-
mechanisms proposed for reservoir souring, face for colonization by SRB. Studies of water
such as thermochemical sulfate reduction and backflowed from Californian injection wells
pyrite dissolution. These have been discussed showed that a region of high bacterial activity
by others (Herbert, 1987; Eden et al., 1993; associated with anaerobic or facultative anae-
Khatib and Salanitro, 1997). It is now widely robic bacteria existed in the reservoir close to
accepted that the reduction of sulfate by sulfate- the injectors (McKinley et al., 1988). Al-
reducing bacteria (SRB) is the most significant though this work failed to detect specific
mechanism of H2S production in reservoir biomarkers for the SRB Desulfobacter sp. and
souring as a result of waterflooding (Ligthelm Desulfovibrio desulfuricans in backflowed water,
et al., 1991; Sunde et al., 1993). The injection later results from an injector in a Canadian
of seawater or other water containing sulfate, field showed H2S concentrations in excess of
with an indigenous population of viable SRB, 120 mg ml1, hydrogenase activity, and viable
is a common practice used to increase oil SRB population densities of 103 ml1 in the
recovery beyond primary production by first two tubing volumes of injection water
maintaining reservoir pressure and sweeping that had backflowed to the surface (Taylor
oil towards production wells. For reasons of et al., 1991). In the Skjøld field in the North
126 & VANCE AND THRASHER

Sea, the presence of viable SRB and the gen- Another mechanism of formation damage
eration of H2S in concentrations up to 60 mg in injection wells (and valve operation in fa-
liter1 within the first 80 m3 of backflowed in- cilities) associated with the reinjection of
jection water have been described (Larsen et al., produced water involves the binding of as-
2000). Similar results have been recorded for phaltene and iron sulfide solids, formation
the Statfjord field in the North Sea, albeit with particulates, corrosion inhibitors, and biomass
a lower maximum concentration of 26 mg of into a paste-like mass, commonly referred to
H2S liter1 (Maxwell and Lejon, 1994). The as schmoo. If these produced water reinjection
dominance of mesophilic SRB in backflowed (PWRI) lines are also used for miscible gas
injection water and the bottomhole tempera- injection, the schmoo solids can dry out and
ture of 278C in the Statfjord wells were both flake off, causing plugging of injection wells.
consistent with the cooling of local zones of Bacterial activity in thick schmoo deposits on
the reservoir from 958C by the injection water pipe walls can also cause underdeposit pitting
and the initiation of SRB activity in the re- corrosion. Treatments for iron sulfide solid-
servoir close to the injectors. Estimates of the related issues may involve acid washes (with
extent of the zone from which the water was consequent hazard of generation of high H2S
returned suggests that significant SRB activity concentrations), tetrakishydroxymethylphos-
is located within a 10-m radius of the injectors phonium sulfate (THPS) biocide in combi-
(Maxwell and Lejon, 1994). Laboratory stu- nation with ammonium salts or organic
dies of oil field propionate-oxidizing SRB in phosphonates (Gilbert et al., 2002), or other
pressurized core floods demonstrated that a solvent and surfactant treatments.
sphere of reservoir rock with a radius of 9.3 m
could support the production of 50 kg of H2S SRB PHYSIOLOGY
day1 (Vance and Brink, 1994). It appears Fourteen species of SRB that have been iso-
feasible, then, that H2S production rates for lated from oil fields have individual growth
single production wells in souring fields of ap- temperatures spanning 4 to 858C (Magot et al.,
proximately 100 kg of H2S day1 (Larsen et al., 2000). Desulfotomaculum spp. isolated from
2000) could be accounted for by relatively North Sea produced water have been shown
small zones of SRB activity near injection to reduce sulfate at 808C when incubated at
wells. Using a specific rate of sulfate reduction pressure up to 4,500 lb/in2 (Rosnes et al.,
of 5  1015 mol cell1 day1 determined for 1991). On the basis of temperature and pres-
a marine sediment (Jørgensen and Bak, 1991) sure tolerance, oil field SRB, therefore, would
and a mass of 8  1013 g cell1 (Lynch, 1988) also be expected to be active in hotter zones of
implies that 0.5 tonnes of SRB biomass would waterflooded reservoirs, further from the
be required to generate the 100 kg of H2S cooling influence of injection wells. As a
day1 produced from a single production well. group, SRB are nutritionally diverse and able
Where injection wells connect with frac- to use electron donors and carbon sources
tures in the rock (whether fractures are natu- present in petroleum reservoirs such as acetate,
rally present or hydraulically or thermally propionate, naphthenic acids, n-alkanes (C6 to
induced by the injection of cold water), co- C20), hexadecene, benzoate, benzene, to-
lonization of fracture surfaces and growth of luene, xylene, and phenol (Widdel, 1988;
biofilms may also contribute significantly to Aeckersberg et al., 1991; Heider et al., 1999;
the H2S generation process. The establishment Lovley et al., 1995; Bak and Widdel, 1986).
of sulfide-producing biofilms in porous rock Since acetate is present in formation waters at
results in formation damage by the production concentrations as high as 1,500 mg liter1, its
of extracellular polysaccharides and precipita- use as an electron donor by SRB has been
tion of metal sulfides, causing plugging and implicated in conceptual models of micro-
reducing permeability (Rosnes et al., 1991). biological reservoir souring:
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 127

