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Section ViI-Paper

CORROSION IN SALT WATER


COOLING SYSTEMS
BY

E. D. DOLAN*
ABSTRACT. Experimental work at BP Refinery (Kent) Limited is described. I n channel ends
and floating head ends of condensers, magnesium anodes (1) directly connected, (2) with
resistance control and (3) with aluminium sheathing were partially successful in preventing
corrosion; zinc anodes gave adequate protection when combined with coatings and stainless steel
facing of the flange mating with the tube plate. Present practice is outlined. A simple method of
protection is suggested, based on epoxy mastic coating and full-face iron anodes. A reliable tube
plate coating is required to increase the life of sacrificial anodes.

A section of 60 inch diameter cooling water main fabricated in steel has been protected
internally by impressed current; the optimum anode spacing is four diameters. At water velocities
up to 2% f.p.s. a current density of 5 m.A./sq.ft. gave protection. Zinc anodes gave barely
adequate protection at 48 spacing in an unlined section; zinc anodes at 98 spacing in a section
lined with coal tar paint gave over-protection.
Promising results were obtained with coatings of epoxy mastic, aluminium-bitumen paint, zinc
rich primer plus coal-tar top coats and a synthetic rubber/cement mastic.

RESUME. Des essais, effectus la Raffinerie BP (Kent) Ltd., sont dcrits dans cet article. Dans
la bote de circulation et la tte flottante de condenseurs, des anodes en magnsium 1) en contact
direct avec le mtal, 2) avec une rsistance intercale et 3) avec un revtement daluminium, ne
parviennent que partiellement viter la corrosion; des anodes en zinc ont fourni une bonne protection lorsque combines avec un revtement en acier inoxydable du rebord en contact avec la
plaque tubulaire, et avec des couches de peinture. La mthode utilise actuellement est dcrite dans
ses grandes lignes. On suggre une mthode simple de protection base sur lemploi dun revtement
d epoxy mastic et danodes en fer recouvrant totalement la section extrme de la bote de circulation. Un bon revtement de la plaque tubulaire est ncessaire pour diminuer la vitesse de
destruction des anodes.
Un tuyau dacier de lm.50 de diamtre pour le raffraichissement de leau a t protg
lintrieur par courant imprim; lcart optimum des anodes est de 4 diamtres. Pour une vitesse
deau de 0,75 m/s une densit de courant de 53 m.A/mJ a donn une bonne protection. Des anodes
en zinc espaces de lm.4 nont donn quune protection peine suffisante dans un tuyau nonrevtu; des anodes en zinc espaces de 3m. ont donn une protection excessive dans la partie du
tuyau revtu de peinture au goudron.
Des rsultats prometteurs ont t obtenus avec des revtements d epoxy mastic, de peinture
de goudron laluminium, une premire couche de peinture riche en zinc recouverte de couches de
goudron, et un mastic de caoutchouc synthtique et de ciment.

* Corrosion

Control Engineer, Refineries and Technical Dept., The British Petroleum Company Ltd.,
London, England.

1o9

110

FIFTH WORLD PETROLEUM CONGRESS

Introduction

The British Petroleum Company Limited is interested in seven refineries with salt water cooling, of
which one is in England, three in Europe, two in the
Middle East and one in Australia. The refinery at
Abadan operated by BP up to 1951 was exceptional
in that it utilised a once-through cooling system of
non-aggressive water from the Shatt-el-Arab; consequently, prior to the post-war refinery development
programme, little direct company experience of salt
water cooling was available, although it was realised
that conventional materials would be subject to
corrosion.
The Isle of Grain Refinery (BP Refinery (Kent)
Ltd.), commissioned in 1953, was one of the first
post-war refineries built for salt water cooling. Plant
trials on methods of protection started as soon as the
first units came into operation. This paper describes
the results obtained on condenser ends and on a steel
salt water main; the general pattern of protection is
coating supplemented by cathodic protection.
The use of impressed current cathodic protection
for condensers has been given due consideration and
it has been decided that the wiring complications
and possible spark hazards render it undesirable in
the danger areas of operating plant.
General Considerations

The cooling water requirements in a refinery are


measured in millions of gallons per hour; the cooling
water system represents a major investment and can
be a heavy burden on maintenance. Because of the
magnitude of the system discretion must be exercised
in choice and cost of materials.
The first and most important corrosion protection
is good hydraulic design of the system. First essentials are: Water velocity in pipework below, say, 7
feet per second; smooth flow; low speed pumps with
drowned suction; exclusion of debris and marine
growths; and selected ranges of water velocity in
condenser tubes. The system should use valves for
isolation rather than for control of flow; if a wedge
gate valve is operated partly open with salt water,
the valve body or the pipework downstream of the
valve will perforate rapidly. Pipes should always run
full. Pipework, tubulars and other vessels should be
drained when not in use, and not, as happens too

frequently, be allowed to remain full of stagnant


sea water for long periods.
Starting with a well-designed system, the protective
measures required are mainly devices to overcome
galvanic couples which encourage local attack and
pitting. Insulation of noniferrous parts from steel or
iron parts is always difficult to achieve in practice
and is of doubtful value in waters of low resistivity.
There is no doubt, however, that reduction of the
cathodic area, for example, by coating a non-ferrous
tube plate, is a most useful device. Reduction of the
anodic area is inadvisable unless cathodic protection
is applied.
Many varieties of protective coating are available,
with many variations in complexity of application
and in first cost. Other things being equal, it is
generally accepted that film thickness is the most
important property. I n the authors opinion, no coating can be guaranteed perfect when finally installed
and coatings subject to immersion in salt water should
be supplemented by cathodic protection where possible. Having accepted this last requirement, it is not
necessary to strive for very high grade coatings; the
standard of coating for use with cathodic protection
becomes a practical proposition for normal refinery
facilities. Coatings in cooling water mains and pipework and condenser ends should not be of such a
character that, if adhesion fails, they can come away
in sheets or large fragments and block the system,
particularly the condenser tubes. For this reason,
heavy coatings of bituminous enamels are not
favoured.
Protection of condenser ends is mainly a large
scale exercise in cancelling a galvanic couple, complicated by the vital consideration that protection
must not decrease the life of the tubes. Pitting attack
in steel pipework is more rarely due to dissimilar
metals, being generally caused by remanent millscale
and by differential aeration cells formed by mud
scabs and other deposits.
Long life, of the order of five years, is a most
desirable property of sacrificial anodes in salt water
cooling systems, so that no part of the system need
be opened for the sole purpose of renewing the
anodes.
The work described in this paper has drawn attention to four devices which are reasonable in cost and
which if used with full knowledge of their capabilities

