Corrosion and

Material
Issues in
Water
Injection
Systems
J T A Smith, I Vance

Sunbury Report No. ESR.96.ER.075

dated August 1996

Main CD
Contents
 STANDARD DATA PAGE

REPORT NO. ESR.96.ER.075 SECURITY

CLASSIFICATION:
ISSUE DATE: AUGUST, 1996 Restricted

MAIN TITLE: CORROSION AND MATERIAL ISSUES IN WATER INJECTION

SYSTEMS

CLIENT: Produced Water MTL

COMMISSIONED BY: Paul Rutter

ISSUING DEPARTMENT/DIVISIONS:
MATERIALS & INSPECTION ENGINEERING
RESEARCH & ENGINEERING CENTRE
BP INTERNATIONAL LIMITED

PREPARED BY: APPROVED BY:

.............................................................. ...............................................................
J T A SMITH, I VANCE D RAY
TEAM LEADER
MATERIALS & INSPECTION
ENGINEERING

DISTRIBUTION: As distribution list

KEYWORDS: corrosion, commingle, injection, microbiology, oxygen, SRB, water

Copyright © BP International Limited 1996"

All rights reserved. None of the information contained in this document shall be disclosed outside the recipient's own company and no
part of this document may be reproduced or transmitted in any way or stored in any retrieval system without prior written permission of
General Management, Engineering Shared Service, BP International Limited.
 CONTENTS
Section Page

1. INTRODUCTION ......................................................................1

2. CONCLUSIONS..........................................................................1

3. RECOMMENDATIONS.............................................................3

3.1 Recommended Actions in the Field ...............................3

3.2 Recommendations for Future Work..............................4
3.3 Procedures for Monitoring Water Quality in the
Field ...........................................................................5

4. UPDATE TO SECTIONS IN GUIDELINES REPORT

FOR SWIS ...........................................................................6

4.1 Effect of Oxygen (Vacuum SWIS).................................6

4.2 Oxygen Limit for Gas Stripped Systems .......................8
4.3 Effect of Chlorine ...........................................................9
4.4 Effect of Velocity ..........................................................11
4.5 Oxygen Scavenger ........................................................12
4.6 Temperature.................................................................13

5. MICROBIOLOGICAL ISSUES IN WIS ................................13

5.1 Microbiologically Influenced Corrosion (MIC) ..........13

5.2 Biocide Optimisation....................................................16

5.2.1 Measurement of Bacterial Population ............17

5.2.2. Optimisation Based on Corrosion Rate..........17
5.2.3. Types of Bacteria and Quantification.............18
5.2.4. Influence of Prodeuction Chemicals on Bacterial
Population........................................................18
5.2.5. Biocide Injection..............................................19
5.2.6. Recent Developments in Bacterial Control.....19
5.2.7. Reservoir Souring............................................20
5.2.8. Raw Sea Water Injection ................................20
5.2.9. Effect of Operating Process Parameters on
Microbiological Control ..................................21

5.3 Summary ......................................................................22

6. PRODUCED WATER SYSTEMS (PWS) ................................23

 6.1 Corrosion Issues and Methods of Controls IN PWS ....23
6.2 Microbiological Activity in Produced Water................23

7. COMMINGLED WATER (PW/SW)........................................24

7.1 Corrosion Issues ............................................................24

7.2 Microbiological Activity ................................................26

8. CORROSION MONITORING IN WATER INJECTION

SYSTEMS ..................................................................................27

9. MATERIAL OPTIONS.............................................................28

9.1 Low Alloy Carbon Steel Downhole Tubulars ...............28

9.2 Polyethylene (PE) and Gas Reinforced Lines (GRP) ......
Carbon Steel Flowlines ..................................................29
9.3 Plastic Coated and GRP Lines Carbon Steel Tubulars29
9.4 Production/Injection Switch Over (ie Production ...........
Materials being used for Sea Water Service .................30
9.5 Raw Sea Water Injection...............................................31
9.6 Preferential Weld Attack in WIS ..................................32

10. MAINTENANCE PIGGING.....................................................33

11. DAY-TO-DAY CONTROL OF WATER QUALITY OF

SWIS ......................................................................................33

12. UNRESOLVED ISSUES IN SEA WATER SYSTEMS ...........34

REFERENCES

FIGURES

APPENDIX 1
1. INTRODUCTION

The main intention of this report is to summarise recent work regarding corrosion in
sea water injection systems as an update to the report on "Minimising Corrosion of
Carbon Steel in Sea Water Systems - Guidelines for Water Quality" (1). The field
experience has been expanded to include BPX Alaska fields. The sections on the effect
of operational parameters such as oxygen, chlorine and velocity have been expanded
and a section on microbiologically induced corrosion (MIC) has been introduced. As
the choice of pipe material is rapidly expanding from soley carbon steel, "new
materials" for water injection service have been discussed.

Where possible, “rule of thumb” values for the operating parameters have been
provided, as inevitably targets are sought by operating personnel and design engineers
alike. Nevertheless it should not be overlooked that corrosion should be managed on a
system by system basis by employing a monitoring strategy in order to achieve
optimum control. To facilitate developing a strategy, recommendations for actions in
the field are given. These include suggested procedures for controlling water quality on
a day-to-day basis.

Throughout the industry, as fields fall off plateau and water handling issues become
more difficult, interest is growing in water flood possibilities other than injecting 100%
deaerated sea water. For this reason the issues associated with corrosion management
of raw sea water, produced water systems and the ever increasing practice of
commingling sea water and produced water have been discussed.

The work was sponsored under the Produced Water MTL.

2. CONCLUSIONS

2.1 For vacuum sea water injection systems (SWIS), more confidence has been attained in
the empirical limit set in the previous guidelines of 20 ppb O2 (zero Cl2, 8 m/s), in
order to keep below a general corrosion rate of 10 mpy (0.25 mm/y). Thus these may
be considered to be good “rule of thumb” values for the operating parameters.

2.2 For design purposes of SWIS, a "rule-of-thumb" correction factor of between 1/3-1/5
should be applied to the Oldfield and Todd model to give a first pass predicted oxygen
corrosion rate. This correction factor is applicable at velocities up to 10 m/s but
assumes a continuous protective scale. If the details of pipe bore are known, then it is
recommended that the API limit using a C factor of 250 is used to calculate the
velocity limit.

2.3 For gas stripped systems it is possible that a dissolved oxygen level greater than 20 ppb
is acceptable but this has not been proven.

2.4 Below are “rule-of-thumb” targets which may be used to balance microbiological
control (and the possibility of microbiological corrosion) with other potential corrosion
problems in a WIS.

1
 OPERATING RULE OF THUMB LIMIT RULE OF THUMB LIMIT
PARAMETER (upstream of tower) (downstream of tower)

Chlorine 0.5 - 1 ppm * Ideally zero

0.2-0.3 ppm max

Oxygen scavenger residual N/A <1ppm sodium sulphite

(equivalent to < 0.64 ppm
bisulphite)

Dissolved Oxygen 8 ppm (i.e. usual concentration <20 ppb

in raw sea water)
Sessile Bacteria
- SRB <102 cm-2 <102 cm-2
- GAB, GnAB <102 cm-2 <102 cm-2

Planktonic Bacteria
- SRB <1 ml-1 <1 ml-1
- GAB, GnAB <104 ml-1 <104 ml-1

* Chlorine will consume oxygen scavenger preferentially which can lead to undesirably
high residual chlorine and dissolved oxygen downstream of tower.

Table 1 : “Rule of Thumb” targets for Operating Parameters in a Sea Water Injection System
and Sea Water/Produced Water Commingled Systems

2.5 The optimum operating conditions should be determined for a specific sea water
injection system by performing field trials to assess the fluid. Thus corrosion control
may be achieved.

2.6 Control of a water injection system may be obtained, if suitable measures are taken
from the beginning and rigorously maintained throughout the life of the system. Loss
of oxygen control for short periods may be rectified. However microbial control, once
lost e.g. by switching off the biocide treatment, may take years to be restored.

2.7 Experience across the assets has shown that areas of potential high risk of corrosion in
water injection systems are :-

• High turbulence and velocities e.g. upstream and downstream of bends,

restrictions, downstream of chokes.
• Carbon steel downhole tubing after installing plastic coated flowlines
• Welds
• Lines which cannot be cleaned by maintenance pigging (especially long, slow
lines)
• locations of oxygen ingress e.g. flanges, pig launchers/receivers, hub seal faces

2
2.8 Produced water (PW) systems will require the use of a corrosion inhibitor for
corrosion control. This chemical can either be carried over from the three phase
inhibition programme or injected directly into the water system. Most corrosion
inhibitors exhibit biocidal properties. Therefore a PW system may not need additional
microbial control.

2.9 Commingling produced water and sea water fluids results in a complex mixture of
corrosion mechanisms. Also the environment gives bacteria the “complete meal”,
increasing the risk of MIC.

2.10 For corrosion control of WIS, it is recommended that produced water and sea water
streams are not commingled, since system optimisation is difficult and costly.

3. RECOMMENDATIONS

3.1 Recommended Actions In the Field

1. Monitoring

Water quality and corrosivity should be monitored. It is recommended that an "action

chart" should be implemented and an example for adaption to suit a specific SWIS has
been given (Figure 1).

2. Corrosion Strategy

As the awareness of corrosion issues with sea water systems is improved and the need
to monitor corrosion and water quality is better understood, a consequent large
amount of data are being collected. These data are only useful if a corrosion
management strategy is implemented. This strategy should detail the roles and
responsibilities for data collection and management.

Procedures to facilitate corrosion control on a day-to-day basis need to be put in place.

As a starting point the "action chart" may be implemented and expanded to suit an
individual asset’s requirements. In addition, methods of handling the data (particularly
oxygen and corrosion) need to be determined for use in the field.

3. Microbiological Control

• In terms of corrosion issues, the surface-dwelling or sessile bacterial

populations are most important. The efficacy of batch biocide treatment in
reducing sessile bacterial population densities should be ascertained for a
specific system. Once an effective treatment has been established, the frequency
of deployment can be optimised in terms of corrosion rate or bacterial numbers.
As the main driver for biocide injection is corrosion control, the former method
is recommended.

• Where possible the use of ammonium based oxygen scavengers should be

avoided as they provide an additional nitrogen source for bacteria. Other

3
 production chemicals may also provide additional nutrients for bacteria in terms
of carbon or phosphorus.

• There are opportunities for reducing operational expenditure by reducing the

throughput of injection systems during batch biocide treatments (see section
5.2.5 for detail).

• Regular review of microbiological monitoring data (and correlation with

corrosion data) should be implemented to ensure that biocide treatments remain
cost-effective.

4. Water Quality Control

• Control of dissolved oxygen by chemical means alone should be avoided. This

is because it increases the risk of overdosing with oxygen scavenger which can
enhance corrosion.

• High oxygen excursions should be avoided (see Figure 1 for guidance).

• Chlorine reacts preferentially with oxygen scavenger. Thus overdosing with

chlorine can result in unnecessary requirement for oxygen scavenger
(with the associated increase in chemical costs ) and possibly increased
corrosion. Also the chlorine injection location should be chosen carefully.