CH3 COO þ SO4 2 ! 2HCO3  þ HS oxidizing bacteria may directly provide elec-
tron donors for SRB (Widdel, 1988). Sig-
Using probes for rRNA sequences, Brink et al. nificantly, H2S generation has been observed
(1994) detected the presence of acetate-oxi- in a sand-packed column model containing
dizing SRB of the genus Desulfobacter in an crude oil and oil field bacteria when flooded
Alaskan seawater injection system, demon- with synthetic seawater, regardless of whether
strating a possible route to the reservoir. Si- the seawater was saturated with oxygen or
milarly, propionate, somewhat less abundant reduced with dithionite (Myhr, 2003). Al-
than acetate in formation waters, is oxidized to though SRB that utilized crude oil were iso-
the level of acetate by SRB, as shown in the lated from the column, they could only do so
following reaction: in the presence of added surfactant, suggesting
4CH3 CH2 COO þ 3SO4 2 ! 4CH3 COO that interaction between components of the
þ 4HCO3  þ 3HS þ Hþ
biofilm would be necessary to sustain H2S
generation under anaerobic conditions.
It must be recognized, however, that reservoir
zones (where mixing occurs between injected PWRI
seawater with a high sulfate concentration and Data from backflowed injection wells pre-
formation water with a high concentration of dominantly on seawater duty show that H2S
organic acid) are spatially limited. In addition concentrations of tens of milligrams per liter
to the short-chain organic acids, hydrocarbons can be generated in injection water in the
such as hexadecane which are constituents of close vicinity of injection wells. The practice
residual oil have been shown to be completely of PWRI as part of a waterflood has the po-
oxidized by SRB: tential to increase H2S production beyond
seawater-induced souring (Tyrie and Ljosland,
C16 H34 þ 12:25SO4 2 þ 8:5Hþ ! 16HCO3  1993). Unlike seawater, produced water often
þ 12:25H2 S þ H2 O contains significant concentrations of elec-
tron donors and carbon sources in the form
Other water-soluble hydrocarbons such as xy- of acetate, propionate, and nitrogen (as am-
lene and toluene are also completely oxidized: monia). Produced water contains different
C7 H8 þ 4:5SO4 2 þ 3H2 O ! 7HCO3  production chemicals compared to injected
þ 4:5HS þ 2:5Hþ seawater, typically, scale inhibitor, corrosion
inhibitor, demulsifier, and wax inhibitor,
Given the abundance of residual oil, even in which may contribute to the nutrient pool
waterflooded zones, and the availability of available to SRB. Over time, produced water
sulfate in deliberately deaerated injected sea- tends to contain a greater proportion of in-
water, it would be surprising if SRB activity jection water that has traversed the reservoir;
did not flourish in zones where the tempera- if this injection water is seawater, it brings
ture was low enough. Although injection abundant sulfate. Even if sulfate availability is
water is deaerated, it can contain low con- low in produced water, it may be commingled
centrations of dissolved oxygen of around 50 with seawater prior to reinjection, thus pro-
ppb. It is feasible that a limited zone of aerobic viding a suitable electron acceptor. Addition-
hydrocarbon oxidizing bacterial activity could ally, produced water often contains much
be supported on residual oil very close to in- higher population densities of viable SRB
jection wells. Under such conditions, car- than seawater. Without additions, SRB pre-
boxylic acids (Widdel, 1988) and alcohols sent in produced water may generate signifi-
(Myhr et al., 2002) may be formed and act as cant concentrations of H2S. In samples of
electron donors and carbon sources for SRB. produced water from a field operated by the
Additionally, cells of aerobic hydrocarbon- BP company that contained 100 mg of acetate
128 & VANCE AND THRASHER

liter1, 50 mg of propionate liter1, and 105 centrations of H2S are produced in the water
mg of sulfate liter1, indigenous SRB pro- phase that could eventually account for hun-
duced 28 mg of H2S liter1. The H2S gener- dreds of parts of H2S per million per volume
ated accounted for almost complete reduction of production gas. Back-calculating the con-
in the available sulfate. Formation waters with centration of H2S in soured seawater necessary
much higher concentrations of organic acids to account for the most sour production gas
are associated with reservoirs currently under gives a figure of approximately 100 mg liter1,
development; if reinjected, these have the which is much less than the 900 mg liter1
potential to generate higher concentrations of that could theoretically be produced if the
H2S. As shown in Fig. 2, the proportion of reduction of all of the sulfate available in sea-
formation water and commingled seawater in water proceeded to completion. It seems clear
such a PWRI scheme influences the max- that SRB activity even in biofilms near in-
imum concentration of H2S generated directly jectors is limited by some factor other than
from the nutrients in the injected water. sulfate availability. By the same token, when
injected seawater breaks through to produc-
LIMITATION OF SULFATE tion wells after it passes through the reservoir,
REDUCTION it still contains much of the original sulfate,
Although thermophilic SRB have been iso- which again implies that bacterial sulfate re-
lated from producing oil reservoirs (Stetter duction is inhibited throughout the reservoir.
et al., 1993; Beeder et al., 1995), their sig- Indeed, produced water often contains con-
nificance in the souring of seawater-flooded siderable concentrations of acetate and pro-
reservoirs is not clear. Injecting large volumes pionate in addition to sulfate. The limiting
of cool seawater even into high-temperature factor, therefore, seems unlikely to be the
reservoirs has a significant cooling effect on availability of an electron donor or acceptor. If
the zone adjacent to the injector. Injector the limiting factor is the lack of a nutrient and
backflows suggest that within this zone, con- this lack is supplied by the injected seawater