CORROSION

IN SALT WATER COOLING SYSTEMS

and limitations should prove valuable aids in protection schemes in salt water. These devices are:
-Zinc alloy anodes.
-One coat linings of epoxy mastic.
-Aluminium-bitumen paint.
-Zinc rich primer sealed with heavy bituminous
paint.
The iron anode, also, is useful and will repay
further study.

Section 1-Channel Ends and Floating Head


Ends of Condensers
Considerations

TUBES

The resistance to corrosion of condenser tubes


depends mainly on a thin protective film which forms
naturally in clean sea water by a slight general and
uniform corrosion all over the tube. From time to
time, condenser tube specialists [i] have issued warnings against interfering with protective film formation, particularly by using sacrificial anodes. Their
reasons are as follows:
-Iron in solution in the sea water strengthens thc
protective film.
-When
sacrificial anodes provide cathodic protection, the tube ends, but not the tube as a
whole, are protected by a cathodic deposit containing calcium carbonate, and not by the
natural film. The cathodic deposit is protective
only while the sacrificial anodes are operating
and rapid tube end attack is possible if the
anodes are allowed to become exhausted.
-Breakaway of anode corrosion products or anode
metal can block tubes or induce failure due to
deposit attack or impingement attack.
-There is some evidence that zinc and tin corrosion products reduce the life of aluminium brass
condenser tubes.
These factors have always been given due consideration, although so far no ill effects have been
noticed due to the use of sacrificial anodes, probably
because the salt water contains iron picked up from
the cooling water system and the tubes most commonly used are Admiralty Brass. However, experience
of sacrificial anodes is comparatively short and at
this stage we can be certain only that cathodic protection does not lead to catastrophic failure of condenser tubes.

111

Sacrificial anodes of iron offer less possibility of


damage to condenser tubes and it may quite well be
that the developments described here will ultimately
result in the use of iron anodes with high grade
coatings, or iron anodes with non-ferrous condenser
ends.
TUBEENDS

Attack on tube ends is very much dependent on


correct design of water spaces and on water conditions such as turbulence and mean water velocity;
most refineries now adopt a range of water velocities
for the various tube alloys [2], although it is doubtful
if these are always closely observed in practice.
Several instances have been encountered of tube
end attack due to lack of a less noble material in the
channel or floating head to provide cathodic protection to the tube end. Condenser ends lined with
rubber and with stainless steel sheet, and also, nonferrous ends, have been observed to cause tube end
attack; condenser ends of this type should be fitted
with an iron anode.
TUBE PLATESA N D TUBEENDS AS CURRENT
COLLECTORS

It is suspected that the tube ends projecting from


the tube plates act as current collectors; also, it is
reasonable to suppose that protective current from
anodes will penetrate a short distance inside the tube.
Thus the effective current collecting area of the
tube plate/tube end complex may be considerably
greater than the nominal area of the tube plate.
Loss rate calculations suggest that the current density demanded from sacrificial anodes by the tube
plate plus tube ends is of the order of one hundred
milliamperes per square foot of nominal area. A
laboratory investigation to define the role of the
tube ends has been started; there is little doubt, however, that coating of the tube plates is most desirable.
CAST IRONWATERBOXES

Cast iron water boxes are still general practice in


stcam condensers. They present special difficulties :
1. When fully graphitised, the graphitised surface
can be noble to the tube ends.
2. Sacrificial anodes cannot be welded in position.
3. Welding repair of wastage, notably of division
plates, is impractical.

112

FIFTH WORLD PETROLEUM CONGRESS

One refinery has- reported that cast iron water


boxes have graphitised to failure, in spite of having
cathodic protection by magnesium anodes which had
been well maintained and had produced a good
calcareous deposit. I t seems that if a graphitised
layer (a conducting layer) is once allowed to form,
then it functions as an electrical shield. The graphitised layer receives protective current and a calcareous deposit forms, but the protective current does
not penetrate to the underlying metal. A galvanic
couple exists between the underside of the graphitised
layer and the base metal and further graphitisation
can proceed.
It appears that cast iron which has started to
graphitise may not obtain full benefit from cathodic
protection unless all graphitised material is first
removed.

local labour in site workshops, which generally have


sand blast equipment.
Stoved phenol-formaldehyde coatings, factory applied, have given good service when supplemented by
zinc anodes. With magnesium anodes some alkali
attack has been experienced, the coating being replaced by a calcareous deposit near the anode. Coatings of this type, however, are not suitable for
application in site workshops.
The various classes of paint tried include asphaltic,
coal tar, chlorinated rubber, neoprene, vinyl and
epoxy; of these, a three- or four-coat epoxy system

w
BARE 4 L B
ANODES

Coatings

Based on theoretical considerations and on observation, and with particular reference to the fact that
the anode and cathode areas in channels and floating heads are of the same order of magnitude, the
following opinions have been formed on coatings in
general :
I. Coatings alone on ferrous components such as
channels are dangerous. The underlying steel
will perforate rapidly at any fault in the coating; the tube ends receive negligible cathodic
protrction.
2. Coatings on non-ferrous components (tube
plates etc.) are useful and are not dangerous,
cxcept that there is some risk of encouraging
dczincification of brass in the absence of any
cathodic protection.
3. When used in conjunction with sacrificial
anodes, coatings on the tube plate and tube
ends would be more useful than coatings on
the ferrous components, since they reduce the
effective area of the more noble metal.
4. The highest grade of non-metallic coating is
imperfect by the time the coated part is installed in the unit. Therefore, coatings should
always be supplemented by cathodic protection.
The trials on coatings have been influenced by the
fact that over a thousand condensers must be maintained in various parts of the world, so that an
acceptable coating must be suitable for application by

STAGE
RESISTA
!3UDS

II

BARE 4LB ANODES


WITH RESISTANCE
WIRE.