3.2 Recommendations for Future Work

1. Determine methods of handling the process data (particularly oxygen and corrosion)
for use in the field to facilitate corrosion control on a day-to-day basis.

2. Compare existing corrosion rates and bacterial data for each system to determine a
relationship and obtain a "first pass" at an acceptable target for microbiological control
based on minimal contribution to corrosion rates.

3. Verify the "rule of thumb" correction factor for corrosion prediction and velocity “cut
off” limit.

4. Quantify the effect of high oxygen excursions.

3.3 Procedures for Monitoring Water Quality in the Field

There are issues regarding the techniques for collecting the important data on water
quality which have been covered in the relevant sections. A summary checklist table is
given below.

4
 TYPE METHOD ADVICE ON GOOD
PRACTICE
Chlorine Colorimetrics Operator dependent so standardise
as much as is practical.

Oxygen scavenger residual Wet chemistry Amount of residual oxygen

scavenger should be expressed as
a bisulphite concentration. 1 ppm
sodium sulphite is equivalent to
<0.64 ppm bisulphite.

Dissolved Oxygen On-line meter e.g. Reliable as long as regular

Orbisphere maintenance is carried out;
membrane easily fouled up.

Sessile Bacteria Flush mounted Enumeration possible by several

bioprobe or methods. Only directly compare
(SRB, GAnB) intrusive corrosion data taken using the same method
coupons and same frequency. Make use of
specialised contractors.

Planktonic Bacteria Grab sample from As above

well flushed sample
(SRB, GAnB) line.

Table 2: Good Practice checklist for Monitoring Water Quality

These good practices should be considered when implementing the "action charts" for
day-to-day water quality control given in Figure 1.

4 UPDATE TO SECTIONS IN GUIDELINES REPORT FOR SWIS

The following sections refer to issues discussed in the previous report (1).

4.1 Effect of Oxygen (Vacuum SWIS)

It is well known that the Oldfield and Todd predictive equation is inapplicable at high
O2 levels and is conservative at low to medium concentrations (<100 ppb), although
this needs to be more precisely quantified. Field trials and laboratory tests in 1995
provided data with which a "first pass" correction factor could be determined (2, 3, 4,
5). Figure 2) shows how the data compare with the Oldfield and Todd model. Chlorine
levels are random for these data. Table 3 gives more data for "normal" operating
conditions ie ~20ppb O2 which have been collected over the past year. It should be

5
 noted that Forties employ a gas stripped system so there may be a synergistic effect
between O2 and CO2 (see section 4.2). Endicott (which also has a gas stripped
deaeration system) has not been included in this table, as it commingles its sea water
with produced water (see section 7).

FIELD OXYGEN GENERAL FLOW COMMENTS

LEVEL* CORROSION RATE
(ppb) RATE (mpy) (m/s)

Magnus 10-20 5 2.4 LPR probe fouled during trial

(June '94)
10-20 6-7 ? Coupon data ( July-Oct '94)

Wytch Farm 30-40 5 2.6 Trial (Sept '94) No Cl2,

Forties (Bravo) 20 15 2.1 Trial ('94).

? 4-8 ? Coupon data (Nov '94)

Prudhoe Bay 10 (but <1 2-5 2-4 Wellhead coupon data ‘96
at wellhead) no chlorine, (Jan 1996)

Sunbury Lab 20 10 4.5 LPR probes

0.1 stagnant 30 deg C (more
representative of downhole)

Table 3 : Corrosion Rates in Some BP Fields at "Normal" Operating Conditions (~20 ppb
Dissolved Oxygen)

Recent data (Figure 2, Table 3) support the empirical dissolved oxygen limit from the
previous guidelines (1). This limit is 20 ppb (8 m/s max, zero chlorine) to control
general corrosion at rates <10 mpy (0.25 mm/y). The oxygen concentration may be
used as a corrosion risk alarm for day-to-day operation (Figure 1). However, this
alarm would not negate the requirement for corrosion monitoring since there will be
other mechanisms in addition to oxygen corrosion in a SWIS. Both oxygen and
corrosion monitoring should be carried out for optimum corrosion control of a SWIS

A prediction model is required for establishing "first pass" design criteria. Comparison
of measured and predicted corrosion rates (Figure 2) yields a "rule-of-thumb"
correction factor to the Oldfield and Todd model of 1/3-1/5. The applicability of the
correction factor of 1/3 is further illustrated by comparing data from Table 3 and
Oldfield and Todd (O&T) predicted data. Table 3 give corrosion rate data (LPR and
coupon) during conditions of low oxygen levels (<20 ppb). The flow rates at the
monitoring locations were in the region of 2-3 m/s. (NB In BPXA typically flow rates
in 6" flow lines are up to 4 m/s. Larger diameter lines, around 28"-36", will have rates
around 0.5-1 m/s). The O&T model predicts 12 and 18 mpy for flow rates 2 and 3 m/s
respectively (20 ppb O2, 6" ID, 15 degC).

6
The Oldfield and Todd model is in fact applicable at low oxygen levels (<20 ppb) and
low flow rates (<1 m/s) (Figure 2). However, these conditions relate to a region of
very low corrosion risk (<10 mpy); thus applying a reduction factor (although perhaps
unnecessary) would not have a major impact on design decisions. It is therefore
recommended that the correction factor is applied for all oxygen concentrations.

The O&T model was never intended to be applied to conditions of very high oxygen
concentrations (>100 ppb O2) (Figure 2).

The "rule-of-thumb" correction factor to the Oldfield and Todd model is only
applicable up to a certain velocity. This “cut off” velocity is 8-10 m/s (see Section 4.4).
However the correction factor (and velocity cut-off point) needs further verification.

It has been recognised that high oxygen excursions, even for short periods, must be
avoided (1). This is not only because of the effect of high oxygen levels on corrosion
of carbon steel but also because protective scale breakdown is more likely which could
lead to enhanced localised attack. However the effect has yet to be fully quantified.
This quantification would be useful for determining internal corrosion damage after
system upsets. Recent laboratory trials showed that the corrosion rate was doubled for
an increase from 20ppb up to 50-100 ppb and a factor of 10 increase in corrosion rate
could be expected for an increase from 20 ppb up to 1000 ppb O2 (9 to 90 mpy) (19).

The above correlation between corrosion rate and oxygen concentration appears to be
contradicted by experiences at Wytch Farm. Problems with the deaerator tower have
resulted in average dissolved oxygen concentrations of 800-1000 ppb. A thorough
inspection review was conducted at the end of 1995 and "incredibly" no damage was
found (20). There was 100% coverage (using UT mapping) of all pipework
downstream of the booster pumps before the pipes went underground. This suggests
that the conditions are ideal for maintaining a stable protective oxide layer. However
break down in that film, due to solids or fluid erosion, will lead to enhanced pitting
attack. This experience may also illustrate the proposed concept of intentionally
maintaining a system at continuously aerobic conditions for corrosion control, rather
than aiming at low oxygen levels and often swinging between aerobic and anaerobic
conditions. However, there is not enough evidence to suggest that operating in such a
fashion is the way ahead.

Finally, dissolved oxygen can be fairly quickly consumed by carbon steel piping but
requires longer lengths of piping than that available on a North Sea platform. The miles
of piping between deaeration and injectors, is likely to be one of the reasons why the
sea water injection systems at Prudhoe Bay, ADMA and Wytch Farm have different
problems/dominant corrosion mechanisms compared with North Sea platforms. The
initial piping in their systems may be considered as almost sacrificial to protection of
the rest of the system regarding oxygen corrosion. Thus downstream areas in these
assets, such as that monitored by wellhead weight loss coupons, will be less sensitive
to high dissolved oxygen spikes from system upsets.

7
4.2 Oxygen Limit for Gas Stripped Systems

Recent trials on Forties Bravo showed that it may be possible to increase the dissolved
oxygen limit above 30 ppb O2. At the recommended Cl2 level of 0.2-0.3 ppm (1),
corrosion was independent of oxygen level up to about 70 ppb (5). This supports
previous work which indicated a threshold limit existed in gas stripped systems.
However a clear interaction between O2 and Cl2 on corrosion rate was observed; when
no chlorine was present, corrosivity steadily decreased as the O2 concentration was
reduced from 400 to 10 ppb. Thus more trials are required before a higher O2 limit can
be allowed.

The coupon data for Forties Bravo (pulled Nov '94) indicated that the general
corrosion rate was 4-8 mpy (with some pitting at 48 mpy). These rates are 50% lower
than the LPR readings taken during the trials (Table 1). This emphasises the fact that
LPR (and ER) data should be used to indicate changes in conditions to enable timely
remedial actions to be taken, rather than absolute measurements of corrosion rate
within the system (see also section 8).

There is evidence of an O2/CO2 synergy ie that the presence of O2 and CO2 is worse
than the corrosion impact of either gas individually or added together. However, BP
assets with gas stripped systems (Forties and Endicott) and Statoil's Statfjord fields,
aim to control corrosion in their sea water injection systems by controlling the oxygen
level rather than the CO2 level.

The important messages are that :-

(a) care should be taken when comparing corrosion data collected from gas stripped
systems with those from vacuum deaerated systems because of the likely synergy
between CO2 and O2. Higher corrosion rates are expected in gas stripped systems for
the same O2 concentration.
(b) Corrosivity should be assessed on a system by system basis. Only then may changes
to the operating parameters (e.g. increased oxygen or chlorine limit) be considered.

4.3 Effect of Chlorine

Chlorine is required for microbiological control of a SWIS. However there are a

significant amount of field and research data that indicate that chlorine causes
corrosion problems in WIS. Thus a balance/compromise must be obtained. Under
normal operating conditions a limit on Cl2 will not be applicable for vacuum tower
systems which also employ oxygen scavenger, since Cl2 content is zero downstream of
tower. However it would still be beneficial to be able to quantify the effect of chlorine
on corrosion rate. This would allow the prediction of corrosion damage over periods
when control has been lost and chlorine levels increased. A limit is essential in gas
stripped systems and/or systems that do not employ oxygen scavenger and thereby
usually maintain a low chlorine residual downstream of the deaerator tower.

Trials on Forties Bravo showed that chlorine accelerated the corrosion rate of carbon
steel. The corrosivity increased four-fold with an increase from zero to 0.4-0.5ppm Cl2
at low O2 levels (<30 ppb) (5). This confirms earlier work on Forties which has been
discussed previously (1). As a consequence Forties Bravo have reduced their maximum

8
limit for chlorine to between 0.2 and 0.3 ppm. Corrosion and microbial data from
pulled coupons from the water injection header have not indicated any increase in
corrosion or microbiological activity and therefore this treatment will continue; March
'95 data showed <2.5 mpy (0.1 mm/yr) with no pitting.