FIGURE 2 Theoretical H2S production


in mixtures of seawater, assumed to contain
no organic acids and 2,700 mg of sulfate
liter1, and produced water, assumed to
contain 115 mg of sulfate liter1, 50 mg of
propionate liter1, and 100 mg of acetate
liter1.
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 129

with its suite of added production chemicals, reported finding framboidal pyrite in core
this will be consumed rapidly in the vibrant material from behind the floodfront, inter-
community of bacteria thriving in the biofilm preted as evidence of scavenging of H2S
close to injection wells. The high specific generated during the waterflood. The pre-
surface area of porous reservoir rock means vailing temperature, pressure, and pH all in-
that oil field bacteria colonizing the surfaces in fluence the mineral solubility and hence the
a biofilm are able to very effectively strip magnitude of the scavenging reaction. The
nutrients from the waterflood. Over 1,300 mg possible degree of scavenging within a re-
of propionate liter1, for example, was oxi- servoir is rather difficult to predict, although
dized across a 15-cm path length of 120-mil- the relative abundance of the minerals in-
lidarcy (mD) sandstone with a flood velocity volved may be available from petrographic
of 0.43 m day1 (Vance and Brink, 1994). analyses of reservoir core samples obtained
Downstream from the zone of activity, which during drilling. However, the heterogeneity
assumes that radial flow will occur in all other of the formation may also mean that vast vo-
parts of the reservoir, SRB activity will be lumes of the reservoir will be of undetermined
inhibited by the lack of the limiting nutrient. composition. Sunde et al. (1993) lists crushed
Since the H2S is a by-product of bacterial reservoir rocks that adsorb between 5 and
sulfate respiration, it is formed in the water 19,600 mg of H2S per g of rock under labora-
phase, the water-rock interface, or the water- tory conditions, although the high figures re-
residual oil interface. Once generated, the H2S ported may be overestimates compared to in
moves through the reservoir dissolved in the situ conditions. For instance, the material was
water phase in the direction of the waterflood. in an oxidized state, and crushing would in-
The fate of the H2S within the reservoir de- crease surface area available for adsorption and
pends upon the prevailing physicochemical other interactions. Other measurements of
conditions; these are reservoir specific. H2S adsorption on uncrushed core have also
been made by Ballard and Beare (1997), for
example, giving values within this range. The
H2S SCAVENGING IN THE
RESERVOIR exact nature of the H2S scavenging miner-
Reaction with iron-rich reservoir minerals is a alogy between an injection well and produc-
significant sink for H2S generated by SRB tion well can greatly influence the timing of
(Ligthelm et al., 1991; Sunde et al., 1993; Eden the appearance of H2S. This is one phenom-
et al., 1993). Siderite (FeCO3), hematite (Fe2O3), enon that can possibly account for the patchy
and magnetite (Fe3O4) have all been implicated distribution of sour gas between production
in the scavenging of H2S from the fluid phase, as wells in one zone of a reservoir, although it
shown in the following reactions: may be more likely to be dominated by dif-
ferences in water movement patterns. In
FeCO3 þ H2 S ! H2 O þ CO2 þ FeS practice, the H2S scavenging mechanism is
Fe2 O3 þ 3H2 S ! 3H2 O þ FeS2 þ FeS thought to be a surface mechanism. This means
Fe3 O4 þ 4H2 S ! 4H2 O þ FeS2 þ 2FeS that even if significant quantities of iron mi-
nerals are present in terms of bulk rock com-
The participation of these minerals in the position, their scavenging capacity is limited
scavenging reactions depends upon their so- by the surface area available for interaction
lubility in the water phase, and this results in with the H2S present in the water traveling
an aqueous solution of ferric ions being pre- through the pore network, as well as other
sent to react with the H2S, which is precipi- specifics of the water-rock interactions in-
tated as iron sulfides—from monosulfides volving mineral dissolution, ion exchange,
ranging in form from Fe1xS to Fe1þxS to oxidation-reduction, and other physical ad-
disulfide pyrite (FeS2). Ligthelm et al. (1991) sorption processes.
130 & VANCE AND THRASHER