STAGE
4LB ANODES
SHEATHED IN
ALUMINIUM

STAGE I
S
!
8 LB AND 25 LB
ANODES SHEATHED
ALUMINIUM

FIG. 1-Types

of Magnesium Anodes.

CORROSION I N SALT WATER COOLING SYSTEMS

appears promising, with zinc anodes. A one-coat


epoxy system, without solvents, has recently become
available and condenser trials over the past nine
months show great promise.

EPOXY MASTIC
The one-coat, solvent free, epoxy mastic is a three
pack system; a liquid epoxy resin, originally developed as a casting resin, a solid hardener which is
melted before mixing, and silica flour filler. The mix
has a reasonable pot life and can be applied by
trowel or, with some difficulty, by brush. The adhesion to blast cleaned surfaces is excellent, although,
when the surface has been deeply pitted, it has been
deemed advisable to wet with a first coat of resin
and hardener without filler. The main coat is then
applied before the wetting coat is fully hardened.
Having no solvents, this epoxy mastic can be
worked in the open shop. The curing time in U.K.
temperatures is one to two days, after which the
coating may be exposed to water. I t is advisable to
shield the coating from dust and other fragments
during curing.
TUBEPLATECOATINGS

An insulating coating of reasonable cost, which


can be applied to brass, resists salt water at temperatures up to 110F in turbulent conditions, and has a
life of several years, is not easy to evolve. Trials on
the laboratory scale show some promise for a priming
coat of epoxy ester pigmented with calcium plumbate,
with a top coat of epoxy mastic.
Sacrificial Anodes

MAGNESIUM
ANODES

The four types of magnesium anode shown in Figure 1 were tried in channels, with the following
results :
i . Anodes direct o n the channel cover.
Single or multiple four-pound anodes bolted to
the channel cover gave more than adequate protection but the life was only about three month:.
2. Anodes on channel cover, with resistance control.
The anodes were bolted to the channel cover
through an insulating stalk carrying a resistance
wire. When the resistance was high enough to
make the anodes last one year, the current output

113

was inadequate for full protection; also, coulomb


efficiency was greatly reduced.
3. Anodes, aluminium sheathed [3], o n channel
cover.
Improved coulomb efficiency is obtained from
magnesium in salt water if current output is restricted by reducing the wetted area, rather than
by introducing an external resistance. Cylindrical
anodes were partially sheathed in aluminurn sheet
S thick, with welded seams, leaving one end bare.
Such sheathed anodes were found to lose weight
at about one-third the rate of a bare anode of
similar dimensions.
Sheathed anodes on the channel cover gave
too little current for full protection, although they
were moderately successful when used to supplement protective coatings.
4. Slab anodes, aluminium sheathed, on division
plate.
Although the channel cover is the convenient
position for anode replacement, anodes in this
position were too far away from the tube plate/
channel galvanic couple. T h e sheathed anode was
redesigned to make casting and sheathing easier
and to allow it to be bolted on the division plate.
After detail modifications to avoid loss of electrical contact and to eliminate bursting of the
aluminium sheath, the sheathed slab anode has
been used with some success. The life, however, is
still too short; also, the cost of sheathing added to
the magnesium cost results in a high cost per
ampere hour.
ZINC

ANODES

Magnesium has many attractive properties as a


sacrificial anode in sea water, but unfortunately these
properties do not, in all respects, fulfil the particular
requirements of condensers in refineries, One important requirement is that the condenser shall not
be removed from service and opened solely to renew
the sacrificial anodes; anode renewal should coincide with unit overhauls. An interval of five years
between major overhauls is desirable, with intermediate shut-down every 2% years. Thus, sacrificial
anodes should have a minimum life of 2% years,
and will be accepted by maintenance engineers far
more willingly if they can be designed for a 5-year
life. T o achieve long life, it soon became evident that

114

FIFTH WORLD PETROLEUM CONGRESS

a sacrificial metal was required with a lower driving


voltage than magnesium, not subject to natural corrosion in sea water and with high density to providc
ample weight in a small space.
At the time when the above facts were realised,
it was fortunate that the self-polarising defect of zinc
was being studied by a number of workers [4,5, 6, 7,
81 and sufficient progress had been made on the study
of the effect of iron impurity and of alloy additions
to justify plant trials. Zinc of the required purity was
readily available in EngIand, at a small premium
since it is in regular production for the die-casting
industry; also, the primary zinc producer was
equipped to cast anodes, thus having full control over
casting technique to avoid contamination and able
to select casts and control analysis.
Figure 2 shows one of the first high purity zinc

FIG. 2-Zinc

anodes in a 24 channel after cleaning. This anode


weighed 42 pounds originally and was being consumed at a rate of 25 pounds per year.
After many experiments, mainly conducted in
operating units, and which cannot be described in a
paper of this length, the following conclusions have
been reached on the use of zinc in condensers:
Sufficient metal to achieve a long life can be
accommodated in channels without serious interference with water flow and without overprotection since zinc is largely self-regulating.
I n floating head covers sufficient space for
anodes of the required size is not always available.
For full protection for as long as five years the
anodes should be assisted by a good quality
coating, which should be applied to the tube

Anode in 24 Channel.