Experience in the field has been verfied by laboratory tests. Recent work in the flow
loops at Sunbury has verified that 0.4 ppm Cl2 residual concentration in the presence
of low levels of oxygen (20ppb O2) results in double the corrosion rate (19). However
Cl2 it did not appear to have much effect at higher O2 concentrations (200ppb O2).
The evidence that Cl2 appears to have more effect at low O2 levels has been discussed
previously (1). Also 0.2 ppm Cl2 was found to have relatively little effect on the
corrosion rate compared with the corrosion rate increase due to O2 (4).

Thus it is recommended that, until more data are available, the limit of 0.2-0.3 ppm
chlorine downstream of the tower for all systems should be set where water is in
contact with bare carbon steel. (NB The industry accepted free Cl2 level upstream of
the tower is 0.5-1 ppm for microbial control.)

Strict control over chlorine dosing is also essential from an economic point of view for
systems employing oxygen scavenger. Oxygen scavenger preferentially consumes
chlorine. 4 ppm oxygen scavenger is required to oxidise 1 ppm of chlorine. Any
remaining scavenger will then remove the dissolved oxygen. Thus it follows that if an
unnecessarily high amount of chlorine is present, an unnecessarily high amount of
oxygen scavenger will be required to reduce the dissolved oxygen level to the
acceptable level for that system. Sometimes it is impossible to inject enough oxygen
scavenger because the rate is limited by the size of the pump. This can lead to
unacceptably high levels of chlorine and oxygen occurring in the system e.g. Wytch
Farm (2).

Other points regarding chlorine in water injection systems are:-

• For each system the actual chlorine content provided by different

electrochlorinator settings must be determined to facilitate control. This was
carried out for Magnus ( 3).

• From a microbiological point of view, ideally a Cl2 residual should be

maintained throughout the SWIS. However the loss of Cl2 (a) across
deaerators and (b) as a result of reaction with oxygen scavenger, may be
balanced by an effective batch treatment regime with an organic biocide such as
glutaraldehyde.

• Chlorine can affect the dissolved oxygen measurement by chemets and possibly
by the orbisphere meter. This was noticed on both counts during corrosion
trials on Magnus (it was noticed that the presence of chlorine affected the
oxygen reading of the orbisphere meter and by chemet); with the
electrochlorinator off the oxygen was measured at 5-10 ppb, but with the
electrochlorinator on (at ~0.4ppm) the oxygen was measured at 40-60 ppb (3).
However during recent trials on Forties the chemet measurement was affected
but not that from the Orbisphere (29). Again it was found that each 0.1 ppm

9
 Cl2 was equivalent to about 10 ppb O2 measured. This effect needs to be
quantified and taken into account when measuring oxygen levels.

• A simple visual colorimetric technique is normally used for determinining

chlorine content. The data are very operator dependent and so the location of
testing and source of illumination should be standardised in order to facilitate
repeatability.

4.4 Effect of Velocity

As discussed earlier, it is generally accepted that the Oldfield and Todd model is
conservative and the "rule-of-thumb" correction factor was shown to be between 1/3-
1/ . This practical reduction in the predicted corrosion rate is normally attributed to the
5
formation of a protective scale.

At low oxygen concentrations a corrosion rate of 10 mpy, up to an empirical limit of 8-

10 m/s, was given in the previous guidelines (1). Subsequent laboratory studies verified
in part this limit up to the velocity limit of the flow loops (approx. 5 m/s) (4, 19).

The "rule-of-thumb" correction factor of 1/3-1/5 for higher oxygen concentrations up to

200 - 1000 ppb can be assumed to be suitable for flow rates up to 10 m/s. This has
been demonstrated up to approx. 5 m/s (4, 19), but the effect still needs verification at
higher velocities. This factor assumes a continuous protective scale.

However, it should be recognised that protective scales can be damaged under

aggressive flow regimes, leading to localised breakdown and attack at the Oldfield and
Todd rate or more (since localised pitting rates are often accelerated by galvanic
effects with adjacent, fully scaled regions). The velocity at which this damage can
occur is not clear and will depend on flow regimes and pipe geometries. The limit of 10
m/s (based on operational experience) is usually in line with work by Conoco which
suggests that scale damage does not occur until the velocity exceeds a critical limit
defined by an equation taken from API RP 14E but with a "C factor" of 250 (6). If the
details of pipe bore are known, then it is recommended that this limit is used. The work
was based on a manifold configuration and so is relevant to turbulent conditions. In
straight tubing, the limit is likely to be higher but is uncertain.

Another way (other than erosion) that scales can breakdown is by operational
excursions, especially oxygen spikes in the system. The higher the velocity, the more
sensitive the system will be to such operational excursions. Thus if the correction
factor is used to estimate the corrosion rate, even more care must be taken to reduce
/eliminate operational excursions.

At the other end of the spectrum, low velocities (<1 m/s) can also lead to problems
with solids dropping out resulting in underdeposit corrosion and/or higher risk of
microbial corrosion. This was found by ADMA in their long, unpiggable distribution
lines and more recently by Shell (see Section 5.1).

10
4.5 Oxygen Scavenger

There are no data at present to allow quantification of the effect of residual scavenger.
This is partly due to the difficulty in simulating this in the laboratory and assessing the
effect, since it is likely to be a long term issue of film breakdown.

However there are numerous field trial observations which are useful :-

1. Take care when measuring the amount of residual oxygen scavenger in the system.
Standardise on how the test is taken and ideally test the solution at the sampling point
(since the oxygen scavenger will deplete rapidly if the time period between sampling
and testing is too long). Take care when quoting residual bisulphite values. The test
gives the quantity of sodium sulphite but correctly speaking a bisulphite value should
be used when quoting the amount of residual oxygen scavenger. The conversion is 1
ppm sodium sulphite is equivalent to 0.64 ppm bisulphite.

2. It is possible to observe residual oxygen scavenger and oxygen co-existing. This has
not been explained theoretically yet. However it is important to record such incidents
and not to dismiss these data as incorrect.

3. Controlling oxygen levels by chemical methods alone is not recommended especially

due to the potential problems arising from overdosing with oxygen scavenger.
However some assets are employing vast amounts of oxygen scavenger due to :

• oxygen ingress into the system downstream of the deaerator (3)

• poor vacuum tower performance (2)
• high chlorine levels (oxygen scavenger consumes chlorine preferentially).

4. Avoid switching off oxygen scavenger (OS) when treating with biocide. Switching of
OS results in high oxygen levels for sometimes significant periods of time which give
high corrosion rates (e.g. 200 ppb O2 results in 15 mpy in the lab). However an even
greater potential corrosion problem is likely to occur in this situation. Switching from a
mildly oxidising /reducing environment to a highly oxidising environment (as occurs
during biociding) is likely to lead to breakdown of protective films. This film
breakdown will result in localised attack and the corrosion rate is likely to be higher
than the general corrosion rate normally observed/predicted on a clean surface.

Even if the biocide does react with oxygen scavenger, it is probably not worth the risk
of it mistakenly not being switched on again after the treatment.

5. The measurement of residual oxygen scavenger should be taken at least once a day,
plus any time there are large changes in corrosion rate as measured by on-line
monitoring techniques (>5 mpy) or high oxygen excursions.

4.6 Temperature

So far most research on the effect of temperature in SWIS has been carried out at ~14
degC which is applicable to flow lines in the North Sea and Alaska but not downhole
where temperatures are more in the region of 50 deg C. Previous work by Marintek

11
 discussed elsewhere (1) indicated 30 deg C to be a critical temperature. However a
recent study at Sunbury carried out at 30 deg C did not demonstrate a significant
difference in corrosion rate of carbon steel (at low dissolved oxygen levels) than had
been observed by Marintek at 15 deg C (19). It is understood that recent tests by
Vallourec investigated 20 deg C and 50 deg C as part of their investigation of the
performance of low alloy tubular steels for water injection and found no difference
(25).

5. MICROBIOLOGICAL ISSUES IN WIS

The previous guidelines report did not consider the effect of microbial activity or
biocide treatments upon corrosion rates. Sea water injection systems are operated
within the environmental envelope which allows microbiological activity to proceed.
Since it is economically unrealistic to completely exclude microorganisms from sea
water systems, it is inevitable that susceptible metal surfaces will be colonised by
bacteria, resulting in the possibility of microbiologically influenced corrosion (MIC).
The issues will be discussed below, along with guidance on how to operate the system
in the most effective manner.

5.1 Microbiologically Influenced Corrosion (MIC)

There are at least eight distinct mechanisms by which bacteria have been proposed to
enhance corrosion rates (7,14). It has been proposed that the high rates of corrosion
associated with MIC are, in fact, a reflection of non-biological mechanisms which
proceed in a protected environment created by the action of bacteria i.e. bacteria are
the catalysts for other corrosion mechanisms to occur. Since there are many possible
mechanisms for MIC, there is no unambiguous method for its diagnosis. Consequently,
the economic importance of MIC in oil field operations is not easily quantified. There
are, however, examples of field data where an empirical relationship between the
population density of surface-dwelling bacteria and corrosion rates have been
demonstrated.

It is clear that, in terms of corrosion processes, the surface dwelling, or sessile,

population of bacteria will have a greater impact than the freely floating, or
planktonic, population found in the bulk water phase.

Historic data at Prudhoe Bay’s SWIS show evidence that corrosion is mainly due to a
combined effect of microbial and oxygen corrosion. Over the past few years the
dissolved oxygen levels have been controlled to <20 ppb and the main corrosion
mechanism is considered to be MIC. In this system a significant correlation (p=0.01)
has been demonstrated between population densities of surface-dwelling sulphate-
reducing bacteria (SRB) and corrosion rates (8,9). Such data cannot prove a cause and
effect relationship between bacteria and corrosion rates; however, they do show
convincingly that higher corrosion rates are associated with locations supporting higher
bacterial populations. From an operational standpoint there is likely to be a benefit in
maintaining bacterial populations at a low level. Indeed, Prudhoe Bay is one asset
where a relaxation and then termination of the organic biocide (glutaraldehyde)
treatment, downstream of the deaerators, resulted in an increase in bacterial

12
populations and corrosion rate measured by weight loss coupons (10). Concern over
the increased corrosion rate resulted in the re-introduction of the glutaraldehyde
treatment. A summary of the various changes to the biocide treatment are given
below:-

Date Concentration Duration Frequency

(ppm active) (hours) (per week)

pre Sept. '90 250 1.5 1

Sept '90 1000 1.5 2
Feb '92 500 1.5 2
Nov '92 250 1.5 1
June '93 0 0 0
Oct. '93 - 500 1.5 2
Mar '96

Table 4 Biocide Treatment History at WOA (PBU, Alaska)

Figure 5 shows the change in corrosion rate by wellhead weight loss coupon over time
at Prudhoe Bay Unit's Western Operating Area (PBU WOA) (31). Average corrosion
rates over the previous 3 months (quarter) and year (annual) are given. It took about
1.5 years after corrosion control was lost before an improvement was seen in the
coupon corrosion rate data. Subsequently, optimisation of the SWIS corrosion
mitigation programme has been an ongoing process; PBU corrosion rate limits are
given in Figure 5.