As the scavenging surfaces of the minerals seawater front and delays its appearance in
become exhausted, H2S dissolved in the water production wells. The partition coefficient of
phase moves with the waterflood to the pro- H2S between the phases depends upon the
ducers at higher concentrations. Changes in temperature, pressure, and chemistry of the
injection water chemistry, temperature, and two phases. Ligthelm et al. (1991) measured
pressure (e.g., on switching from seawater in- the H2S partition coefficient between a si-
jection to PWRI) during a waterflood may mulated North Sea oil and seawater under a
also influence the solubility of previously range of conditions relevant to North Sea
generated iron sulfide solids, thereby increas- reservoirs and reported that the coefficient
ing or decreasing the H2S-scavenging capacity only changed between values of 18 and 19.5
of the rock. Some H2S will also dissolve or for conditions of 258C at 35,000 kPa to 1008C
partition into the residual hydrocarbons be- at 15,000 kPa, respectively.
hind the floodfront, which therefore acts as an The concentration of H2S partitioned into
additional sink for H2S. Given these uncer- residual oil behind the floodfront is up to
tainties, analog field examples can help define approximately four to five times that in in-
expectations of formation scavenging capacity jected seawater, i.e., around 400 ppmw. As-
and general souring development, while also suming a residual oil saturation of water in the
taking into account different fluid properties, region of 35%, a porosity of 25%, and a rock
assumptions of injection water movement, and density of 2.8 g/cm3, the mass of H2S dis-
aquifer activity. solved in residual oil behind the floodfront
would be on the order of 11 mg of H2S per g
WATER MOVEMENT of rock. This is an order of magnitude less than
In addition to formation mineralogy, the the > 100 mg g1 determined in mineralogy
proximity of production wells to injectors and scavenging experiments, and so it is expected
the water injection rate influence the timing that the mineralogy aspects dominate over
and extent of H2S appearance in produced dissolution into residual fluids in terms of re-
fluids. Production wells relatively closer to servoir sinks for biogenic H2S.
injectors experience breakthrough of injected As discussed earlier, when the reservoir
seawater earlier than those located more re- fluids reach the surface, the H2S in the water,
motely. With the seawater eventually comes oil, and gas will partition in test and produc-
H2S that has been generated in the reservoir. tion separators according to the pressure, tem-
Fractures or high-permeability streaks carry a perature, and chemical characteristics of the
greater throughput of injection water, leading produced fluids. Other factors, such as ki-
to earlier breakthrough of H2S and higher netics, gas stripping effects, and mineral pre-
souring severity. Clearly, a short path length cipitation, may also cause measured partition
between injector and producer, in combina- coefficients to deviate substantially from ther-
tion with a high seawater injection rate, means modynamic equilibrium estimates. Thermo-
that any scavenging effect of the mineralogy dynamic models of the production process can
will become exhausted relatively quickly and be used to estimate how H2S will distribute
that H2S will arrive at the producer after a between phases throughout the plant to aid
relatively short period. Conversely, longer facility design and determine when metallurgy
path lengths and lower water injection rates and export thresholds could potentially be
delay the appearance of H2S at producers. exceeded (Al-Rasheedi et al., 1999). Typi-
cally, the highest concentration of H2S is
H2S PARTITIONING found in the gas phase, and it is dependent
Partitioning of the H2S from the relatively upon the total mass of H2S produced and the
faster-moving water phase to the oil phase water cut and GOR. Additionally, if sour field
effectively removes H2S from the injected gas is used to gaslift production wells, this will
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 131

have the effect of souring gas from wells that mally be expected to be carried out). On a
are intrinsically sweet and could dilute the H2S single-well basis, it can be constructive to plot
concentration in gas from sour wells. the sour water concentration or the injection
water sour water concentration over time.
DIAGNOSIS The sour water concentration is simply the
Routine well surveillance is often accom- total mass of H2S produced by the well per
plished with gas detection tubes to sample unit of time divided by the mass of water
production gas and quantify the concentration produced by the well per unit of time. This
of H2S present. This is a useful way of mon- approach also normalizes for changes in pro-
itoring a sweet reservoir, since any instances duction rates of the different phases and pro-
of H2S presence would warrant further in- vides an index of souring severity that can be
vestigation. It is also less complex than mon- compared between wells. A refinement of this
itoring H2S in other phases. However, in a method can be applied if the injected water is
field where sour gas has been produced from sufficiently different in chemical composition
start-up, surveillance at this level cannot on its to allow an estimation of its contribution to
own provide enough information to judge if the total water cut. Dividing total H2S pro-
further souring is occurring. By using the duction by total injection water production
measured concentration of H2S in the gas gives a value for injection water sour water
phase and multiplying this concentration by concentration. Monitoring injection water
the gas production rate from the test separator, sour water concentration can be particularly
it is possible to determine the mass of H2S insightful if it is accepted that injected water
produced in the gas. Similarly, simultaneous contributes most of the H2S observed at pro-
measurements of H2S concentration in the duction wells.
water and oil phases, in combination with
water and oil production rates, allow the cal- PREDICTION
culation of the mass of H2S produced in these There is obviously a potential commercial
phases. Adding these rates gives a value of total advantage in being able to predict if an un-
H2S produced per production well per day. developed reservoir is likely to sour or if
This approach is less susceptible to the influ- changes in reservoir management of a produ-
ences of changes in operational conditions cing field will increase the probability of
than determining the concentration of H2S in souring. In this context, the timing, the extent
the gas phase alone (Larsen et al., 2000). By of souring, and knowledge of the wells most
adding up the total H2S production rates for likely to be affected are important in for-
all production wells, a figure for the whole mulating options for possible control mea-
field is calculated; this can be useful in mon- sures. Details of several mathematical models
itoring the effect of treatments aimed at con- of microbiological reservoir souring have been
trolling souring when these are applied across published, which allow prediction of sour-
the whole field if production is relatively ing patterns in waterflooded reservoirs. The
stable. models differ in terms of the detailed concept
For the reasons discussed above, it may be upon which they are based. One concept is
of particular value to monitor H2S production based upon H2S being formed by SRB only in
rates and water chemistry closely to determine reservoir zones where mixing occurs between
injection water breakthrough in sentinel wells the sulfate-rich but organically impoverished
that are expected to show injection water injected seawater and sulfate-depleted but
breakthrough relatively early in field life, since organic-acid-rich formation water (Ligthelm
these are likely to be the first to show the et al., 1991). This mixing zone, which is driven
effects of souring (although regular monitor- by diffusion and dispersion processes, is con-
ing during production well tests would nor- sidered to move through the reservoir in the
132 & VANCE AND THRASHER

