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SPE 78572

Microbial Monitoring to Minimise Corrosion and Formation Damage in the Oil Industry
I.Spark and K.Mutch Commercial Microbiology® Ltd

Copyright 2002, Society of Petroleum Engineers Inc.


oilfield process systems pit corrosion can result with
This paper was prepared for presentation at the 10
th
Abu Dhabi International Petroleum subsequent expensive equipment/pipework replacement being
Exhibition and Conference, 13-16 October 2002.
necessary. In addition to SRB corrosion, the growth of GHB
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
can result in polymer precipitation and acid production which
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to can further aid the corrosion process and act as a substrate for
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 sessile biofilm development.7
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
In seawater injection systems SRB/GHB growth is most
for commercial purposes without the written consent of the Society of Petroleum Engineers is evident within the deaerator towers and downstream into the
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous injection downhole tubulars. In production systems the
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. activity of SRB/GHB can occur both downhole in the
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
reservoir, production tubulars and topside in the separators and
downstream process equipment towards the export oil
Abstract pipeline.
It is accepted that sulphate reducing bacteria (SRB) and Oil and water pipelines can also suffer SRB/GHB related
certain general heterotrophic bacteria (GHB) can promote pit corrosion particularly in the six o’clock position where
corrosion of topside and downhole equipment and cause abrasion of the sulphide layer can occur. This results from
formation damage in the reservoir including H2S souring. In particulates (sand, corrosion fragments) dragging along the
order to inhibit microbial growth and hence minimise these bottom of the pipeline exposing fresh metal to SRB pit
damage mechanisms, it is necessary to impose a strict corrosion with a pronounced groove being developed.
microbial monitoring regime that can be used to optimise any In order for SRB to grow, sulphate together with a suitable
biocide treatments. There are two major considerations carbon source, usually volatile fatty acids such as acetate, are
relating to microbial monitoring which must be taken into necessary. The source of carbon in seawater injection systems
account which are planktonic microbes (those in suspension) is normally from bacterial breakdown of algae and
and sessile microbes (those attached as a biofilm). By zooplankton (copepods) which is greatest during bloom
monitoring the numbers of SRB/GHB entering and leaving periods in the local region. In the North Sea the algal and
each component of the topside process system it is possible to copepod bloom occurs twice a year around the end of spring
determine whether each is under good microbial control. If and again in the autumn, with promoted SRB growth at these
numbers are found to increase from inlet to outlet, then times in response to the elevated carbon in the injection
biocide treatment at a suitable concentration, can be used to topside equipment. The source of sulphate is present in the
treat the fouled components before pit corrosion or H2S seawater itself. The source of carbon in production systems is
production becomes a serious problem within the component. mainly volatile fatty acids from the crude oil such as formate,
If the biocide treatment is not performed in time the system acetate, propionate and butyrate. The sulphate in the
downstream may also become contaminated. By carefully production system originates from either the native formation
monitoring each process system including injection water, brine (connate water) or a mixture of seawater (from injection
firewater, cooling medium, and production systems, it is seawater break-through ) and formation brine. The higher the
possible to extend the process equipment lifetime carbon and sulphate concentrations then the more likely a
considerably, resulting in a major saving in equipment system will support SRB growth and be more prone to suffer
replacement and lost shut down time. This paper describes the microbially influenced corrosion.
microbial monitoring techniques required to minimise The temperature of a process system dictates whether
corrosion, biopolymer, insoluble metal sulphide and H2S SRB/GHB growth is mesophilic (greatest around 30ºC),
production both topside and downhole. thermophilic (greatest around 60ºC) or hyperthermophilic
(greatest around 90ºC). In seawater injection process systems
Introduction the growth is predominately mesophilic, whereas in
The action of SRB in causing microbially influenced corrosion production process systems growth can be a combination of
of steal is well documented.1-6 If allowed to go unchecked in
2 [I.Spark a nd K.Mutch] SPE 78572