CORROSION IN SALT WATER COOLING SYSTEMS

plate and tube ends, as well as to the channel


and cover.
Zinc anodes are sensitive to contact resistance
because of the low driving voltage, and should
be welded in position wherever possible.
Pure zinc with alloy additions of aluminium and
silicon corrodes more smoothly than pure zinc
alone, which tends to pit heavily.
The re-entrant angle between the tube plate
(non-ferrous) and mating flange (ferrous) resists the flow of protective current and the galvanic attack is most rapid on this flange and
the division plate. The best practice is to face
the flange and division plate with a resistant
material, such as two layers of molybdenumbearing stainless steel weld metal, bringing the
facing back about 1 into the body of the
channel to make the galvanic couple accessible
to protective current.

115

IRONANODES

As stated earlier, non-corroding channels and floating head covers present a very real danger to tube
ends. After some unfortunate experiences, iron anodes
in non-ferrous or fully lined channels and floating
head covers are now regarded as esssential; the best
design of iron (mild steel) anodes has still to be
resolved. The requirements are:
A minimum life of 2% years, preferably five
years.
A low resistance contact, ultimately to the
tube ends.
Secure attachment throughout the life, bearing in mind that welding or brazing of mild
steel to non-ferrous metals is never simple and
can be very difficult in the case of some cast
copper alloys, such as high tensile brass, which
is liable to crack.
Anode corrosion products must neither block
the tubes nor encourage deposit attack inside
the tubes.
One cast steel 24 channel was lined with monel
sheet f/8 thick by welding. The channel cover was
not lined; a full-face iron anode [2] was fitted across
the channel with an external insulated cable to
ensure good connection between the anode and the
tube plate. The channel cover and the back of the
anode were lined with three coats of bituminous
ZINC ANODES
paint. The anode was sandblasted to remove millFULL WIDTH
scale, etc., and to reduce pitting.
When this channel end was inspected after approxiFLOATING HEAD END
CHANNEL END
mately two years in service, the tube plate, tube ends
and monel lining were in perfect condition. The
FIG. 3-Present Practice-Faced Flanges, Zinc Anodes,
full-face anode, originally 3/8 thick, was wasted
Painted Internally Including Tube Plate.
about 50% and was fit to return to service. There
was no wastage under the gaskets, indicating that
Figure 3 illustrates the latest practice on leakage at the anode joint will not be a problem
channel ends. I t shows the standard zinc anode, until the anode is in the last stages of exhaustion.
28 x 4 x 1%) weight 42 pounds, with mul- There was no evidence of tube blockage by corrosion
tiple welding tags; this anode fits 33 and 29 products.
I n the above experiment the anode area is equal
condensers and can be cut to fit smaller condensers. The shape and the galvanized insert to the tube plate area. Some non-ferrous floating head
are designed for easy casting in open-top covers were fitted with iron anodes only one quarter
moulds and this anode is now finding applica- of the tube plate area and after six months the anodes
tions outside refineries. The flanges are faced were almost exhausted. Circular plate anodes, dished
with stainless weld metal and the internal sur- to fit the floating head covers, can be purchased at
reasonable cost and are being tried in one refinery.
faces are painted.

116

FIFTH WORLD PETROLEUM CONGRESS

The consumption of iron is expected to be about


one pound per year per square foot of non-ferrous
surface.
BOLTEDANODES

It is generally recognised that, because of low


driving voltage against polarized steel, zinc anodes
can tolerate little or no contact resistance and should
be welded in position. The same applies to iron
anodes protecting non-ferrous components. But in
refineries a fire permit for welding cannot always
be obtained; also, welding to cast iron is undesirable.
A possible solution to the problem of making a low
resistance bolted connection, with long life, is offered
by a special type of lock washer. This washer was
originally developed for securing fan blades on the
shaft and is known as the fan disc washer. The
hardened serrations overlap and cannot be flattened
by pressure, and so dig into the anode core and the
nut a t all times.
Discussion-Condenser

Protection

prove to be undesirable, suitable aluminium alloy


anodes with similar characteristics are now available,
although the greater bulk of aluminium for the same
life may prove difficult to accommodate.
Because condenser ends are large scale galvanic
couples, reduction of the wetted area of the cathode
is of primary importance. When a reliable coating
is found which can be applied on site to the tube
plate and tube ends, then the pattern of protection
may be simplified, possibly to the following scheme as
shown in Figure 4:
BOND

WISKET

IRON
ANODE

T h e experiments have shown that conventional


steel channels can be protected by facing the
FLOATING HEAD END
CHANNEL END
flange and the edge of the division plate mating with
DISHED IRON ANODE
HIGH DUTY COATING
the tube plate, plus a good quality coating assisted
WELDED ON COVER
ON CHANNEL AND
HIGH DUTY COATING
TUBE PLATE.
by sacrificial anodes (see Figure 3 ) . A long anode
ON TUBE PLATE,
N L L FACE IRON
life is possible when zinc anodes are employed. The
FLANGE FACE AND
ANODE WELDED ON
ANODE WELD.
COVER
most promising coating tried so far is a one-coat,
solvent-free, epoxy mastic.
FIG. &Predicted Design for Condenser Ends for Five
Year Service on Sea Water Duty.
Because less space is available, less success has been
achieved in protecting floating head covers. Non-ferrous floating head covers are not a complete answer;
-Tube plate and tube ends coated.
they encourage tube end attack and should be fitted
-Channel, channel cover and floating head cover
with sacrificial anodes, which can be iron.
coated, including flange faces.
One channel lined with monel and fitted with a
-Floating head cover in steel, with expendable
full-face iron anode has been successful. The disdished iron liner welded in.
advantages are the high cost of lining and the prob-Full face iron anode across channel cover.
ability of galvanic attack on the supply and effluent
pipes. Another channel, recently installed, is fabricated in aluminium bronze; its performance promises Section 2-Cooling Water Mains
to be the same as the monel lined channel.
Considerations
Adverse effects on the tubes and tube plates must
The Isle of Grain Refinery has steel cooling water
be avoided. Tube end attack can be greatly reduced, supply mains, buried in corrosive soil at depths up
but effects on the long-term pexformance of Ad- to 15 feet. Externally the mains are protected by
miralty Brass tubes are still uncertain. However, the coating and wrapping, supplemented by magnesium
protection methods now being evolved are fairly anodes. Internally, because no proved protective linversatile; for example, if zinc corrosion products ing of reasonable cost was available a t the time. the