direction of the waterflood; its presence im- nents are turned over as additional nutrient
plies that in a mature waterflood the mixing sources. The SRB growth is modelled ac-
zone, and hence the zone of SRB activity, will cording to conventional Michaelis-Menten
be deep in the reservoir, remote from the kinetics with a fraction of available nutrients
injection well. Since the nutritional require- assumed to be consumed by biofilm-dwelling
ments of SRB will be fulfilled only in the bacteria other than SRB. All H2S generation
water-mixing zone, which is at the seawater takes place within a limited volume around
front, SRB activity will proceed only where the injection well in this model. Scavenging of
suitable temperatures coincide with mixing H2S in the reservoir is treated as a two-step
zones. This particular model, however, does process: the first step involves dissolved com-
not consider the effect of temperature upon ponents and the second phase involves solid-
SRB activity and hence H2S generation. If the phase components. The model is sensitive to
initial reservoir temperature is higher than the the nutrient status of the injected water, since
injected water temperature, a zone of cooled this is assumed to provide the limiting nutrient
reservoir will develop, moving in the direc- for SRB growth.
tion of the waterflood but lagging behind the All three models contain terms that describe
mixing zone. The model implies that ther- the scavenging mechanism which contributes
mophilic SRB, flourishing in higher-tem- to attenuation in the breakthrough of H2S
perature regions of the reservoir, must be relative to the breakthrough of injected sea-
responsible for H2S generation. The effects of water. The terms describing the generation of
phase partitioning and mineral scavenging are H2S by SRB and the location of the zone of
included in the modelling approach. sulfate reduction are, however, different in
The establishment of reservoir zones in each model. To some extent, these differences
which temperature conditions are suitable to may not be important. The most significant
support mesophilic and thermophilic SRB virtue of any model is that it can be shown to
activity is a key feature of the souring model predict actual field experience and hence may
described by Eden et al. (1993). The re- be used with some certainty as a basis for
quirement for a mixing zone between injec- commercial decisions.
tion and formation waters is not essential to
this model. The nutritional requirement of the A FIELD EXAMPLE
SRB is satisfied by a term for sulfate conver- A typical example of a seawater-flooded re-
sion ranging between 1 and 5% of the available servoir that soured during production lies in
concentration, which is equivalent to a sour the United Kingdom sector of the North Sea,
seawater concentration of 9 to 45 mg of H2S northeast of the Shetland Islands at a water
liter1. depth of 160 m. The field consists of a typical
A more detailed modeling approach to the Brent Group Middle Jurassic sandstone re-
generation of H2S by SRB in the reservoir is servoir containing light 388 American Petro-
described by Sunde et al. (1993). This model leum Institute (API) gravity crude oil at a
assumes that a biofilm containing SRB is es- total depth of 2,750 m. Production com-
tablished close to injection wells, the growth menced in the late 1970s, reaching more than
of which is determined by the concentration 100,000 barrels per day (bpd) after 4 years.
of a limiting nutrient present in the injected Seawater injection was used to provide sweep
seawater. During the initial growth phase, an and pressure support with injection rates ex-
exponential increase in H2S production is ceeding 200,000 bpd. The field has a fault
expected, but this reaches a maximum when block structure with five major compartments,
the limiting nutrient has become exhausted. and there is limited aquifer influx into only
The production rate of H2S continues to in- two of these. Initial reservoir temperature was
crease at a lower rate as the biofilm compo- 1048C with an initial pressure of around 6,100
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 133