mesophilic, thermophilic and hyperthermophilic depending on device. This device is non invasive to the system and biostuds
the temperature gradient throughout the system. can be removed on a regular basis such as once a week or once
By careful SRB/GHB monitoring of each component of a month depending on the process system and how
the process system and chemical analysis of sulphide and microbiologically clean it is (Figure 2). The studs are each
volatile fatty acid (VFA) concentrations of the process water, placed in sterile seawater brine containing sand and agitated
optimised biocide treatments can be used to ensure minimal for a few seconds to remove each biofilm. The resulting
growth thus lower corrosion, H2S and biopolymer production liquid containing the biofilm cells is inoculated and incubated
rates. This will extend the life of the process equipment as before and numbers enumerated using the triplicate MPN
resulting in significant cost savings in equipment replacement. technique remembering to take into account the dilution factor
The major problems associated with SRB/GHB downhole in of the volume of seawater/sand diluent and area of the coupon
the tubulars and reservoir rock formations are H2S, insoluble or stud. In the case of corrosion coupons a known area of the
metal sulphide precipitation and biopolymer production, the coupon is swabbed using sterile swabs and placed into a
latter can block pores with a loss in production or injection known volume of sterile seawater/sand and agitated. The
rates. The microbial cells can also block pores. Adding liquid containing the biofilm cells is inoculated and incubated
suitable biocides to the injection water can help mitigate in the same manner as the biostuds.
downhole microbial problems. It is very important to monitor both sessile and planktonic
numbers since it is possible to have very low numbers of
Microbial Monitoring Techniques planktonic cells but high numbers of sessile cells and vice
The online fluids are sampled into sterile 30ml plastic versa. These cell numbers are plotted on graphs versus time
universal tubes, filled to the brim, and sealed prior to and if numbers of cells start to increase the system has lost
immediate inoculation into the relevant media. Online microbial control and thus optimisation of a suitable biocide
samples are taken at the inlet and outlet of each major treatment can be made immediately before significant
component of the injection or production process system corrosion, formation damage or H2S production has taken
equipment, so that cell numbers going in and out can be place.
monitored. The online fluid is inoculated into either API In addition to the microbial monitoring, chemical analysis
Medium8 which is more suited for Middle East Fields or of the online fluids should also be performed to quantify the
Modified Postgate B Medium8 which is more suitable for the sulphide and VFA content of the fluids. For the sulphide
North Sea (Figure 1) to determine planktonic SRB numbers. measurement a 29ml volume of online fluid should be added
The online fluids are also at the same time inoculated into to a 30ml borosilicate glass universal containing 1ml of 20%
Phenol Red Dextrose Broth (PRD)8 which is designed for Zinc Acetate solution to which 1 Sodium Hydroxide Pellet
general aerobic and facultative anaerobic acid-producing should be added. The analysis should be performed using the
heterotrophic bacteria (GHB)(Figure 2). The inoculated methylene blue technique10 and expressed as mg/litre soluble
media are incubated at + or -5ºC of the process system from sulphide. For the VFA analysis 30mls of online fluids should
which the samples were taken. For the GHB the PRD media be placed in a plastic universal and a Sodium Hydroxide pellet
is normally incubated for seven days and for the SRB a period added. Analysis should be carried out using a Dionex fitted
of 28days. After incubation the SRB and GHB are with an ion pack ICE-AS1 column and formate, acetate,
enumerated using the triplicate most probable number (MPN) propionate and butyrate concentrations in ppm determined.
method.9 It is advisable to repeat the analysis until a
background level of bacteria is determined for the system. Results
This is because individual sample points can be fouled, The following outlines the data which is gathered from a
particularly if long dead leg areas occur between the typical field in the Northern North Sea area and is summarised
equipment and sample point, which may yield artificially high in Table 1.
bacterial numbers. If much higher numbers of cells come out In the case of the water injection system it can be seen
of the system compared to what went in, then the component from Table 1 that mesophilic SRB and GHB numbers increase
is likely to be fouled and should immediately be treated with a from the Deaerator Tower (DA) and downstream to the
suitable biocide to minimise or prevent corrosion or H2S Injection header indicating that the system is microbially
production. fouled and optimisation of the biocide treatment is necessary.
To monitor sessile SRB/GHB is more difficult and can The biostuds taken from the sidestream device also show high
only be determined online from corrosion coupons, bioprobes numbers indicating that a sessile biofilm has developed inside
or online sidestream monitoring device (Figure 3). The main the process system pipework and again should be biocide
problem with using corrosion coupons or bioprobes to treated. The sulphide levels increase downstream of the DA
determine sessile SRB/GHB numbers is that they are often Tower again confirming SRB activity and the need for biocide
only retrieved at three, six or twelve month intervals. This treatment.
long time period between retrievals may result in an active In the case of the production system it can be seen from
biofilm being undetected with corrosion having already Table 1 that numbers of m-SRB and GHB increase through
occurred before corrective action can be applied. A more the 1st stage separator indicating that this is microbially fouled.
efficient and easier system to use is the online sidestream This has resulted in systems downstream of this having higher
SPE 78572 [Microbial Monitoring to Minimise Corrosion and Formation Damage in the Oil Industry] 3