It was decided to stop sea water injection on the WOA mid '96. Unfortunately the
reason for the increase in corrosion rate from late '95 was not clarified before sea water
injection was stopped. There were a number of possibilities for the higher corrosion
rates of the few remaining injectors, including:

• commingling of PW and SW due to leaky valves.

• injectors were at the far end of the system so they would receive slugs of
biocide which had possibly been consumed to below the effective treatment
concentration.
• lower than average flow rates

Recent inspection of the S risers (piping between the wellhead and choke valve) for
these injectors revealed extensive damage and confirmed the coupon data. However,
coupon data for other injectors suggest that there will be an improvement in the
corrosion rate of the wellhead coupons of these last injectors to be switched to
produced water.

In general, the North Sea fields have considered that oxygen is the main culprit in the
fight against corrosion. This is understandable as any operational problems with
controlling the dissolved oxygen will effect most of the pipework and (perhaps more
importantly) are more likely to cause corrosion of the downhole tubing as the injection

13
wells are relatively close to the deaerator (compared with a field like Prudhoe Bay).
However, North Sea assets are beginning to see signs that microbiological control is an
important part of corrosion management. In order to minimise chlorine /oxygen
induced corrosion, Forties have reduced their maximum limit for chlorine to between
0.2 and 0.3 ppm. Bioprobes and coupons are being pulled every 3 months and the
effect of system changes on bacterial numbers and corrosion rates are being closely
monitored. March 1995 data indicated that Forties Alpha had high populations of GAB
and SRB and also a high general corrosion rate (0.75 mm/yr) and high pitting
corrosion rate (0.31 mm in 118 days = 1 mm/yr). This has been attributed to irregular
biocide treatments and intermittent Cl2 injection due to pump problems since Jan '95.
On the other hand, Forties Charlie, which has regular biocide treatments, has low
bacterial populations and low corrosion rates (<0.1 mm/yr). As the data accumulate, it
will be informative to assess if there is any correlation between bacterial populations
and corrosion rates in a similar way to PBU.

The type of damage observed in sea water injection systems ranges from discrete pits
all round the circumference of the pipe to a linked network of pits or “trough-like”
damage all along the length of a pipe at the bottom of line (BOL) location. This is
illustrated in Figures 3 and 4 from PBU.

The BOL trough or groove like damage was also observed recently in Shell's
Cormorant field's subsea water injection distribution system. The 8" injection line from
Cormorant to the Underwater Manifold Centre failed by perforation over a length of
about 2 m after 11 years service (average material loss rate of 2 mm/y). The groove
began 1.6 km from the platform and then increased in depth over the next 1.5 km. The
final 3 km had a groove of approximately uniform depth with the exception of the
failed section. The operating regime was that of tight control of oxygen, no biociding
(other than chlorination) and no pigging. However, for a period of unknown duration
the oxygen monitor had become fouled giving readings not representative of the
injection water. The flow velocity was 1.2 m/s.

A section of the line was retrieved and the following was noted:-

• A hard scale had formed on the pipe from the 8 o/c around to the 4 o/c
position.
• The groove itself had no scale.
• The groove was mildly asymmetric.
• The scale contained iron sulphide and oxides with some radial (layered)
variations.

Locations at particular risk from MIC include pockets of static water in pipe work
dead-legs. Pipe work and vessels which are not continuously flushed or carry low flow
rates are also at risk from MIC, particularly if the bacteria are protected under surface
deposits on pipe walls (7). Regular maintenance pigging is very important in long lines.
Welds have also been cited as regions prone to MIC owing to preferential bacterial
colonisation of these regions (14). Evidence of this has been found by inspection of
lines at Prudhoe Bay.

14
 The operational risk of MIC to the SWIS will be minimised by controlling the bacterial
populations to a low level. Unfortunately, as yet, there are no analytical techniques
which determine the actual rate of MIC (microbiological induced corrosion) in
operational systems, regardless of the mechanism involved. Current methodology can
only point to the potential for microbiological damage to the system by assessing the
size of the bacterial population, or quantifying the activity of an enzyme system, which
might play a part in the MIC mechanisms.

5.2 Biocide Optimisation

It is perhaps logical to assume that optimisation of biocide treatments should be in

terms of a reduction in bacterial populations. However, it is also possible to work on
the basis of impact to corrosion rate, especially as corrosion control one of the main
driving forces behind biocide treatments in SWIS.

It is recommended that the biocide type and dose are initially optimised in terms of
bacterial numbers. Once it has been established that the treatment is effective
microbiologically, the frequency of application is driven by changes in corrosion
rate.

5.2.1 Measurement of Bacterial Population

It has been mentioned that, in terms of corrosion processes, the surface dwelling, or
sessile, population of bacteria will have the greatest impact on corrosion.
Consequently, biocide treatments tend to be assessed and optimised using some form
of monitoring for sessile populations. In some cases the corrosion coupons used for
weight loss measurements are also used as test surfaces for microbiological analysis.
Ideally, flush-mounted bioprobes should be used in locations where greatest
microbiological activity is expected in relation to flow rates, system temperature
changes and nutrient additions in terms of production chemicals addition. Obviously,
trends in monitoring data can only be identified if a standardised methodology has been
used. Experience has shown, for example, that higher bacterial population densities
tend to be recovered from bioprobes rather than intrusive corrosion coupons in the
same system.

Analysis at a single time point will only give a "snap shot" of sessile bacterial
populations. Thus, the effect of batch dosing of biocides is more realistically assessed
by harvesting test surfaces at time intervals before and after the biocide slug has passed
the test surface location. To enable a time series of analyses to be made relative to a
biocide slug, side stream devices of various designs have been used to determine the
effect upon bacterial populations. Such devices house multiple test surfaces in
mountings, which allow easy access and retrieval of the exposed surfaces.

The availability of multiple test surfaces also allows the precision of the
microbiological analysis to be determined. It is important to check the variation in
bacterial populations between single test surfaces to allow an appreciation of the
precision of the technique and so determine how different subsequent results must be
to signal a significant change in microbiology.

15
5.2.2 Optimisation Based on Corrosion Rate

This approach is taken at Prudhoe Bay. Weight loss coupons at the wellheads and in
the facilities are used to monitor the corrosion rate and give an indication of
improvement to the corrosion control of the system (see Fig 5). Dissolved iron
concentrations are also monitored as an indicator of corrosion rate.

Duration of the slug of biocide versus concentration of the slug is a very important
consideration regarding the biocide effectiveness. Tests by Union Carbide are currently
in progress on behalf of EOA of Prudhoe Bay to give an indication of the important
factor (ie concentration, duration or just bulk amount in ppm-mins) on the
effectiveness of bacteria kill. When EOA decide to reduce the current biocide
treatment level, this information will aid decisions on whether the concentration or
duration should be reduced.

5.2.3 Types of Bacteria and Quantification

The analysis of bacterial populations on the test surfaces may be carried out in a
number of different ways. The technique must measure a phenomenon which will be
influenced by the action of the biocide in a time scale which is consistent with the
interval between the application of the biocide slug and the removal of the test surface
from the system. Enumeration of viable bacteria is often used to determine the effect of
biocide treatments. Of greatest concern is the population of sulphate-reducing bacteria
(SRB) and a measurement of general heterotrophic bacteria, characterised as general
aerobic bacteria (GAB) or general anaerobic bacteria (GAnB).

The SRB have always been of particular concern in the context of corrosion since they
produce corrosive sulphide films and have been shown to depolarise the cathode of
corrosion cells. The SRB are found in association with other bacteria, typically forming
films of biomass (biofilms) on the metal surfaces of the SWIS. The population density
of heterotrophic bacteria gives an indication of the extent of colonisation of the system
surfaces. Figure 6 illustrates the events leading to the formation of a biofilm on a metal
surface, resulting in enhanced corrosion.

Figure 7 is a scanning electron micrograph of an actual biofilm on a bioprobe stud;

individual bacteria are clearly visible. A great range of values has been reported for
sessile SRB in SWIS, ranging from fewer than 1 SRB per square centimetre of metal
surface to 1 million (1x106) SRB per square centimetre (8). It helps to visualise these
numbers if one assumes that a single bacterium has cell dimensions of 1µm by 0.5µm.
It would then require two hundred million (2x108) bacteria per square centimetre to
cover the metal surface in a layer one bacterium deep. The impact of (1x106) SRB cm-2
on the SWIS is potentially severe. Such a population density would be expected to
generate up to 3.4 mg H2S m-2 day-1, on the metal surface of the system.

5.2.4 Influence of Production Chemicals on Bacterial Population

Statoil have demonstrated that production chemicals commonly added to SWIS, such
as oxygen scavengers (OS), scale inhibitors and anti-foams can be used as nutrients by
bacteria (15). Indeed, Statoil data indicate that the nutrient status of injected sea water

16
 can be increased by a factor of 400 for carbon, 20 for nitrogen and 2 for phosphorus.
Assuming that all of the carbon (1 mg/l) contained in anti-foam and scale inhibitor
were converted into bacterial biomass this would result in the formation of an
additional 106 bacteria ml-1 of injection water.

Production chemicals used in BP operations have also been shown to be utilised by

bacteria (16). In this case, however, the chemicals were additions to a produced water
system. Interestingly, not only does the addition of ammonium bisulphite oxygen
scavenger increase the availability of nitrogen to bacteria by a factor of 10 but
increases the potential for H2S generation. Some of the general anaerobic bacteria,
which are not able to reduce sulphate to sulphide can convert sulphite to sulphide (17).
However operational problems with sodium bisulphite due to crystallisation at low
temperatures (e.g. found recently on Forties) may limit the desire of OS (29).

5.2.5 Biocide Injection

Prudhoe Bay has saved operational expenditure by decreasing the throughput of the
SWIS during batch biocide injection. Although the dose rate of chemical remains
constant, a smaller amount of biocide is required since less water is treated per unit
time. However, in systems with long lines to injection wells, such as Prudhoe, shutting
in injection wells during biocide dosing results in large areas of pipe surface not being
treated by the biocide. Clearly, this should be avoided.

A number of assets have found that the biocide injection location makes a large
difference to the sea water quality. It was found that moving the biocide injeciton point
from downstream to upstream of the deaerator towers at PBU’s sea water treatment
plant in November 1995, significantly reduced the number of planktonic SRB in the sea
water leaving the plant. This in turn is considered to be partly responsible for the
reduction in the population of sessile bacteria and thereafter corrosion rates measured
by weight loss coupons. A number of assets already have the injection location
upstream of the tower (e.g. Statoil’s Statfjord field, Miller). It requires more careful
control of the antifoam during biociding to ensure continued optimum tower
performance, but nevertheless can be employed successfully.

5.2.6 Recent Developments in Bacterial Control

Gluteraldehyde has been found to be very effective for microbiological control in the
oil field. However it is expensive and toxic. Kathon is also used by some companies
(e.g. Statoil) which is also very toxic. Thus the drive to find a different biocide is based
on economic and environmental considerations.