lb/in2. The natural GOR of the oil is low, at Part of the field development involves a
around 220 to 290 standard cubic feet per single injection well, supporting six producers
stock tank barrel (scf/stb), and as gaslift has in an isolated fault block. Injection water
been used in only a small number of wells, this movement is accelerated through part of the
means that gas-phase H2S concentrations are formation by a high-permeability streak near
very sensitive to the sour water concentration, the base of the section. Phasing of drilling the
even at low water cuts. The formation water production wells has also resulted in changes
has lower salinity than seawater (chloride to the pattern of water movement through
concentration is around 13,000 mg liter1), each of the fault-constrained segments of this
with acetate concentrations in the range of sector of the field. The water cut (Fig. 3), gas-
600 to 1,400 mg liter1. High-permeability phase H2S concentration (Fig. 4), and sea-
streaks of around 4,000 mD and rapid water water-sour water concentration profiles (Fig.
breakthrough have resulted in some wells 5) show how souring develops after the wa-
producing at very high water cuts and ex- terflood front reaches each producer. The
ceeding 1,000 to 3,000 ppmv of H2S in the seawater sour water concentration profiles also
gas phase at surface, giving 500 ppmv in bulk show consistency in the degree of souring
field gas. The field was originally designed for severity, timing, and rate of increase, de-
sour service, so the main constraint on H2S pending on where the wells are located in the
production was the gas export specification. sector, and the process was modelled in detail
Several alternative techniques were used (in- on the simulator described in Al-Rasheedi
cluding organic peroxide, acrolein, dichlor, et al. (1999). At any one time, there are only one
triazine, and a molecular sieve) to sweeten the or two really dominant H2S producers out of
export gas to pipeline specifications as H2S the six involved in this sector, as the wells start
concentrations rose through time (L. Cowie, to sour with different timings. It is therefore
personal communication). More recently, as important to define the key producers that
production declined in the field, there was no influence the overall H2S production profile
longer sufficient gas being produced to supply in any H2S forecast. These wells are typically
fuel for operations, so the field subsequently the ones that have the shortest injection water
became an importer of gas for fuel. breakthrough times and/or produce injection

FIGURE 3 Well water cut profiles in an example of a seawater-flooded, souring


reservoir.
134 & VANCE AND THRASHER

FIGURE 4 Well gas-phase H2S concentration profiles in an example of a seawater-


flooded, souring reservoir.

water for the longest time. Therefore, they value across the formation. Simplification of
have the highest pore volumes throughput. the fluid movement complexity into a single
Conversion of the seawater sour water parameter of this sort of course has its limita-
concentration profiles from time into pore tions compared with more-detailed simulation
volume throughput is done based on cumula- techniques. Nonetheless, rapid transit of in-
tive incremental injection steps, typically nor- jection water through a reservoir to a pro-
malized against injection water breakthrough duction well is a key factor in influencing the
time as a first approximation. The pore volume severity of souring, and the injection water
throughput estimate is by necessity an averaged breakthrough time therefore represents an

FIGURE 5 Well seawater sour water concentration profiles in an example of a


seawater-flooded, souring reservoir. The total well H2S production is estimated from
gas-phase H2S concentration, allowing for H2S partitioning between gas, oil, and water
phases. The seawater fraction in produced water is estimated from chloride
concentrations.
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 135

important parameter for H2S production. formed, and those that reduce the mass of H2S
Normalized seawater-sour water concentra- that is generated. If microbial souring is lik-
tion profiles for two of the wells are shown in ened to a disease caused by bacteria, the first
Fig. 6, wells 1 and 2. They differ from those methods seek merely to mask the symptoms,
presented by Sunde et al. (1993), as a result of the second are prophylactic, and the third are
influences from a number of possible factors partial cures.
including mineralogy, reservoir heterogeneity,
and nutrient inputs in the injection water. MASKING SYMPTOMS
Two other wells (Fig. 5, wells 3 and 4) show The surveillance of individual wells described
different normalized seawater sour water con- previously allows the relative degree of sour-
centration profiles, but again they are con- ing to be mapped for all of the producing wells
sistent with their relative locations in the in the field. It is then possible to select can-
sector and potential differences in water didate wells for shutting in on the basis of their
movement. Despite the uncertainties involved, contribution to total field production and the
such sour water concentration profiles not tolerable concentration of H2S. This approach
only have uses in forecasting future H2S pro- can have a significant effect on field H2S
duction to make commercial decisions affect- production, with reductions of 20% achieved
ing oil field developments, they also provide by shutting in producers with high water cuts
information on measures of the success (or (Larsen et al., 2000). Significant effects can
otherwise) of souring control treatments. also be achieved by slightly less terminal
measures by isolating zones producing sour
SOURING CONTROL water under different circumstances. This can
Methods of controlling microbial reservoir be done by mechanical means (plugs or liner
souring are of three types: those that attempt patches) or by squeezing cement or other
to deal with the H2S after it has been gener- chemicals such as gels into the relevant zones.
ated and produced from the reservoir, those Water shutoff can have a double impact on
that attempt to prevent H2S from being reducing souring by both decreasing H2S rate

FIGURE 6 Seawater sour water concentration profiles against normalized pore


volume throughput in an example of a seawater-flooded, souring reservoir. Pore
volume throughput is based on the dominant analog well 2 injection water
breakthrough time.
136 & VANCE AND THRASHER

