Egyptalum

Control Of Acid Corrosion

In Cooling Water Systems
(( A Total Technical Approach ))

Chemist / Hassan . M . Abd - allah

Why pH Control became Important ?
Chromate inhibitor treatment programs are being replaced and
Higher cycles of concentration are being used in cooling systems
to minimize blowdown

Control of Cooling Water pH and alkalinity is usually required for

proper performance of treatment program

Major causes of acid attack in cooling water systems

(( Acid corrosion is usually caused by an upset ))
Acid spills or process leaks

Airborne gas contamination

Overfeed of acid in pH adjustment

Wrong selection or application of solvent (descaler)

in chemical cleaning
 Acid corrosion & Metallurgy
1- Steel (carbon steel & most cast iron)
Corrosion rate of C.S in pure water is about constant between pH 4-10
Acid strength
depends on

H2 Evolution
begins
its tendency to
dissociate into
hydrogen ion and
counter ion

Solutions of strong acid such as HCl & H2SO4 , dissolve

protective iron oxides below pH 4

Dissolving of iron oxide occurs at slightly higher

pH (5 - 6 ) in weaker acids such as carbonic acid

Weak acids, (carbonic & organics) dissociate only

slightly compared to strong mineral acids
 H2 ions consumed in corrosion cant be replaced in strong
acid solutinos (dissociation is complete)

In weak acid solutions, more H2 ions is produced by

dissociation as H2 ions consumed by corrosion
Iron is dissolved at exactly the rate of cathodic process
Fe Fe + + + 2 ( Anode ) Main anodic and
2H + 2 H2 (Cathode) cathodic reaction
in acid solutions
Thus,hydrogen gas is generated in most acid solutions

If dissolved oxygen is present , the cathodic reaction can be

accelerated by depolarization

4H+ + O2 + 4 2H2O
Oxygen effects are largest for weak and dilute inorganic acids

When acids are concentrated , H2 evolution is so great that

Oxygen cannot easily reach the corroding surface
The addition of oxygen has little or no effect on corrosion rates
in oxidizing acids
 Effect of Acid Under O2 Under H2 Ratio

Dissolved O2 6 % acetic 0.55 0.006 92

on corrosion 6 % H2SO4 0.36 0.03 12
of Mild Steel in 4 % HCl 0.48 0.031 16
Acids Corrosion 0.39 0.0055 71
0.04 % HCl
Rate ( in./y )
1.2 % HNO3 1.82 1.57 1.2

Fluid velocity can influence the amount of oxygen reaching the

metal surface and , therefor , the corrosion rate

During acid cleaning or sever acid upsets, F+++ concentration

may increase to high levels , Resulting corrosion can be severe

Iron is oxidized , and ferric ions

reduced on bare steel surfaces
that develop during system
cleaning or upset

Fe + 2 Fe + + + 3 Fe + +
Carbon steel pipe attacked by a
strong mineral acid
2- Stainless steel
Acidic attack on Stainless steels differs from
corrosion on steels in two important respects

First , nonoxidizing acid corrosion is usually more

severe in deaerated solutions

Second , oxidizing acids attack stainless steel far less

strongly than carbon steel

Hence , nitric acid solutions at low temperatures cause

only superficial damage , but hydrochloric acid causes
truly catastrophic damage

Stainless steels tend to pit in acid solutions

Pits form local areas of metal loss associated with

breakdown of a protective oxide layer
 Breakdown is stimulated by low pH as well as by
decrease
the of dissolved oxygen in occluded regions

Small,active pit sites form and remain stable because of large ratio
of cathodic surface area (unattacked metal surface) to pit area

Active corrosion in the pit cathodically protects immediately

adjacent areas

If the conditions become very severe, pitting will give way to

general attack as more and more of the surface becomes actively
involved in corrosion

Pitting on 304 S.S coupon caused Austenitic S.S pipe that carried sulfuric
by acidic,chloride-containing acid . Failure was caused by severe
water. general wastage from internal surfaces
3 - Copper alloys
Copper corrosion by mineral and organic acids is controlled
to a large degree by the presence of oxidizing agents

nonoxidizing acids such as organic acids cause very

little corrosion if oxygen concentration is very low

Hence , just above boiling temperatures copper is virtually

impervious to attack

If cupric or other metallic salts that might be reduced

are present,attack may be severe,even in absence of
oxygen

Oxidizing acids such as nitric acid cause severe attack

Zinc brasses and cupronickels behave in much the

same way as copper
 The corrosion of copper by carbonic acid
deserves (special attention ) There is a ( Synergism )
between oxygen & carbonic acid with regard to corrosion