CORROSION I N SALT WATER COOLING SYSTEMS

surface was simply sand blasted to remove millscale


and coated with bituminous paint. Similar mains
constructed more recently in this and other refineries
have been cement lined.
T h e system is partly a ring main, thus enabling
internal inspection to be made without major interference with refinery operations. The first inspection
after 20 months service showed that the internal
surface was suffering some general attack and pitting
up to 1/16 deep beneath mud scabs, as shown in
Figure 5. The maximum rate of pitting was estimated
as 37 mils per year, which indicated that major
renewals would be required after about ten years if
no protection was applied. Fortunately, this allowed
a few years in which to carry out a technical and
cconomic assessment of protective measures.

FIG. 5-Pitting

117

The cooling water carried by these mains is taken


from the River Medway, about one mile from its
junction with the Thames Estuary. The river has an
average tidal range of about 17 feet at the cooling
water intake. An artificial basin formed by building
a foreshore wall across a small natural bay is filled
by the tide, assisted by vertical spindle pumps, which
simply lift the estuary water over the wall into the
basin. From the basin a canal takes the water to the
Cooling Water Pumphouse as shown in Figure 6. The
pumphouse forebays have coarse screens and mechanical fine screens ; chlorine is injected before the
pumps.
The water is regarded as 90% sea water; its main
characteristics are given in Table I. The reservoir
and canal probably play a significant role in im-

under Miid Scabs in 60 Cooling Water Main.

118

F I F T H WORLD PETP:OLEUM CONGRESS

fineries and associated plants are obtaining practical


experience with internal linings, which include heavy
reinforced concrete (Preload Process, 1% thick),
thin concrete (Centriline Process, about 3/8 thick),
bituminous enamels, and sheet rubber.

COOLING WATER
CHANNEL.
CONCRETE
3.000 LONG
45 WIDE
IO DEEP

INTAKE
WMPHOUSE

o STEEL ANODES ON PIPE AXIS


0

FIG. 6 - B P Kent Refinery Cooling Water


Reservoir and Channel.

proving the quality of the water by providing a


sedimentation basin.
Four methods of protecting the interior of the
steel cooling water mains are being investigated.
These are:
1. Cathodic protection by impressed current.
2. Cathodic protection by sacrificial anodes.
3. Linings of paints and similar materials.
4. Cathodic protection by sacrificial anodes in
combination with linings.
Concurrently with these investigations, other reTABLE I

AqlAgCi HALF CELLS ON PIPE WALL

FIG. 7-Impressed Current Experimenta in 60


Cooling Water Main.
Impressed Current Cathodic Protection
Eleven experiments were carried out with the ap-

paratus shown in Figure 7, in a length of 60 diameter Cooling Water Main. The most important information obtained was as follows:
1. The optimum spacing between anodes is four
times the pipe diameter, that is, 20 feet for
this main. At greater spacing the total power
demand increases due to excessively high potentials near the anodes.
2. At anode spacing of 8 diameters a protective
potential could not be maintained at the mid-

ISLE OF GRAIN REFINERY


COOLING WATER CHARACTERISTICS
PH
8.1 to 8.3
Specific Resistivity
a t 50F
27 ohm. cm.
20 * *
9)
a t 75F
a t 100F
16 *

Chlorides
18350
19100 p.p.m.
23602600
Sulphates
Calcium
568713
Magnesium
6801040
Free Carbon Dioxide
414
Free Ammonia
Nil
Sulphate Reducing Bacteria
Present hut not active.
Samples become clear and colourless on
standing, with a buff coloured fine sandy
deposit.
Temperature Range (inlet 38-72F).
Design Outlet Temperature for Condensers.
llOF.

0.9

<

c /

w
z

0.8

MIDWAY BETWEEN ANODE5

O .7
AVERAGE CURRENT DENSITY 5 u*/%
ANODE5 20 FT APART

0.6
O

100

200

FT

300

HOUR5

FIG. &Effect

of Water Velocity on Potential.

400

/SILVER

B PA1NTED

A BARE
1.0

POTENTIAL
JUNE 1957

0.6

SEPT

I
a

DEC

3-

MAR

l
-

lmd 2 -

t-

LL

VELOCITY

I-

1
0-

c;
u.

5-

<

CURRENT DENSITY

O
FIG. ,%Zinc Anodes in 6 0 Cooling Water Main.
119

..

120

FIFTH WORLD PETROLEUM CONGRESS

point between anodes unless unreasonably high


current densities were applied.
3. With anode spacing four diameters and average
Current density 5 milliamperes per square
foot ( 2 amperes per anode), a minimum protective potential of -0.80 volts against
silver was attained after four days and was
maintained at flow rates of 1.22 ft. per sec.
and 2.48 ft. per sec. The water temperature
was about 50'F. Figure 8 shows the effect of
water velocity on protective potential.
The experimental work employed steel plate as
anodes. For any permanent impressed current system,
possible anode materials are impregnated graphite,
silicon iron, silicon iron alloyed with molybdenum,
platinum and its alloys, lead alloy [9] and platinised
titanium. [lo] Tests on the last two materials are
now in progress.