into the well and reducing the partitioning active biofilm is close to injection wells, then
effect by lowering the water cut. However, it should be more easily controlled by treat-
success is not guaranteed with these tech- ments that are applied by way of the injection
niques, due to operational difficulties or geo- water. Once an active biofilm of considerable
logical factors affecting water movement in proportion has been established in the re-
the near-well bore region. servoir, it can only be treated successfully by a
Treatment of sour gas with liquid H2S large mass of biocide. Clearly, if the mass of
scavengers may be achieved in two ways. SRB in the biofilm close to an injector is on
Scavengers such as those based on triazine the order of tonnes, it will require large bio-
chemistry are typically injected into the sour cide doses to kill only the SRB. Since bacteria
gas stream through atomizing nozzles. Effec- other than SRB are also present in the biofilm,
tive dose rates of approximately 7 to 15 parts the demand for biocide will be even greater
(by weight) of scavenger to 1 part of H2S because the biocide will react indiscriminately
scavenged mean that scavenger consumption with all types of biomass. The application of
can be significant on large, sour fields. Alter- batch doses of THPS biocide in the injection
natively, the sour gas can be treated in a water, for example, has been shown to de-
bubble tower contactor containing the liquid crease the H2S production rate by up to 25%
scavenger, such as amines including triazines, (Larsen et al., 2000). To maintain control,
sodium hydroxide, aldehydes, metal oxide batch doses must be repeated at a frequency
slurries, and nitrites. Solid-phase scavengers related to the regrowth or recolonization rate
based on iron or zinc oxide in contactor ves- of the SRB. To maintain the H2S production
sels are generally used where weight and space rate within 1 order of magnitude, an effective
considerations are less important. biocide treatment must be applied at a fre-
Sturman et al. (1999) carried out 36-h quency of three doubling times or less. Figure 7
squeeze treatments on production wells with shows an example where the SRB biomass in
nitrite and demonstrated a significant drop in a reservoir is assumed to grow with a doubling
H2S production for up to 7 months. Nitrite is time of 4 days. The effect of repeated biocide
known to inhibit SRB activity and is also an doses which kill 90% of the SRB present, at a
H2S scavenger, but the authors suggested that frequency of 7 days, is to delay H2S produc-
the most significant mechanism was the re- tion. In Fig. 7, a threshold level equivalent to
oxidation of H2S-scavenging, iron-rich mi- 5 mg of sour water liter1 is shown, assuming
nerals near the production well bore. Once an injection rate of 20,000 barrels of water per
reoxidized by reaction with nitrite, the H2S day (bwpd) and no scavenging. If the biocide
sinks participate in scavenging reactions that kill efficiency is greater, the frequency of
lower the concentration of H2S in the fluids dosing is higher, or the doubling time of SRB
moving into the production well. Eventually, is longer, there will be more benefit from such
however, the sulfide capacity of the miner- treatments.
alogy becomes saturated, and the H2S pro- A partial cure for souring may be achieved
ductivity of the well increases. This approach by selecting production chemicals that are
seems best suited to wells with low H2S pro- added to the injection water to exclude those
ductivities to avoid the need for frequent that provide additions to the nutrient pool
treatments with nitrite, which carry a penalty available for SRB. Ammonium bisulfite is
of deferred production. commonly used as an oxygen scavenger in sea-
water injection systems, for example, despite
PARTIAL CURES the fact that it provides a source of reduced
The use of biocide to control microbiological nitrogen for bacterial growth (Sunde et al.,
reservoir souring has been attempted with 1990). Indeed, these workers suggest that pro-
varying degrees of success. Arguably, if the duction chemicals may increase the availability
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 137

FIGURE 7 Impact of a biocide


treatment that kills 90% of an SRB
population every 7 days. It was
assumed that the initial SRB popula-
tion was 1 cell; the population had a
doubling time of 4 days and a specific
rate of sulfate reduction of 5  1015
mol cell1 day1. The daily produc-
tion rate of H2S assumes that water
from a 20,000-bwpd injection well
reaches a sour water concentration of
5 mg liter1.

of carbon, nitrogen, and phosphorus in in- as an injection test or fracture initiation, has
jected seawater by factors of up to 410, 19, and the potential to introduce SRB into a near-
3, respectively. Careful control over produc- well-bore zone, which will eventually be
tion chemicals could restrict the growth rate of subject to a high flux of nutrients in the in-
SRB in the reservoir and hence have a positive jected water stream. As previously noted,
impact on souring. If, for example, restriction the injection water itself also introduces ac-
of growth rate by a factor of 4 is achievable by tive SRB into the reservoir. Even if the viable
avoiding the use of production chemicals that SRB population density is low, the high rate
are potential nutrient sources, it would take of water injection into each well ensures that
four times as long to reach a particular rate of the near-well-bore region receives a sig-
H2S production. nificant level of inoculation each day. None-
theless, concern is often expressed over the
PROPHYLAXIS impact that the SRB population of injected
If SRB could be excluded from oil field op- water may have on the degree of reservoir
erations, then it would be possible to control souring. Given injection rates in the region of
reservoir souring. There is, however, growing 20,000 bwpd per well, it would require a
evidence that petroleum reservoirs have in- complete removal of SRB to make a sig-
digenous microflora that may include meso- nificant impact on the rate of souring. Figure 8,
philic and thermophilic SRB (McInerney for example, shows that an initial SRB po-
et al., 1993; Magot et al., 2000). Even if the pulation near an injector of 1, 10, or 100 cells
producing zone of a reservoir did not have an makes little difference to the development of
indigenous SRB population, it is well known significant production rates of H2S.
that drilling muds often contain viable popu- If sulfate could be removed from injection
lations of SRB (Dow, 1987), and this is a water, this would inactivate the most sig-
vehicle for contaminating the waterflooded nificant metabolic pathway to H2S produc-
zones at an early stage of reservoir develop- tion. Other oil field chemicals such as
ment. In addition, any activity that requires thiosulfate and sulfite can also be converted to
injection of liquid into an injection well, such sulfide by SRB (Widdel, 1988); hence, the
138 & VANCE AND THRASHER