Carbonic acid in the absence of oxygen is not corrosive to

most copper alloys , corrosivity can be appreciable if
oxygen is present

Smooth,wavelike contour in a region

of general metal loss on copper due to
carbonic acid

Grooving was caused by carbonic

acid containing high concentration
of dissolved Oxygen

The groove patterns

indicate channeling of
corrosive fluids by flow Deep groove in region of locallized
metal loss on a copper tube
4 - Aluminum
Aluminum corrodes at a fairly low rate between a pH
of 5.5 and 8.5 at room temperature

At concentrations between 50 % and 95 % sulfuric acid

causes rapid attack ; below 10 % corrosion is much less

Hydrochloic acid is quite corrosive in all but

dilute concentrations

The corrosion rate in hydrochloric acid increases 100

fold as temperature increases from 50 F ( 10 C ) to
176 F ( 80 C ) in a 10 % hydrochloric acid solution

Aluminum is resistant to nitric acid at concentrations above

80 %.At 50 % nitric acid concentration at room temperature
corrosion rates are as high as 0.08 in. (0.20 cm)\y = 80 mpy
 Phosphoric acid can be used to etch aluminum
uniformly at dilute concentrations . At higher
concentrations , attack is rapid

Organic acids except formic acid , oxalic , and some

chlorine containing acids do not appreciably
attack aluminum near room temperature

In most acids , the corrosion rate

increases slightly with flow velocity

Pitting corrosion of aluminum mould cross section .

casting mould Note the irregular
contour surface
caused by corrosion
 Locations
any cooling water component contacting lowpH water may corroded

However,there are differences as to corrosion severity and initiation

times depending on alloy composition, kind of acid, and location

In general, the higher the residual or applied metal stress,

the more severe the corrosion at a given acidic pH
This explains why heat exchanger
tube ends are attacked so severely
Tube ends that have been rolled or
welded often contain high residual stress

crevices are sometimes present in which acidic species concentrate

Screens,rolled sheet metal,and other highly worked metals

( not stress relieved ) are also prone to attack

Alloys whose corrosion resistance depends on forming a protective

oxide layer,such as S.S are susceptible to severe localized attack if
pH falls due to nonoxidizing acid excursions
However, there is a period of immunity from attack corresponding
to the time necessary to breach the protective oxide layer
Hence,copper As low
So,S.steels experience little attack during brief Fe+++pH excursions
heat exchanger concentration
tubes
Duringhandling
long acidic exposure, pits may beginincreases
and grow atduring
ever acid
acetic acid can
increasing ratebe
. Surfaces containing pits , crevices , and other
cleaning,the
more seriously
shielded areas are more likely to be attacked by lowpH conditions
corrosion rate of steel
corroded at low
Occluded
than at highsites allow concentration of acidic increases rapidly
materials and
assist the so called Autocatalytic pitting process
temperatures
Corrosion involving Sulfuric acid at acids
nonoxidizing roomcan be highly sensitive to
flow.regions of hightemperature is handledare more severely
flow and turbulence
attacked than more inquiescent
carbon steel drums,
regions
when water
concentration
Weires, lips,and other is low,but
flow obstructions increase turbulence and
thus corrosion.Pipe it elbows,tees,
becomes extremely
and joints are frequently attacked
corrosive as water
locations,althoughconcentration
widespread,are dependent on many factors,
increases
metallurgy,deposition,design,temperature,pH,flow and other
factors all influence attack

Dissolved O2,water,acid,and metalion concentrations can have

a pronounced effect on acid corrosion

For example,copper is attacked by acetic acid at low temperatures,

above boiling,no attack occurs because no dissolved O2 is present
 Critical Factors
1- Intermittent attack
Acid attack is caused by an upset, intermittently, consequently

periods of attack may be separated by intervals of no acid corrosion

Fresh acid attack is recognized by the absence of corrosion

product in wasted areas and the sharpness of attack

Oxide layers are easily stripped by a test drop of HCl acid in

freshly corroded areas

Deposits are almost always absent and Edges of attacked

areas are sharp and angular , as intervening corrosion has
not recently occurred

In stainless steels such distinctions blur , as corrosion in

intervening periods is usually slight
2 - Mixed acids
corrosivity of solutions containing more than one acid
may be unrepresentative of the corrosivity of either acid
alone
Such mixtures are used widely in a variety of industrial applications