A recent development in the control of SRB is a chemical treatment which does not kill
SRB but inhibits the ability to reduce sulphate to sulphide. The product, named Super
Sulf Control (based on anthraquinone) has been shown to work successfully in
produced water at Kinneil (18) and was tested in the SWIS on the Eastern Operating
Area (ARCo operated) of Prudhoe Bay in 1995. Initial results suggested that Sulf
Control treatments maintain soluble iron levels (as an indication of corrosion activity)
at low levels for about 20 days and may be more cost-effective than glutaraldehyde

17
 treatments. However a number operating changes during the tests made it impossible
to draw any conclusive evidence. Statoil will soon be testing the product on Gullfaks.

5.2.7 Reservoir Souring

The main reasons for microbiological control in SWIS is to prevent system fouling,
MIC and, possibly, injectivity decline. Microbiological control of surface facilities in
SWIS is unlikely to have any impact on reservoir souring. Even under the most
rigorous microbiological control programme, millions of live bacteria are injected into
the formation each day. Theoretically, infection of the reservoir by a single SRB could
result in reservoir souring, provided that the SRB could grow and replicate under the
prevailing environmental conditions.

Probably the most important parameters in controlling the manifestation of reservoir

souring are the transit time between injector and producer and the ability of the
formation mineralogy to scavenge H2S.

5.2.8 Raw Sea Water Injection

The possibility of injecting oxygenated sea water during secondary oil recovery has
raised concerns over the extent of deleterious effects of aerobic microbiological
activity upon injection facilities and reservoir rock. Mathematical modelling suggests
that the extent of aerobic microbiological activity would be restricted to a zone within
1 metre of the injection well bore.

It should be noted that carbon steel would not be used for these applications due to the
corrosive nature of oxygenated water. However MIC can still occur with metals of
higher metallurgy and thus control of bacterial growth is still an issue (other material
options are discussed in Section 9.5).

The operation of a SWIS under continual aerobic conditions is expected to result in an

increase in biomass production and encourage types of bacterial metabolism which do
not cause problems in deoxygenated systems. However, microbiological growth in
oxygenated SWIS could be controlled by the rigorous application of continuous
biocidal measures. Laboratory experimentation has suggested that treatment with 1
ppm residual chlorine with a 2 minute contact time would control planktonic aerobes
to a minimum level and minimise the bacterial colonisation of pipe surfaces.

A Joint Industry Programme at CAPCIS on raw sea water injection is considering the
impact of raw seawater microflora on the reservoir (eg. sulphide production, crude oil
degradation) and also the implication of injection on plugging.

The principal findings to-date have been:

• In a pre-soured and oil-free system sandpack containing active SRB, the

introduction of aerated sea water did not affect sulphide production in either
the cool (mesophilic) zone around the injection point or the warm
(thermophilic) zone where SW/PW mixed.

18
 • Oxygen was rapidly consumed by microbial activity resulting in anaerobic
conditions throughout most of the system. Sulphide production was limited
only by the available concentration of organic carbon (mainly acetate) in the
thermophilic zone and, probably, of hydrogen in the mesophilic zone.

• Continuous injection of 1 ppm chlorine together with dissolved oxygen did not
affect the production of sulphide in either zone.

• Continuous injection of 10 ppm chlorine largely eliminated sulphide from the

mesophilic zone. There was no effect on the much more active thermophilic
zone.

• The bioreactor is currently being run with oil-soaked North Sea crude oil. So
far no significant H2S generation has occurred in the mesophilic zone around
the point of sea water injection. However, reports of oil-utilising SRB indicate
very slow growth rates.

• The plugging study element, using equipment supplied by Sunbury, has so far
shown a steady increase in pressure running for 8 weeks at 30oC, but there is
some concern about corrosion of the internals of the cell contributing to this
observation.

5.2.9 Effect of Operating Process Parameters on Microbiological Control

The design and operation of SWIS has an impact upon the microbiological loading
observed under field conditions. In general, water velocities above 3 ms-1 will tend to
minimise (but not eliminate) biofilm accumulation on pipe surfaces (Figure 8).
Similarly, a low concentration of dissolved nutrients in the water stream will minimise
bacterial colonisation. This can be achieved by careful selection and use of production
chemicals such as anti-foam and oxygen scavenger. In microbiological control terms,
the "ideal" SWIS would feature a continuous, high residual concentration of an
effective biocidal agent throughout the system. Financial and corrosion issues force a
compromise on this issue. Oxygen control is less important microbiologically. As
illustrated in Figure 6, even when aerobic conditions prevail in the bulk water phase,
conditions at the biofilm/metal interface (i.e. the area of most importance from a
corrosion point of view) are likely to be sufficiently reducing to allow the activity of
SRB and other anaerobes to proceed.

5.3 Summary

Since each SWIS is different in terms of intake water quality, process design,
production chemicals addition etc, it is difficult to set generic targets for acceptable
microbiological control. In addition it could be argued that corrosion rates should be
the overriding controlling factor on a day-to-day basis. However, in terms of biocide
optimisation, batch treatments should show an impact on the level of sessile
populations in the SWIS. Changes in concentration, duration and frequency of biocide
treatment can be assessed using side stream devices by monitoring the extent of
reduction of bacterial population density and its subsequent duration of reduction.

19
 Enumeration of bacteria in the bulk water phase, (the so-called planktonic population)
provides additional information on the general status of the microbiological control
programme. Ideally, the total number of viable bacteria leaving the SWIS should be
less than that entering the system. In practice, the sloughing of sessile bacteria from
heavily colonised pipe surfaces will tend to increase the population of planktonic
bacteria in downstream regions.

The following targets for bacterial populations are suggested as a general "rule of
thumb" for an ideal system under corrosion control.

Target Population Density

Sessile Bacteria

SRB <102 cm-2

GAB or GAnB <102 cm-2

Planktonic Bacteria

SRB <1 ml-1

GAB or GAnB <104 ml-1

6. PRODUCED WATER SYSTEMS (PWS)

Although Forties reinjected produced water for a short time, normally the North Sea
assets do not reinject produced water, although they have produced water systems:
there are concerns over scaling issues and damage to the reservoir. Other assets, e.g.
Prudhoe Bay, have less of a scaling tendency and have been reinjecting produced water
for a number of years.

6.1 Corrosion Issues And Methods of Control in PWS

The main corrosion concern in PWS is due to dissolved carbon dioxide. Chemical
inhibitors should be used to control the corrosion if the rate is deemed to be
unacceptable high. The corrosion inhibitor can be injected directly into the produced
water stream but may be present in sufficient concentration carried-over from the
upstream multiphase system if carbon steel flowlines plus inhibitor are being used. The
latter is done successfully at Prudhoe Bay and Figure 10 shows how average coupon
corrosion rates have remained under 2 mpy for the past year (31). Further information
and advice on CO2 corrosion may be found in previous guidelines for wet gas and oil
pipelines (21).

Maintenance pigging of produced water lines is particularly important to avoid build

up of “gunk” especially at the 6 o’clock position. The “gunk” consists of organic
matter, biomass, iron sulphide, iron carbonate and, to a large degree, corrosion
inhibitor, and is often referred to as “schmoo” at Prudhoe Bay. If large amounts are
allowed to build up on the bottom of the line, this can cause corrosion problems due to

20
 underdeposit corrosion and/or MIC. This was probably the cause of the trough like
damage shown in Figure 4. There is one theory that the “schmoo” forms a protective
layer on the pipe wall although this has not been proven. It is still recommended that
regular pigging is carried out, since it is likely that a thin layer will remain on the pipe
wall anyway and the corrosion risk, especially to the BOL location, of not pigging is
significantly higher.

6.2 Microbiological Activity in Produced Water

In general, produced water handling systems are likely to suffer greater effects of
microbiological activity than seawater systems. Produced waters contain a range of
organic materials which are present at concentrations many times greater than in
seawater. Of particular interest are short chain organic acids which are known to act as
carbon sources and electron donors for sulphate-reducing bacteria. Concentrations of
acetate, for example, in produced waters may be several hundreds of mg/l but be
undetectable in seawater.

Unlike seawater, the concentration of sulphate in produced water tends to be low.

Where seawater breakthrough has taken place, however, the concentration of sulphate
shifts towards the seawater concentration of approximately 2700 mg/l.

In seawater, the activity of SRB , therefore, is more likely to be limited by the

availability of carbon and in produced water it is more likely to be limited by sulphate
availability.

Clearly MIC is also a concern in produced water systems and microbiological control
should be maintained in a similar way to that discussed for sea water injection systems
in Section 5. The rule of thumb targets will also apply. However, they will probably be
more difficult to achieve, since gluteraldehyde will be consumed by the components in
produced water and this reaction is exacerbated by the higher temperatures. Thus it is
likely that higher concentrations and greater frequencies of biocide treatments will be
required in systems containing produced water than those only containing sea water.

At Prudhoe Bay it was decided to stop biocide treatments after sidestream tests
exhibited little/no benefit from the treatment. On the EOA approximately 2000 ppm
formaldehyde gave insignificant benefit. On the WOA, sidestream tests showed
insignificant benefit; however the gluteraldehyde was being greatly diluted in a skim
tank. The corrosion inhibitor that was being used on the WOA also had a biostatic
portion, which may have been a contributing factor here.

In summary, the cost of microbiological control of a specific produced water system

versus benefit must be evaluated carefully.

7. COMMINGLED WATER (PW/SW)

For operational reasons it is sometimes expedient to commingle produced water and

seawater. Field experience with such systems has been obtained at Endicott, who have

21
 run a commingled system for a few years, and Ula, who started switching between sea
water and a commingled stream on their injectors at the end of 1994. This experience
will be useful for effective corrosion control of water systems of assets who intend to
commingle water in the future e.g. Niakuk.

7.1 Corrosion Issues

Unfortunately, commingled systems have all the corrosion issues from the previous
sections combined together. For corrosion control therefore, the following are
required; corrosion inhibitor injection, oxygen reduction (by mechanical and chemical
means) and microbiological control by biocide treatment. The wellhead temperature is
also higher in commingled systems than in sea water injection only systems (generally
from approx. 15 degC to 40 deg C), which will increase the rate of electrochemical
corrosion reactions.

The most comprehensive experience available for commingled water injection systems
comes from BPX Alaska. A good example of increased corrosion due to commingling,
which is subsequently brought under control by an aggressive chemical treatment
programme, is illustrated by Endicott's Inter Island water line (IIWL); a 14" water
injection flowline connecting the main production island with a satellite island. Data
from quarterly UT scans, at more than 14 BOL locations, show the average corrosion
rate increasing to >50 mpy from late '93 (Figure 10). This corrosion rate increase
coincided with the introduction of SW injection which rapidly moved to full field
commingling of SW/PW. Figure 10 also shows that corrosion of IIWL has been
controlled to <10 mpy since end '94. This is mainly attributed to the stringent biocide
treatment programme initiated at end of '94 (see Section 7.2 for further information).
Other contributing factors are a monthly mechanical pigging schedule and improved
sea water clarification. As part of the ongoing optimisation of the corrosion control
programme, the corrosion inhibitor (injected directly into the PW stream, as duplex
piping is used for the multiphase system) has been changed recently to an improved
performance chemical as a result of field trials in the PBU/WOA production system.