FIG. 10-Zinc

Cathodic Protection by Zinc Anodes

The results on the trial section of 60" C.W. Main


with 42 Ib zinc anodes (28" 4" 1%") are shown
in Figure 9. Main obse-vations were:
1. Welding of anodes in position is simple and
cheap.

2. With no internal lining and one anode to each


4'8" length of 60" pipe, the minimum protective potential was barely achieved. At a later
stage the number of anodes was doubled,
making two discontinuous lines of anodes at
4 o'clock and 8 o'clock, and the protective
potential overall exceeded -0.80 volts against
silver.
3. When the internal surface was lined with two
coats of heavy coal tar paint, one anode to
every 9'4" length of pipe gave over-protection.

Anode w i t h Corrosion Product Intact.

CORROSION IN SALT WATER COOLING SYSTEMS

The current density on the bare section, with


poor protection, was about five times that on
the painted section, with over-protection.
Protective Potentials were not seriously affected
by variations in water velocity between 1 and
3% feet per second, or by temperature variations from 42F to 72F.
Protective Potentials were decreasing towards
the end of the 11-month run, probably because
the corrosion product from the zinc anodes remained in place, the anodes retaining their
original shape. The shaped corrosion product,
which is white, was covered with a thin film of
a black sludge deposit. The corrosion product
was soft and cheesy and could be removed by
rubbing with the fingers. Figures 10 and 11

FIG. 11-Zinc

121

show a zinc anode before and after removal of


corrosion product.
7. Zinc alloyed with aluminium and silicon corrodes more uniformly and yields a softer corrosion product than pure zinc.
Internal Linings

Ten foot lengths of the 60 C.W. Main (160 sq.


ft.) were lined with selected coatings, which were
exposed for eleven months in the water conditions
described in Figure 9. The appearance of these coatings at the end of the test period is described in
Table II.
Discussion-C.W.

Main Protection

The experiments on a 60 cooling water main


show that cathodic protection is possible by impressed

Anode with Corrosion Product Removed.

122

FIFTH WORLD PETROLEUM CONGRESS

TABLE II
COATINGS IN 60 C.W. MAIN
Tvpe of Coating
Aluminium-Bitumen Paint 2 coats

Surface
Preparation
Wirebrush

4 coats

Zinc Rich Primer 2 coats


1 coat Zinc Rich

2 coats Coal

N07niM.l
Thickness
Mils.
2

Barnacles
per sq. f t .
21

None

Severe blistering. Complete failure.

None

Excellent, apart from fine crazing


of coal tar paint.

11

Tar Paint
Wax/Rubber Paint 2 coats
Wax/Rubber Mastic
brushed

Small isolated breaks.


Onc or two minute breaks.

N o blistering. Adhesion good.

1 coat, hot

Proprietory Cement/Synthetic Rubber Mastic Sprayed


Trowelled

Appearance after
11 months

Sand Blast

10

10

Breakdown starting.

260

67

Rough surface. Heavy barnacle


growth. Small isolated breaks.

250

Smooth surface. No breaks.

current, by zinc anodes alone, or by zinc anodes plus to thank his colleagues who participated in its
a paint lining. The experiments continue, but it is preparation.
already evident that the method of cathodic protecReferences
tion may be chosen on economics, on ease of installa1. Gilbert, P. T., The Resistance to Failure of
tion and maintenance, and on the desirability or
Condenser and Heat Exchanger Tubes in Marine
otherwise of introducing large amounts of anode Service. Trans. Inst. Mar. Eng. 66 No. 1: 1-20
corrosion products into the system.
(January, 1954).
The bulk of the zinc anode corrosion product
2. Munro, J. D., Corrosion and Prevention-Heat
is retained on the anode at water velocities up to Exchangers in cooling water servi ce.^^ proc. A.P.I.
3% feet per second. It would be advisable to fit 34 (III) : 19-36 (1954).
permanent reference electrodes in any protected main
3. British Patent No. 699239.
to indicate, by falling potential, if the main should be
4. Crennell, J. T., and Wheeler, W. C. G., Zinc
entered to remove corrosion product.
Alloy Anodes. J. Appl. Chem. 8: 571 (1958).
Considering the selection of a protective lining to
5. The American Zinc Institute. New York. Cabe used in conjunction with zinc anodes, the choice thodic Protection with Zinc Anodes. (June, 1953).
seems to lie between the aluminium-bitumen ships
6. Tytell, B. H., and Preiser, H. S., Cathodic Probottom paint mentioned in Table II and the plas- tection of an Active Ship using Zinc Anodes. J. b.
ticized coal tar paint tried with the zinc anodes. The soCa
Nav. Eng. (November, 1956).
coal tar Paint was in a more advanced Stage of
7. Teel, R. B., and Anderson, D. B., The Effect of
breakdown than the aluminium-bitumen paint after rron in Galvanic Anodes in Sea Water. Corrcsion.
eleven months exposure. This supports the generally 12 N ~ 7:. 53-59
1956).
accepted opinion that heavy pigmentation with leaf8. U.S. Military Specification MIL-A-18001C.
ing aluminium increases the water resistance of the Anodes, Corrosion Preventive, Zinc: Plate, Slab,
medium in conditions of complete immersion. A Disc and Rod Shape& (October, 1956).
similar effect of aluminium pigmentation has been
9. Morgan, J. H., Lead Al:oy Anode for Cathodic
noted in other trials in which epoxy paints were Protection, Corrosion Technology. 5 No. 11: 347-352
employed.
(November, 1958).
10. Cotton, J. B., Platinum Faced Titanium for
Acknowledgements
Electro-Chemical Anodes. Platinum Metals Review.
The author wishes to thank the Chairman and 2 No. 2 : 45-47 (April, 1958).
Directors of The British Petroleum Company Limited
This paper was presented on June 2, 1959, by
for permission to publish this paper. He also wish=? E. D. DOLAN.