numbers of cells present when compared to the original fluids in the Corrosion of Steel,” Biochemical Biophysical
coming up at the wellhead (Table 1). The sulphide levels have Research Communications, 221, p 414-421(1996).
also increased from the 1st stage separator downstream and
VFA concentrations show utilisation of formate and acetate 3. Beech, I.B. et al.: “Direct Involvement of a Extracellular
through the 1st stage separator and downstream of this Complex Produced by a Marine Sulphate Reducing
equipment. This indicates that the production system, and in Bacterium in the Deterioration of Steel,” Geomicrobiology
particular the 1st stage separator has lost microbial control and Journal, 15, p119-132(1998).
a suitable optimised biocide treatment regime should be
initiated. 4. Edyvean, R.G.J. et al.:”Microbially Influenced Corrosion-
Has Industry Learnt its Lesson,” Proceedings of Eurocorr
Conclusions 2000, Institute of Materials, ISBN1-86125-127-0.
Based on the data gathered together in this study the following
conclusions are made:- 5. Gubner, R. and Beech, I.B.:”Field and Laboratory Studies
of Marine Biocorrosion of Carbon Steel,” Proceedings of
• By monitoring the online fluids which enter and leave the 2nd NACE Latin American Congress on Corrosion, 9-
each piece of topside process equipment for planktonic 13 Sept, Rio de Janeiro, Brazil, Paper LA 96175(1996).
SRB/GHB it is possible to identify which are fouled by
bacteria and to optimise biocide treatment to prevent 6. Beech, I.B. et al.:”The Role of Surface Chemistry in SRB-
significant corrosion, biopolymer, insoluble metal Influenced Corrosion of Steel,” International Journal of
sulphide and H2S from occurring. Marine Biology and Oceanography, OEBALIA 13, p243-
• Utilising corrosion coupons, bioprobes or sidestream 249(1993).
biostuds, the sessile numbers of SRB/GHB can be
enumerated to determine whether or not a biofilm has 7. Beech, I.B. et al.:”The Effect of Marine Pseudomonas
developed and whether biocide treatment is required to NCIMB 2021 Biofilm on AISI 316 Stainless Steel,”
prevent microbial damage mechanisms. Biofouling, 15, p 3-12.
• By careful microbial monitoring the equipment lifetime
can be extended considerably by maintaining good 8. “Standard Test Method-Field Monitoring of Bacterial
microbial control throughout the process system avoiding Growth in Oilfield Systems,” Nace Standard TMO194-94,
early equipment replacement due to corrosion and H2S Item NO.21224(1994).
production.
• By monitoring SRB/GHB numbers, VFA and sulphide 9. Harrigan, W.F.and McCance, M.E.:”Laboratory Methods
levels in produced water at the riser or production in Food and Dairy Microbiology,”Pub:Academic
manifold headers, it is possible to determine whether Press(1976).
downhole or reservoir souring to H2S, corrosion of
production tubulars and isoluble metal sulphide 10.Garbar, N.:”Direct Spectrophotometric determination of
precipitation have occurred. inorganic sulfide in biological materials and in other
• By monitoring SRB/GHB numbers, VFA and sulphide complex mixtures,” Analytical Biochemistry, 43, p129-133
levels in produced water at the injection header it is
possible to predict whether downhole growth of
SRB/GHB is likely with loss of injection due to corrosion
products, insoluble metal sulphide precipitation, and
biopolymer precipitation blockage of reservoir rock pores.

Acknowledgments
Thanks to Commercial Microbiology® Ltd for permission to
present this paper.