The IIWL is considered separately from the rest of Endicott's water injection system.
This is because the IIWL can be mechanically pigged which should enhance the
effectiveness of the biocide treatments. However smaller diameter flow lines and
downhole tubing are not cleaned and are expected to react differently and/or more
slowly to corrosion control measures. Wellhead weight loss coupon and ER data
support this and current valves are given in Table 5. To monitor the effectiveness of
corrosion control measures on the corrosion of downhole tubing, annual kinley caliper
surveys are carried out. Corrosion rates are calculated from the maximum pit depth
valve for an injector between one year and the next. Initial average kinley corrosion
rate data for '95 - '96 (<10 mpy indicate an improved performance compared with '94 -
'95 data (approx 50mpy).

22
 FIELD OXYGEN GENERAL FLOW COMMENTS
LEVEL CORROSION RATE
(ppb) RATE (mpy) (m/s)

Endicott 10 (but <1 <10 0. 0.1 - 4 Wellhead Coupon

at wellhead) 40-120 and flush ER probe data
no chlorine, (Dec '95)

Ula 10 3 8 Wellhead coupon data

<1 3-7 no chlorine
(July '95 - Dec '96 data)

Table 5: Wellhead Corrosion Rates (Weight Loss Coupon and ER Probe) for
Commingled Systems

Ula platform began commingled water injection in Feb '95. Currently the composition
of the injection water varies between 100% SW (25% of the time) and
75%PW/25%SW (although the PW volume is increasing rapidly). Corrosion inhibitor
has been injected into the produced fluids since June '95, as part of a combined scale
inhibitor/corrosion inhibitor package (Corexit 6209). This is assumed to carry over into
the produced water at a concentration of 30 ppm of PW volume. Biocide is also
injected (see Section 7.2). Corrosion rates from wellhead weight loss coupon data
indicate that these control measures are working (Table 5). These data also suggest
that corrosion is increased above flow rates of 7 m/s.

7.2 Microbiological Activity

Commingling is likely to result in increased SRB population densities and greater

sulphide production. Figure 11 shows the theoretical maximum concentration of
sulphide that could be generated by SRB in mixtures of different proportions of
seawater and produced water. In this example, the seawater is assumed to contain no
acetate but 2700 mg/l of sulphate. The produced water is assumed to contain 300 mg/l
acetate and 10 mg/l sulphate. The reduction of sulphate at the expense of acetate is
assumed to proceed as follows:

CH3COO- + SO4-- ---------> 2 HCO3- + HS-

which is the pathway used by some species of the genera Desulfobacter, Desulfovibrio
and Desulfotomaculum. Mixtures of all strengths of seawater and produced water have
the potential to support more sulphide production than either seawater or produced
water alone. In this example, by theoretical extrapolation, 20% SW is the worst case.
Up to about 20% seawater the production of sulphide is limited by sulphate
availability. Above 20% seawater SRB activity would be inhibited by acetate
availability.

23
 The commingling of seawater and produced water will also have an effect on the
maximum population density of SRB which can be generated by the available nutrients.
The yield of SRB biomass is up to 4.8 g dry weight for each mole of acetate oxidised.
Figure 11 also shows the maximum SRB population density that could be generated by
the use of available acetate coupled to sulphate reduction, assuming that 1g of SRB is
equivalent to 1011 individual bacteria. At all strengths of mixtures of seawater and
produced water, more SRB are likely to be produced than from seawater or produced
water alone.

Field examples of commingling include Endicott and Ula:-

• Endicott have batch treated with 500 ppm active gluteraldehyde for 1 hour
twice a week since end of '94. Bacterial monitoring is carried out monthly for
planktonics (100-104 SRB per ml) at a number of locations throughout the
system. The average count has decreased from >105 to 103 per ml, since the
batch biocide treatments began, indicating an improvement in the general
cleanliness of the system. Quarterly average sessile SRB numbers are in the
range 103 - 106 cm-2. These numbers fluctuate with the time of year and
correlate with average wellhead weight loss coupon data. It is expected that
this is due to fluctuating % SW/PW; data will be analysed through '96 to
attempt to verify this theory.

• Ula has batch treated with 500 ppm 25% gluteraldehyde 2 hours once a week
from the beginning of sea water injection and did not change the treatment
when PW was introduced in Feb '95. Bacterial monitoring is carried out
monthly for planktonics (10-100 per ml) and 6 monthly for sessile bacteria (104
cm-2).

For microbiological control, it is strongly recommended that produced water and sea
water streams are not mixed, since by doing so the bacteria are given the “complete
meal”. Thus there is a high risk of MIC and corrosion control becomes difficult and
costly.

8. CORROSION MONITORING IN WATER INJECTION SYSTEMS

The corrosion monitoring methods available are Linear Polarisation Resistance (LPR),
Electrical Resistance (ER) and weight loss coupons. These are discussed in detail in
BP guidelines (11).

If the system is clean, then intrusive LPR probes should be used for picking up
transients in corrosion rate. Thus they are useful for investigating the effect of different
parameters on corrosion rate in short term trials e.g. Wytch Farm (2) and/or the
corrosivity of the system in normal operating conditions.

Fouling of the probes can be the biggest problem when trying to carry out corrosion
monitoring in WIS. This occurred on Magnus SWIS (3) when trials were attempted. A
typical problem is that LPR is slow to indicate changes in corrosivity.

24
 Another corrosion monitoring method is "iron counts". This method has been
successfully used as a corrosion indicator in Alaska due to the long lengths of piping
and thus large amount of pipewall available for corrosion. It would be less useful
offshore. Currently the EOA are investigating the usefulness of manganese counts.

The optimum monitoring method needs to be assessed on a system-by-system basis. It

must be remembered that electrochemical methods are a useful aid for indicating
relative changes in system corrosivity and enabling a remedial response to be taken
quickly. The probes should be placed such that they will indicate the highest possible
(general) corrosion rates. They should not be used to give absolute values (weight loss
coupons and inspection data should be used).

9. MATERIAL OPTIONS

For replacement of old water injection systems or development of new fields, materials
other than carbon steel are sometimes being chosen. This is because high corrosion has
been observed in the existing water injection system or because minimal risk is allowed
in design (especially subsea wells) or due to a low degree of confidence in water
quality control. Current alternatives in material selection for water injection flowlines
and downhole tubing will be discussed. Material selection issues for subsea equipment
has been discussed in detail elsewhere (22).

9.1 Low Alloy Carbon Steel Downhole Tubulars

In 1994, work carried out at Sunbury highlighted that corrosion in sea water injectors
may be reduced by using 0.5% Cr steel (12). A number of field trials with sea water
systems have been carried out across the industry to try to verify this.

Statoil used low alloy carbon steel coupons (Sumitomo 0.5 - 1 % Cr) alongside "no
Cr" carbon steel ones of matched chemistry, downhole in their injectors. These tests
were intended to explain the improvement in tubular performance since statoil began a
policy of using 0.5% Cr tubing. However, initial results indicate no difference between
corrosion rates with and without the Cr content. Vallourec carried out laboratory tests
on their 0.5% Cr steels at typical sea water downhole conditions with dissolved oxygen
and carbon dioxide. It is understood that they found no improvement over carbon steel
except under more aggressive conditions of low pH and high velocities (25). At BP,
laboratory tests showed no difference between 0.5% Cr and carbon steel (19). Field
data from Magnus are currently being evaluated.

Therefore, currently there appears to be no proof of the perceived benefit in using

0.5% Cr steels for sea water injection. To date, there are no data for 0.5% Cr in PWS;
Statoil and BP are starting test programmes. Also Endicott have recently started
testing 0.5% Cr coupons at a few wellheads in their commingled system.

9.2 Polyethylene (PE) and Glass Reinforced Lined (GRP) Carbon Steel Flowlines

The use of PE and GRP lined carbon steel is becoming more popular within the
industry, especially for new projects. However care should be taken when selecting a
lining for produced water flow lines, as most have limited hydrocarbon service

25
 capablities. Advice on the employment of these materials may be found elsewhere (26,
28). New BP developments e.g. Foinaven, Schiehallion and ETAP are using PE lined
water injection flowlines.

It should be recognised that the method of employing PE lined flowlines for sea water
injection has the potential of pushing corrosion problems further down the system,
since any dissolved oxygen will not be consumed by topsides pipework. This has
possibly been illustrated by the Magnus D4 failure. However it was difficult to know
for certain if the carbon steel tubing failed in 9 yrs (total life) or 2.5 yrs (ie since the PE
lined flowline was installed).

9.3 Plastic Coated and GRP Lined Carbon Steel Tubulars

BP's experience with coated tubing will increase over the next few years as more
developments consider its use for water injection. For example, the first Foinaven
water injector was completed with carbon steel tubing internally coated with
Tuboscope TK-236. The technical and economic aspects of the non-metallic coating
and liner options available for the carbon steel tubing on a second injector can be found
elesewhere (27).

Previous R&D at BP Sunbury has shown that there is the potential for enhanced
crevice corrosion at places where the coating is damaged (13). Coatings are considered
to be of better quality than the past. However it is still recommended that the risk of
imparting mechanical damage is minimised e.g. by limiting well intervention. This is
Arco’s policy after bad experience with damaged coatings.

Glass reinforced plastic (GRP) lined pipe is used widely for injection purposes. Field
experience in the US suggests that GRP lined pipe offers more consistent long term
performance than plastic coated tubing (PCT). The GRP liner is typically 1 to 2 mm
thick, which means that the "holidays" and the susceptibility to damage, associated
with coatings, are less problematic.

It should be noted that there is very little experience in the use of GRP lined tubing for
producers. Nevertheless, GRP lined tubing is economically attractive for producers as
there is a 33% cost saving over 13% Cr. For this reason BPX Alaska are currently
considering its use as an alternative to coated tubing. (Elsewhere PCT has been used
for producers but only with chemical inhibition). However it is recommended that
more field experience is gleaned with injectors before moving on to producers.
Currently Statoil and BP have a joint programme investigating the issues with GRP
liners, mainly under producing conditions.

9.4 Production/Injection Switch Over (ie Production Materials being used for Sea Water
Service

There is growing interest in switching producing wells over to sea water service e.g.
Ula, Gyda, Endicott, PBU. This results in corrosion resistant alloyed (CRA) tubular
materials, e.g. 13%Cr, which have been chosen for produced service, being used in an
environment for which such materials would not normally be selected.

26
A Well Productivity Lever 1995 R&D objective was aimed at investigating corrosion
issues surrounding production materials for sea water injection service (19). A number
of production service materials were evaluated including 13%Cr, "super" 13% Cr,
duplex and low alloy (0.5% Cr) carbon steel. Carbon steel was the control material for
comparative purposes. Loop run trials were conducted in the laboratory to evaluate
these materials' operational limits in sea water injection duty, especially tolerance to
dissolved oxygen and chlorine. It was beyond the scope of the work to cover the
effects of dissolved CO2 (and the likely corrosion synergy with dissolved oxygen),
which would be present after gas stripping of oxygen from sea water. This is mostly
because BP assets (except Forties and Endicott) employ vacuum stripping in their
water injection systems.