FIGURE 8 Effect of initial SRB population. It was assumed that the initial
SRB population was 1, 10, or 100 cells. The population had a doubling time
of 1 day and a specific rate of sulfate reduction of 5  1015 mol cell1 day1.
The daily production rate of H2S assumes that water from a 20,000-bwpd
injection well reaches a sour water concentration of 5 mg liter1.

complete removal of sulfate alone may not voir souring but would not be a total cure.
totally prevent sulfide production. Rizk et al. Interestingly, the half-saturation concentration
(1998) have shown that desulfated seawater of sulfate for bacterial sulfate reduction is very
from the Marathon Brae platform, which had low. Widdel (1988) gives a range of 0.5 to 20
a sulfate concentration of 160 mg liter1 (after mg liter1, while Sunde et al. (1993) consider
50% dilution), resulted in sulfide production 0.1 mg liter1 to be typical of marine SRB.
of 50 mg liter1 in a sand pack reservoir model Desulfation to an extremely low concentra-
flooded with synthetic formation water in tion, therefore, would be required to have an
addition to the desulfated water. These au- effect on the rate at which SRB produce H2S,
thors suggested that sulfate concentrations but desulfation to moderate concentrations
as low as approximately 50 mg liter1 are would limit the maximum concentration of
achievable by applying nanofiltration tech- sour water that could be produced. Some in-
nology to water injection facilities. Potentially, jection facilities are now being designed to
however, even 50 mg of sulfate liter1 in in- remove sulfate from seawater to concentra-
jected water could give rise to 16.6 mg of H2S tions significantly below 50 mg liter1 with
liter1 in reservoir sour water. Once the ef- mitigation of the barium sulfate scale as the
fects of scavenging and partitioning in the primary economic driver. This will have the
reservoir have proceeded to completion, additional benefit of limiting the maximum
production of this concentration of sour water potential reservoir souring severity.
would give rise to the gas-phase concentra- Manipulation of the reservoir environment
tions shown in Fig. 1. Partial desulfation in a way that discourages SRB activity can be
would be expected to slow the rate of reser- achieved by additions to existing waterfloods
7. RESERVOIR SOURING: MECHANISMS AND PREVENTION & 139

or by using alternative sources of water. Ma- technology has been demonstrated to be ef-
nipulation of salinity is one parameter that has fective at reservoir scale (Sunde et al., 2004;
been used to positive effect. Postgate (1984) Larsen, 2002; Jenneman et al., 1997). A po-
described a halotolerant strain of D. desulfur- sitive impact on H2S production after treat-
icans that was grown in a medium containing ing injected seawater with calcium nitrate has
11% NaCl, and Cord-Ruwisch et al. (1987) also been observed on the BP Foinaven float-
suggested that the activity of most SRB is ing production, storage, and offloading vessel
inhibited in NaCl concentrations above 5 to site. Well P27 was chosen as a sentinel well,
10%. Significantly, Cord-Ruwisch et al. de- since it was predicted to sour early in field life
scribed SRB from an oil field production due to the relatively fast breakthrough of in-
system that grew slowly in 27% NaCl, al- jected seawater. The prediction was shown to
though concentrations above 15% were in- be accurate when H2S was first detected in
hibitory to all other SRB isolated from the well P27 in March 2000. Nitrate treatment
same source. Tinker et al. (1983) described the started in May 2001 at a dose of 56 ppmv of a
souring of a Michigan oil field resulting from 45% Ca(NO3)2 solution in the 140,000-bpd
the initiation of waterflooding with low- seawater injection system. Breakthrough of
salinity water with NaCl concentrations of up the nitrate-treated water was predicted in May
to 0.03% into formation waters with NaCl 2002; at this time, a large decrease in sour
concentrations up to 36.6%. Production of seawater concentration was observed, as illu-
H2S occurred when the NaCl concentration strated in Fig. 9. This was interpreted as an
produced fell below 12%. Subsequent changes early indication of the success of the treat-
of the waterflood to higher-salinity water in- ment. Since that time, H2S production from
hibited H2S production. the well has remained significantly lower than
Treatment of injection water with nitrate is predicted by comparison with analog wells in
a relatively new technology for control of the field example that had produced a similar
souring and is discussed in chapter 10. The number of pore volumes of injected water

FIGURE 9 Effect of continuous calcium nitrate treatment of injection seawater on seawater


sour water concentration in the Foinaven reservoir. The seawater sour water concentrations for
two untreated wells in the analog field are shown for comparison.
140 & VANCE AND THRASHER

FIGURE 10 Effect of continuous calcium nitrate treatment of injection seawater on H2S


production in the Foinaven reservoir. The H2S production rate that would normally be expected,
based on the number of pore volumes of injection water, is shown for comparison.

(Fig. 10). Based on the comparison with the Canadian oil fields; in 44% of samples, NRB
analog wells, a >90% reduction in daily H2S outnumbered SRB (Eckford and Fedorak,
production has been achieved. Similarly, in 2002). Nitrate treatment may, therefore, have
terms of sour seawater concentration, >90% a wider application than injection water.
reduction has been observed. Other wells
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