References

1. Videla, H.A., et al.: “The Role of Iron in SRB-Influenced


Corrosion of Mild Steel,” Corrosion 98, Paper 289, NACE,
Houston, Texas(1998).

2. Pereira, A. et al.: “Characterisation of Representative


Enzymes from a Sulphate-Reducing Bacterium Implicated
4 [I.Spark a nd K.Mutch] SPE 78572

Figure 1- SRB Media. This media is designed to turn a black


colour in the presence of SRB. There are twelve media bottles
per pack grouped in sets of three to undertake triplicate MPN
enumeration of cells.

Figure 3-Sidestream Biostud Monitoring Device. This device


is fitted vertically online to the process equipment with flow
rate being controlled by the two valves either end of the device
which should be 0.1-1 metre/sec or 1.5-15 cubic cms/sec. A
pressure guage measures the system pressure and the device is
rated to 3500 psi. Flow should be from bottom to top so fluid
remains inside if a shut down of the process system occurs.
Twenty four biostuds can be inserted simultaneously.
Figure 2- PRD Media. This phenol red dextrose media is
designed to turn from red (right bottles) to yellow (left bottles)
in the presence of acid producing GHB. There are twelve
media bottles per pack grouped in sets of three to undertake
triplicate MPN enumeration of cells.
SPE 78572 [Microbial Monitoring to Minimise Corrosion and Formation Damage in the Oil Industry] 5

SAMPLE LOCATION mSRB tSRB mGHB tGHB mAPGHB tAPGHB sulphide VFA
cells per ml cells per ml cells per ml cells per ml cells per ml cells per ml mg / l (formate, acetate,
propionate, butyrate)
ppm
WATER INJECTION SYSTEM
Upstream of Deaerator < 0.3 x 100 N/A 0.6 x 100 N/A < 0.3 x 100 N/A N/A N/A
Tower
Downstream of 3.5 x 100 N/A 1.5 x 101 N/A 0.3 x 100 N/A 0.350 N/A
Deaerator Tower
Injection Header 3.0 x 101 N/A 1.1 x 102 N/A 0.9 x 100 N/A 0.450 N/A

Biostuds 4.5 x 102 N/A 6.5 x 103 N/A 1.5 x 102 N/A 1.50 N/A
cells per cm2 cells per cm2 cells per cm2 µg / cm2
PRODUCTION SYSTEM
Wellhead 1.1 x 101 < 0.3 x 100 2.0 x 102 < 0.3 x 100 1.4 x 101 < 0.3 x 100 0.450 80, 120, 20, <2

Inlet to 1st Stage 1.1 x 101 < 0.3 x 100 2.0 x 102 < 0.3 x 100 1.4 x 101 < 0.3 x 100 0.420 80, 120, 20, <2
Separator
Outlet to 1st Stage 3.0 x 104 1.1 x 101 2.5 x 105 3.5 x 101 2.0 x 102 4.5 x 100 0.995 60, 100, 10, < 2
Separator
Outlet to 2nd Stage 2.5 x 104 < 0.3 x 100 2.5 x 105 < 0.3 x 100 2.0 x 102 < 0.3 x 100 0.652 58, 97, 10, < 2
Separator
Inlet to Hydrocyclones 2.5 x 104 < 0.3 x 100 2.5 x 105 < 0.3 x 100 2.0 x 102 < 0.3 x 100 0.652 50, 85, 5, < 2

Outlet to Hydrocyclones 3.0 x 104 < 0.3 x 100 4.5 x 105 < 0.3 x 100 3.0 x 102 < 0.3 x 100 0.650 50, 85, 5, < 2

Export Oil Pipeline 3.0 x 101 < 0.3 x 100 2.5 x 102 < 0.3 x 100 1.4 x 101 < 0.3 x 100 0.550 80, 120, 20, <2

Corrosion Coupon ex 1st 2.0 x 103 1.5 x 101 4.5 x 104 2.0 x 102 0.7 x 103 < 0.3 x 100 1.35 µg / N/A
Stage Separator cm2
Corrosion Coupon ex 2nd 0.3 x 101 < 0.3 x 100 0.7 x 102 < 0.3 x 100 < 0.3 x 100 < 0.3 x 100 0.30 µg / N/A
Stage separator cm2

Table 1

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