13% Cr stainless steel was found to experience substantial crevice corrosion above 10
ppb O2. Pitting was also observed between 20 and 200 ppb O2. Super 13% Cr and
duplex stainless steels did not crevice. However all stainless steels experienced pitting
above 0.4 ppm Cl2. Vallourec’s study found very similar behaviour (25); note they used
dissolved CO2 and O2, to simulate a gas stripped deaeration system.

Field experience has shown varying performance of 13% Cr for SWIS:-

• Gyda has switched four wells, completed with 13% Cr, from production to sea
water injection service; they have tubing/annulus communication on all of them.
BP Norway do not run any Kinley calipers in Gyda's 13% Cr injectors, because
experience on Ula showed them to under-predict pitting corrosion. However,
they have run Sondex 40 arm calipers (Maritime Well Service) in two of the
wells and these have shown quite severe pitting.

• Statoil (Gulfaks) experienced crevicing and pitting of 13%Cr stainless steel and
have since abandoned using this material for water injection.

• PBU have apparently been successful using 13%Cr stainless steel for water
injection; kinleys are not run but weight loss coupons have not shown any
damage The absence of pitting could be due to their long carbon steel flowlines
acting as very effective oxygen scavengers. Measured oxygen levels at the
wellhead have been <5ppb O2 in the past which suggest hat all is well in terms
of operational control. However, the point remains that if replacement or repair
is needed upstream of the well line, it is possible that oxygen levels could be
high for a time when the line comes back on stream. R&D shows that this short
burst of O2 would be all that is needed for pit and crevice initiation, which
could then lead to severe localised attack. Crevice coupons could be
considered.

• Endicott has one PW/SW injector completed with 13% Cr, as a test site since
early 1994. It is being kinleyed every 6 months and has shown no damage. As
mentioned above, although a kinley caliper survey would detect severe crevice
attack, it is unlikely to detect localised pitting attack, so a 13% Cr weight loss
coupon has been installed at the wellhead. A crevice coupon will also be
installed soon. Alternative inspection techniques are being considered eg the
Sondex 40 arm caliper and Schlumberger’s Ultrasonic Imaging Technique.

27
 No field experience exists with super 13%Cr stainless steel because it is a relatively
new material. However it is certainly an area worthy of further study. There could be a
prize to be had at little extra cost (compared with duplex) if this material performs
satisfactorily for produced water/seawater injection duty. Loop tests are being carried
out at Sunbury for Miller.

9.5 Raw Sea Water Injection

Raw sea water injection requires in principle the deployment of exotic materials and
solutions to the difficult problems posed by the highly corrosive conditions. It should
be recognised that many items are likely to have long lead times and will inevitably be
'specials' (i.e. not available off the shelf).

A Joint Industry Project at CAPCIS is being undertaken on raw sea water injection. In
'94 a literature review was carried out. This was used as a part of a separate
engineering feasibility study/economic analysis conducted with respect to possible
application on Foinaven (30). It was concluded that GRP lined tubulars (using Rice
Engineering Douline system) was necessary to become economically attractive over
conventional sea water treatment. Statoil's Yme and Norne fields use GRP lined tubing
with titanium, Inconel 625 and 686, Incaloy 725 and Hastelloy C726 used for
jewellery, cross-overs, pup peices, hanger, Xmas tree etc, with an upper temperature
limits set on the CRAs eg. 725 16oC, C276 30 - 35oC, 686 48 - 50oC.

CAPCIS testing of different materials started in Feb '95 using a once through flowloop
located at a coastal site constantly drawing in fresh sea water. The materials being
tested are 3 Ni-based CRAs (alloys G-50, C-22 and C-276), one GRP lining (Duoline
20 produced by Rice Enginering) and one coating (TK-236 produced by Tuboscope
Vetco). Straight pipe sections and VAM-ACE joints are being tested together with
standard castellated crevice samples. The JIP saw no added value in testing titanium as
all available evidence suggested that this material was acceptable for raw sea water
service; although care in choosing the right alloy needs to be exercised (eg. Ti - 6V -
4Al used by Statoil).

To-date all three CRAs have exhibited only slight crevice corrosion activity. This was
observed both in the presence and absence of chlorination. Outside of crevices,
electrochemical measurements indicate short lived transient localised corrosion
activity, which always repassivates. The two non-metallic lining and coating systems
have so far shown no signs of degradation.

Whilst the JIP is not testing any duplex CRAs, a separate programme funded by one of
the Japanese steel manufacturers is testing a super duplex stainless steel alloy under
similar test conditions. The limited feedback from this programme indicates that this
alloy is not performing any worse than the alloys being tested within the JIP at this
stage in the programme.

28
9.6 Preferential Weld Attack in WIS

Work by CAPCIS recommended the use of high Ni residual welding consumables for
SW service ie. suppress preferential weld attack due to O2 corrosion. However where
there remains a concern is for PW as the corrosion mechanism is driven by CO2. Work
at CAPCIS with PW, subsequent to that for SW, was totally inconclusive and so BP
was consequently forced fall back to running welded weight loss coupons on Forties:
this is still ongoing and the results to-date are proving no more conclusive. There is
collaboration with Statoil and there is also the Ula experience of using a 0.5%Cr
welding consumable in repairing a failed production flowline. However, the consensus
view within BPX North Sea is moving closer to standardising on using a Ni
consumable since it does not appear to have a significant adverse effect on corrosion in
PWS.

10. MAINTENANCE PIGGING

It has already been mentioned that an important part of corrosion control is regular
pigging of water distribution lines. This is to try to prevent solid build up in the line
and minimise underdeposit corrosion. It also allows the biocide treatments to be more
effective and thus minimise MIC.

Kuparuk (Arco operated oil field on the North Slope) carried out tests this year to
determine the optimum pigging frequency of water injection lines (23) . By measuring
the rate of build up of solids, it was determined that the optimum frequency for sea
water injection lines was 3 monthly and monthly for produced water lines. This is the
same frequency employed by Prudhoe Bay. There is evidence to suggest that being
unable to pig sea water injection lines results in increased corrosion rate as measured
by flush weight loss coupons. Corrosion rates subsequently reduced when pigging was
resumed. However other operational changes (e.g. Summer shutdown) may well have
influenced the corrosion rates too.

A concern on the North Slope are the 4-6” well lines (from the manifold building to the
well pads) which cannot be pigged. Kuparuk tested Acrolein over a 3 month period in
their produced water system; it was found to be unsuccessful at removing existing
solid deposits in produced water lines (24). However the treatment was found to be
successful at reducing the accumulation of solids on coupons, reducing general and
pitting corrosion rates and scavenging sulphides. Thus Acrolein would be more useful
at keeping new piping clean, rather than cleaning up old piping. It may also be used as
an alternative to film-forming corrosion inhibitors (despite being environmentally
unfriendly and very toxic to handle).

11. DAY-TO-DAY CONTROL OF WATER QUALITY OF SWIS

It is important to stress the need for accuracy of the laboratory and on-line data and
setting the appropriate frequency at which it is collected if a successful corrosion
control of the system is to be effected. To facilitate this process, an "action chart"
(Figure 1) has been developed for use in the field. It is only a starting point towards

29
 gaining optimum control of the system and can be adapted for specific use by
individual assets.

12. UNRESOLVED ISSUES IN SEA WATER SYSTEMS

There are a number unresolved issues regarding the effect of water quality on
corrosion, which would further facilitate operation of a sea water system with
minimum risk of corrosion:-

• What is the detrimental effect of residual oxygen scavenger? Is 1ppm residual

bisulphite an acceptable maximum level? Currently the perceived dangers are based
largely on empirical data.
• What is the optimum factor which should be applied to the Oldfield and Todd
prediction model for oxygen corrosion? The current design factor is 1/3-1/5 up to a
"cut-off" velocity, based on empirical and some laboratory data.
• Verify the "cut-off" value above which protective scales will be destroyed and the
design factor (applied to the Oldfield and Todd model) cannot be applied.
• Quantification of corrosion damage is required for periods when operational control is
lost e.g. when O2 spikes occur in the system, or when Cl2 residuals are high (>0.4
ppm).
• What should be done for microbiological control of systems which are fouled due to
historically poor bacterial and oxygen control? Attempt to get down to bare metal and
"start again" or try to treat the system as it is?

30
 REFERENCES

1. Minimising Corrosion of Carbon Steel in Sea Water Systems - Guidelines for Water
Quality, ESR.94.ER.005, J T A Smith

2. A comparison of corrosivity with operational parameters for the Wytch Farm seawater
injection system, ESR.94.ER.120, S Webster, J T A Smith

3. Magnus Trials, BPX internal memo, July '94 , P Smith, J T A Smith (see Appendix 1)

4. The Effect of Chemical Drag Reducers on Sea Water Injection Line Corrosion: Data
from Conoco Flow Loop, A J McMahon, ESR.95.ER.082, August ‘95

5. Forties trials, S Cooper, C White, internal memo

6. Erosion Velocity Limits for Water Injection Systems, M Salama, Materials

Performance, pp44, July '93.

7. Microbiologically Influenced Corrosion (MIC) In Oil Production Operations, BP

America Report No 8615, dated 2.4.93, I Vance

8. Prudhoe Bay Unit, Critical Review of Microbiological Issues, Report No

ESR.93.ER.131, dated October '93, I Vance

9. Prudhoe Bay Unit (Western Operating Area). Correlation of Microbiological &

Corrosion Coupon Data, September 1990 to June 1993, Report No ESR.94.ER.001,
1994, I. Vance.

10. 1993 SW System Corrosion Monitoring Review (Prudhoe Bay) December 1993, R.C.
Woollam.

11. Corrosion Monitoring Guidelines, S Webster, R C Woollam, in press

12. 0.5% Chromium Steel Downhole Tubulars - Availability and Limits of Application,
ESR.94.ER.096, dated 30.9.94, J T A Smith, J Martin

13. The effect of wireline damage on the corrosion of plastic coated downhole tubulars,
dated 9.8.92, Report No ESR 124411, G Clayton, R. MacCuish

14. Blackwood, D.J., de Rome, J.L., Oakley, D.L., Pritchard, A.M., Walter, E.R. MTS
Environmental DEgradation Programme. Project 4-Microbially Induced Corrosion.
Critical Review of Microbially Induced Corrosion. Atomic Energy Authority, 1994.

15. Sunde, E., Thorstenson, T., Torsvik, T., Growth of Bacteria on Water Injection
Additives, SPE 20690, 1990

16. Dobransky, D., Production Chemicals as Nutrient Sources for Bacteria from Prudhoe
Bay WOA Production Facilities. Warrensville Topical Report No. 8482, 1992

31
17 Vance, I., Hydrogen Sulphide production fro Sulphite and thiosulphate by non SRB
Isolated from Oil Separators on North Sea Platforms. Sunbury Tech. Memo. 135710,
1987.

18 Vance, I., Non-Biocidal Treatments for the Inhibition of Microbiological H2S

Generation. Sunbury XTP Report 1995 223644.