CORROSION I N SALT WATER COOLING SYSTEMS

Discussion
A. J. VAN RIEMSDIJK
(Koninklijke Shell-Laboratorium, Amsterdam, The Netherlands). Mr. Dolan
has given us a very complete survey of ali modern
methods used for combating corrosion in salt water
cooling systems. I t is gratifying to notice that the
techniques used by the B. P. refineries have so much
in common with those used in the Royal Dutch/Shell
refineries; it goes to show that everywhere in the
oil industry the struggle against our common enemy
corrosion is being carried on with determination.
There are, of course, some technical differences
between the methods described by Mr. Dolan and
those applied in our refineries, of which I would
like to mention a few:
Mr. Dolan pointed out in his paper that coatings
are always to be supplemented by cathodic protection.
This is quite true for thin and brittle coatings: We
have found, however, that in the steam condensers
of a power house of one of our major refineries relatively thick layers of soft, rubber based materials
stand up perfectly, unaided by cathodic protection.
We think this to be the best protective measure for
cast iron and steel parts.
Concerning the use of sacrificial anodes; we agree
that the consumption of magnesium anodes is too
high; we are not keen on the use of zinc anodes,
having generally obtained poor results probably because of insufficient purity. It is rather difficult for a
refinery to check for trace metals! We prefer the use
of iron anodes; this choice is related to our preferred
constructional materials for coolers and condensers,
viz. :
Tubes : aluminium brass, inhibited with, e.g.,
arsenic to prevent dezincification (British specification 1464).
Tube sheets: aluminium bronze, ASTM B 171,
alloy E, which we order with a minimum aluminium content of 7% and a miximum aluminium
content of 10%.
Floating-head covers : aluminium bronze ASTM
B 148 alloy 9 D (with the same restrictions on
aluminium content as for B 171).
Channels and channel covers : tin bronze,
ASTM B 143 alloy 1 A.

123

For salt water lines we prefer centriiining: we


have no experience with internal cathodic protection
of such lines. Could Mr. Dolan supply any information on the relative costs of these two possibilities?
As a final remark I would like to point out that
Mr. Dolans aim at a five years life of sacrificial
anodes etc. seems excessive, as in our normal operation units have to be shut down after running
periods of up to two years anyhow.
E. D. DOLANreplies. I should like to thank Mr.
van Riemsdijk for his remarks and also for giving
me an advance copy of his discussion.
Rubber lining of water boxes is often successful,
as Mr. van Riemsdijk said. But I do know of cases
where rubber lining has been damaged on installation and could not be repaired on site. I also know
of cases where rubber lined water boxes have encouraged tube end attack. Again, heavy linings of
rubber lined materials should be applied by specialists.
The refinery maintenance engineer does not have
the equipment or the know-how for such work.
The methods I have described-mastic coating,
weld metal on the flanges, zinc anodes welded inare within the capacity of a normal refinery workshop
in any part of the world, including the wilder areas
of the Middle East, and can be applied to the steel
components which are already on site.
I, myself, would prefer to rely on an epoxy mastic,
or epoxy paint multi-coating supplemented by zinc
anodes, than on the heavy rubber coating, which is
only as good as its bond to the base metal. Just a?
Mr. van Riemsdijk, we also had some disappointments at first with zinc anodes; but the modern
British alloy anode, and I emphasize alloy anode,
which is made from selected casts and with careful
control of foundry practice to avoid iron pick-up,
seems quite reliable. The purchaser must insist on
precise analytical control by the supplier. It should
not be necessary for iron impurity to be checked by
the refinery although the British Admiralty workers
in this field have developed a reasonable wet-method
for iron determination.
Most important, we have found that zinc alloy
anodes in condensers must be helped by a reasonably
good coating such as epoxy mastic.
Results with zinc anodes used by themselves have
been disappointing.

124

FIFTH WORLD PETROLEUM CONGRESS

Mr. van Riemsdijk has described the non-ferrous


materials preferred by Royal Dutch Shell for condenser ends. I n a recent economic survey, we found
that non-ferrous channels and floating heads of that
type cost about three times as much as similar components made in cast steel. And in my present experience, even for new components, I would still
advocate cast steel with the protection method I
described.
But, my paper is mainly concerned with steel components which are already in existence in large numbers, and which should not require replacements in
either steel or non-ferrous for many years.
Regarding non-ferrous channel ends, I would like
to ask Mr. van Riemsdijk if he gets galvanic attack
on the steel pipe work immediately adjacent to the
non-ferrous end.
Regarding iron anodes, in a recent visit to a
Middle East refinery I found that iron corrosion
products were responsible for deposit attack in Admiralty tubes operating with low water velocity and
I now doubt if iron is as safe to use as zinc.
A five year life of sacrificial anode was also a
good thing to aim at and our latest results suggest
that we should achieve it without great difficulty, at
least in the channel end. At a two-year overhaul,
the maintepance department is very fully occupied
with all the other jobs and if we can relieve them of
welding in new anodcs, so much the better.
Regarding cement lining of mains, we have many
that were lined in situ, and they still are satisfactory
so far after five or six years.
For smaller pipework on units we are trying steel
pipe, spunlined with concrete in the factory, and
jointed with an epoxy mastic and a fully-welded
sleeve.
Factory-spun lining is very much cheaper than
in situ lining and I think is a much more reliablc
job. For the 60 inch main described at the Isle of
Grain Refinery which would have to be cleaned, dried
for lining in situ by, say, the Cientriline or Preload
Process, protection with zinc anodes would be cheaper
and would involve a shorter shutdown time.
The cost of zinc alloy anodes for this main should
not be more than five cents per square foot per year,
plus the cost of fitting and renewal, say, every ten
years.