19 Gourdin R, Production/Sea Water Injection Switchover Of Wells-Effect On Corrosion

Of Tubular Materials, ESR.96.ER.018, 22.2.96

20 Webster S, Wytch Farm Corrosion and Inspection Review, Sept '95.

21. "A Corrosion Philosophy for the Transport of Wet Hydrocarbon Gas Containing
CO2", I Parker, J Pattinson, A S Green, ESR.94.ER.016, 28.8.94

22 Corrosion Issues In Material Selection For Subsea Equipment, J T A Smith, D Harrop,

J W Martin, D Fairhurst & J Pattinson, ESR.95.ER.135, 23.12.95

23 E. van der Wende, C. L. De Rienzo, E.R. Goldmann, A Study to Determine the

Optimum Pigging Intervals for Water Injection Lines, NACE Canadian Region
Western Conference, February 1996, Anchorage, Alaska.

24 E. van der Wende, C. L. De Rienzo, M Harless, S T Paakkonen, P B Simons, and F F

Summerfelt, The Effect of Acrolein Treatment on the Corrosion Rates of Mild Steel
piping of a Secondary Oil Recovery Produced Water Flood, NACE Canadian Region
Western Conference, February 1996, Anchorage, Alaska.

25 C Linne, Corrosion Test Simulating Water Injection Wells, Vallourec Report No 3605,
Nov ‘95 (author awaiting copy)

26 S Groves, Low Cost Pipeline And Flowline Options, ESR.95.ER.134, 18th December
1995

27 S Groves, Internally Lined And Coated Options For Foinaven Water Injection Tubing,
ESR.96.ER.021, 8th March 1996

28 S Groves, Corrosion Control Using Polymeric Materials - GRP And Liner Update,
ESR.94.ER.125, 21st Dec ‘94

29 A J McMahon, H Macdonald, Oxygen Scavenger Trials on Forties Charlie and Bravo

Sea Water Injection Systems, 11-17 April ‘96, Aug '96, ESR.96.ER.068

30 Seabed Rawwater Injection Study - Study Report Volumes 1 & 2, Prepared by

CAPCIS Ltd, Mentor Engineering Consultants Ltd, and XTP/XFE, XFE/026/94, July
1994

31 R Woollam, CIC Performance Indicator Review, Jan '96

32
32 J T A Smith, Endicott Water Injection System Review, May '96, Produced Water
Lotus Notes

33
 APPENDIX 1

CORROSION TRIALS ON MAGNUS SEA WATER INJECTION

SYSTEM (2-716194)
Corrosion Trials on Magnus Seawater lnjection System
(2nd-7th June 1994)

BACKGROUND

The most corrosive species in a sea water injection system is dissolved oxygen, the
concentration of which is therefore controlled. The rule of thumb for "safe" operation
is "less than 20ppb oxygen". On Magnus the oxygen concentration is typically 10ppb,
which is achieved by vacuum deaeration, in conjunction with injection of oxygen
scavenger.

A previous review of corrosion in seawater injection systems, by GRE Sunbury,

highlighted other parameters, in addition to oxygen, which impact upon the corrosion
rate. These include chlorine concentration, excess bisulphite concentration, flow rate
and microbiological activity. There will be an acceptable range for these variables
which will be dependent upon the allowable corrosion rate for the system. In order to
control the corrosion rate in the Magnus seawater injection system, the acceptable
values of the above variables need to be identified and adhered to.

TRIALS

A series of trials were carried out on Magnus (2-7 June 94), the aim of which was to
identify the impact of oxygen, chlorine and residual bisulphite concentrations on the
observed corrosion rate. The oxygen concentration was varied by adjusting the oxygen
scavenger injection rate and the chlorine concentration was varied by adjusting the
electrochlorinator voltage. Oxygen, chlorine and residual bisulphite concentrations
were measured throughout the trials. The oxygen content was measured using both an
Orbisphere and chemets, and the output from the Orbisphere was continuously logged.
The corrosion rate was monitored use two Capcis March probes, both of which were
in 20" lines. Although velocity is expected to have a large impact on corrosion rate, it
was not varied during these trials due to the location of the probes. The impact of
velocity will be assessed when a corrosion probe is installed in a well flow line (well C5
has been selected).

The "baseline" operating conditions for the system during the trials were 250,000 bpd
water injection, 6.4 L/hr oxygen scavenger injection and a 38% setting on
electrochlorinator. This typically resulted in 10ppb oxygen at the injection pumps.

DISCUSSION

Corrosion Data

Some difficulties were encountered in monitoring the corrosion rate during the trial.
This was due to a combination of the logarithmic display on the Capcis March system
on Magnus, and the fact that it was not possible to download data whilst onboard.
Consequently, it was not possible to determine whether the corrosion rate stabilised
after each trial before commencing the next trial. When the data was downloaded
onshore it became obvious that several trials should have been run for longer.

At baseline conditions, a corrosion rate of 4.7mpy (0.12mm/yr) was observed, which is

similar to research data published previously (for example, 1-3mpy at 20ppb oxygen
and <15¡C). At high oxygen levels (~200ppb), the corrosion rate increased by 34% to
6.3mpy (0.16mm/yr). This is lower than expected when compared with published data
which show general corrosion rates increasing to 20mpy (0.Smm/yr) with rates as high
as 200mpy (5.2mm/yr) at weldments. The highest corrosion rate observed during the
trials occurred when the plant shutdown; this resulted in a corrosion rate of 13mpy
(0.325mm/yr).

Corrosion rates can be predicted in water injection systems. For the probe locations
used in these trials (20" line,7-8 ft/sec), a corrosion rate of 8mpy (0.2mm/yr) is
predicted at 10ppb oxygen and 134mpy (3.4mm/yr) at 200ppb oxygen. The predicted
rate at low oxygen concentration is similar to the rate observed in these trials.
However, at high oxygen concentration the predicted rate is much higher than the
observed rate. Although it is suspected that the prediction method overestimates the
corrosion rate at high oxygen concentrations, the discrepancy in these trials is much
larger than expected.

Over dosing of the oxygen scavenger did not have an obvious impact on the corrosion
rate whereas increasing the chlorine concentration (when no oxygen scavenger was
being injected) increased the corrosion rate to 4mpy (0.16mm/yr). However, the
corrosion rate was still rising when the test was stopped. Previously reported data has
shown corrosion rates up to 0.2mm/yr with increases in chlorine at low oxygen
concentrations.

It must not be assumed that since relatively low corrosion rates have been
observed then this is true for the whole system, particularly as much higher
velocities are observed elsewhere.

Monitoring Equipment

The LPR did not respond as expected in two ways. Firstly, it was too slow to react
after a change in operating conditions. Secondly, it did not reach a significantly high
corrosion rate at high oxygen concentrations. This poor response was probably due to
filming of the probes (either by a biofilm or with corrosion products); hence we are
measuring a mass transfer effect through the film rather than an actual corrosion
response. Consequently, cleaning the probes may improve the quality of data that is
collected.

Electrochemical noise showed a similar trace to the LPR. The sampling frequency
currently being used is unsuitable for this technique. The data needs to be taken more
frequently so as to allow pitting corrosion rates to be assessed. The electrochemical
noise data would also be improved if the probes were cleaned.
General Observations

The vacuum tower performance was good, with 5- 10ppb oxygen being measured at
the outlet of the towers, although this increased to about 180ppb upstream of the
water injection pumps unless oxygen scavenger was added. This is probably due to
oxygen ingress at pump seals or flanges. Oxygen scavenger is only required on a
continuous basis to negate the effect of this "leak" into the system.

The oxygen measurement at the outlet of the vacuum towers was affected by the
residual chlorine level. With the electrochlorinator off the oxygen was measured at 5-
lOppb but with the electrochlorinator on the oxygen was measured at 40-60ppb.

The oxygen scavenger took ~30 mins to return the oxygen concentration to baseline
conditions after a high excursion. The corrosion rate took longer to return to the
baseline, probably l-2 hours; this needs to be confirmed in a future trial. The shutdown
of the water injection system resulted in the oxygen content increasing to 430 ppb.

The oxygen content was observed to oscillate in a cyclic fashion 10 ppb about a mean
value. This only occurred when oxygen scavenger pump was in use,and suggests that it
is related to the pump stroke.

RECOMMENDATIONS

Corrosion Data

Repeat specific trials (particularly at high oxygen levels and including some at higher
chlorine contents) ensuring that the probes are clean and that the tests are carried out
for long enough. Perform additional trials to assess the impact of velocity, when a
probe is installed in C5 flow line.

Monitoring Equipment

Pull probes, visually inspect surface for evidence of biofilming/general corrosion/

pitting and take samples of any deposits. Clean the probes thoroughly by rinsing with
xylene, polishing with 600 grit, followed by a final xylene wash. Recommission each
probe by using the CML data to check that all connections have been made and a
sensible response is being recorded.

Assess speed of fouling by analysing data before and after probe pulling.

Increase frequency of collection of electrochemical noise data.

Identify the cause of oxygen ingress into the system. Preventing the ingress of oxygen
would reduce the required concentration of oxygen scavenger.
 EXPECTED CHLORINE RESIDUALS FOR VARIOUS
ELECTROCHLORINATOR SETTINGS

DIAL SETTING (%) CHLORINE (PPM) CHLORINE (PPM)

PRE-VAC TOWER POST-VAC TOWER

38 0.6-0.7 0.1-0.2

58 1.3-1.5 0.7

68 1.3-1.5 1.0

Notes:
Chlorine is measured using colorimetric technique.
80% setting would not be used as cells would be destroyed.

P Smith Dyce x4493

J T A Smith Sunbury x3900

17.6.94
 “ACTION CHART” FOR SEAWATER INJECTION SYSTEMS

Oxygen concentration data preferably from

on-line dissolved oxygen meter
Main process checklist immediately and
report to supervisor

No

Are all parameters

within recommended
Yes limits?

Is oxygen Yes
concentration Interim checklist once per shift
<20ppb?

No Yes

Is oxygen Yes Is time duration

concentration of excursion
<50ppb? <30mins?

No Interim checklist immediately and thereafter

No every hour until control is regained - report to
supervisor

No

Is oxygen Yes Is time duration Yes Does excursion

concentration of excursion repeat within
<100ppb? <5mins? 30mins

No No Yes
Main process checklist immediately
and report to supervisor

Interim Laboratory Checklist Main Process Checklist

To be carried out once per shift
routinely at outlet of tower plus
whenever an oxygen alarm
occurs
• Dissolved oxygen
• Oxygen scavenger residual
• Chlorine
(Use colormetric or other lab
method)
To be carried out whenever a
specific alarm suggests it is
required
• Oxygen scavenger pump rate
• Residual oxygen scavenger
level
• Chlorinator setting
• Leak check (possible ingress)
Notes
• Regular maintenance of on-line oxygen meter is
essential.
• Recommended oxygen concentration limits and
time durations of excursions may vary for
individual systems depending on the flow rate
through the system. Thus the corrosivity of the
system under different operating conditions
should be assessed.
XTP 36725