A. J. VAN RIEMSDIJK.I have really only one


question, and that is the couple action between all
this copper alloy and steel piping. I think, in most
cases, it has been taken care of by means of a waste
insert in the flanges or just a waste spool which is a
rather cheap thing to replace.
A. C . VIVIAN (Metal and Pipeline Endurance,
Ltd., London, England). This paper is full of useful
information and the presentation, too, contained additional information for which, Mr. Chairman, you
already thanked the speaker.
I want to raise a couple of points. You say that
coatings should always be supplemented by cathodic
protection and you are referring there to nonmetallic coatings. Would you apply that also to
modern metallic coatings and, more particularly,
would you apply it to cement lined mains? You have
referred, in your reply to the last speaker, to the
use of cement mains, but I am not quite sure from
your reply whether you would normally use cathodic
protection in addition to the cement lining.
Coming to my second point, it is this matter of the
internal protection of water mains by impressed current which is of particular interest. You are here
dealing with a large main, five foot diameter, but it
is considered reasonable to apply cathodic protection
for the internal protection of much smaller diameter
mains. My company is at present setting up a test
circuit. We shall have about 20-foot run of 18 inch
diameter main and we shall have a feed tank for
sea water and a 6000 gallon a minute pump. That
will enable us to try out various spacing of anodes
in the way you described in your paper.
Now, if we find that the optimum distance, as you
described for five-foot main, is four diameters, then to
protect an 18-inch diameter main one should have
the anodes a t six-foot spacings, which considerably
runs up the cost for electrical connections. I would
like to have your opinion on whether we might possibly get to five or six diameters, and I would value
your opinion also on water velocity. You were
limited in your experiments to about 2% ft. per
second.
We are set up, if necessary, to run up to about
8 ft. per second. If we get any useful results out of
this we will be only too happy to pass them on. But
I welcome your opinion.

CORROSION I N SALT WATER COOLING SYSTEMS

E. D. DOLANreplies. Mr. Vivian first asked if we


would apply cathodic protection to metallic coatings.
I would interpret that as meaning sprayed metal
coatings. And, of course, we would only use zinc or
or aluminum as a spray metal coating and they would
be sealed with some sort of sealant. Our experience
has been that heavy coal tar paints are very good
sealants for metal spray in immersed conditions.
So, we would not apply cathodic protection from
an external anode to aluminium or zinc metal sprays
-and of course, we would not use any other type of
metal spray in salt water duty.
Regarding spun-line cement pipe, cement lined by
spinning, we did not intend to use cathodic protection
initially, although I had done preliminary designs
where zinc anodes were inserted at the joint, being
the most likely place to have a weakness. I am a
firm believer, as I said in my paper, and I still
emphasize it, that there is no such thing as a perfect
coating in practice, and if I can get some sacrificial
anodes that take care of the imperfections in the coating, I do that as much as possible.
But, initially, the cement lined pipes will not have
sacrificial anodes. They may have to have them
eventually.
Regarding cathodic protection of pipes smaller
than 5 ft. diameter, I have a trial run going on a
14-inch pipe. Now, the method I described on the
five-foot pipe is block anodes taken in by a man,
and welded in, because a man can go inside but he
cannot go inside a 14-inch pipe. And there we make
zinc anodes like a string of beads. They are three
feet long and two inches square, they are welded
together in long lines, and they rest on the bottom
of the main. We are trying that out on a 14-inch
main.
With regard to Mr. Vivians question on spacing
between anodes, the four diameters, as I said, is the
optimum spacing (the power costs the lowest at 4
diameters, because you get the least overprotection
near the anodes). A commercial installation I know
of has been made at five diameters, and, I think,
that is about as far as y m can go without running
into unfavorable kilowatt hour costs.
As for water velocity, I cannot say anything on
that. You cannot operate a refinery main at a
velocity the operating people do not want. I n fact,

125

it was a grudging concession that we were allowed


to double the water velocity from 1% to 2I/2.
Acutally, since then, we have run as high as 3%) as
shown in the last slide. And 3% made no difference
at all to the protective Potentials.
C. A. BRECKON(Yorkshire I m p . Metals, Leeds,
Yorkshire, England). There is just one small point
on which I should like to comment, concerning
the use of iron anodes in the protection of nonferrous parts of the system. It has been my lot to
examine corrosion in a number of salt water systems
and as a result I am quite convinced that iron
corrosion products do very greatly help to develop
the maximum corrosion resistance of non-ferrous
alloys like cupronickel, aluminum bronze or aluminum brass and so on.

There are a number of examples I could give on


that. I have never comte across a case where
iron appears to have caused a difficulty. I wonder
if the case quoted by Mr. Dolan might be similar to
one where apparently iron had caused some trouble.
The deposits which were adhering very firmly to the
tube were obviously iron corrosion products; but
when we examined them carefully and got down to
the matter, we found the pieces of iron, which,
originally had been small pieces of cast iron, and it
was only where the iron had been completely corroded away that corrosion had taken place, and we
were left with small areas of the graphite, with no
metallic iron present. While there was still metallic
iron present it did not appear to have caused any
very local corrosion, not the deposit type of attack
he referred to, but instead a local impingement attack
where you had this small area of graphite firmly
imbedded in a matrix of iron corrosion products.
My comment mainly is that we endorse the experience of some of the oil refiners, particularly in
the Caribbean area where iron corrosion products do
materially h e l p - o r appear to-in the protection
films.
E. D. DOLANreplies. I agree entirely that iron
in solution in the cooling water helps to strengthen
the protective film. But, of course, in a refinery,
unlike in a ship, you often have half a mile of iron
pipes picking up iron. Mr. Breckon quickly gave a
list of tube alloys, aluminium brass, aluminum bronze,
cupronickel.

126

FIFTH WORLD PETROLEUM CONGRESS

Regarding the defective iron deposits I saw recently


in the Middle East, they were definitely there as a
hard cubicle. I n other words, they were there as a
foreign body. Exactly the same effects would have

come from a pebble. The iron deposit was there


simply as a foreign body lodged in the tube and not
scavenged away because the water velocity employed
at that time was exceptionally low.