3 Corrosion products
Acid attack causes damage directly by wastege and
indirectly by increasing and/or moving deposits

For example, during severe acid

excursion, large amounts of Fe,
Cu, zinc, or other materials may
be solubilized, resulting
corrosion products will be moved
and can foul heat exchanger
tubing, blockage of pipes,
screens may occur due to solid
material sloughed from corroed
and fouled surfaces . A fouled condenser
due to corrosion
 Identification
Attack by strong acids tends to produce intense localized wastage

Weak acids cause more general corrosion,however numerous

exceptions to these general rules exist

Fortunately, corrosion caused by acids has many unique

features that allow easy recognition in most cases

Strong acids
Pit growth
When most metals exposed to highly acidic conditions,
pitting results.a pit has a depth greater than its width

In strong mineral acid attack,not only is depth greater than width

but undercutting is pronounced. Cavernous chambers from just
below the surface because of segregation of aggressive anions
within the pits

When corrosion begins a small amount of positive ion is put

into solution at the corroding surface
The positively charged ion attracts negatively charged ion from
the acid solution

Hydrolysis in the growing pit produces ever decreasing

internal pH , leading to more metal dissolution

The pit begins to undercut, reflecting the increasingly acidic

conditions
As within.(pH
pH remains within
low,corr. active
products pitsreadily
dont may fall to much lower
precipitate in the pit
values than bulk water pH )

So,pits usually
A striking contain
feature only small amount
of mineralacid of is
corrosion corr.
the Product,although,
directionality of
areas surrounding
pit growth. Becausepits may
pits contain
entrap precipitates
metal formed
ions and acidic by normal
anions , the
pHprecipitation process
density of fluid within canor
beby oxidation
much of than
greater ions leaking out density
bulk water of pits

Pits forming on roof or ceiling surfaces tend to drain by

convection that is stimulated by the density difference between
the fluid within the pit and the bulk water
 This
Contents
process
leak
tends
out of
to pit
decrease
interiors
acidity
and depassivate
within pits, Thus
areas, pits
growing
immediately
in thebelow
direction
the active
of gravity
corrosion
are favored
sites

Depassivation
by pit leak out
due to density Pits growth in
difference the direction of
gravity

Pit morphology varies with acid strength,metallurgy, and many

It is noted
Thus,in early
that
stages
all corrosion
of acid attack
beginsitas
is localized
not all clear
attack(since
that pits will
some
other factors.As acids become weaker,pit interiors tend to become
area on metal
eventually develop,even
surface must
whenbe localized
cathodic forattack
corrosion
is present
to occur )
less jagged and more rounded.Also,flow tends to smooth pit edges

Cross section through a mild steel pipe

wall suffering severe acid attack

Note. the narrow pit mouths and

pronounced undercutting
 Grooving Strong acid corrosion will often highlight microstructural
features in steel and other formed and rolled alloys
Grooves appear as the acid attacks microstructural irregularities.
Mutual intersection of pits lead to a jagged surface contour

Irregular grooving can occur,especially on copper alloys after acid

cleaning.Tubes can be only partially filled with cleaning solution
Condensation & running of the fluid down the tube interior cuts
Network of shallow ditches
caused by condensation of
acidic fluids during acid
cleaning of a copper
condenser tube

Weld attack Welds are more susceptible to corrosion than other areas

Welds may contain porosity,crevices,high residual stresses& other

imperfections that favor attack. C.S welds are ditched by acid attack
Severely attacked weld on
a large-diameter steel pipe
by an acid upset
Weak acids ( Carbonic Acid )
carbonic acid ( as do most weak acids ) produces smoother
attack than stronger acids
Smooth attack Jagged tree
on C. steel by pattern of
H2 CO3.Note metal loss
the vivid red caused by
color of condensing
hematite, steam with
indicating high high CO2 &
oxygen Con. oxygen Con.

Pitting and surface roughness on carbon steel increase as the

amount of dissolved oxygen increases

In regions of condensation , grooving frequently occur

Grooves are caused by the flow of acidic condensate across surfaces

Friable , light colored corrosion products containing carbonate

are often present and sometimes form during cooling

Similar products may surround leaks and failure sites . Carbonate

containing material effervesces strongly if exposed to mineral acids
 Attack is frequently severe if cooling waters contain large amounts
of condensate, since CO2 is a condensable gas attack is most severe
at the point of condensation, before mixing with the cooling water
C.steel gas cooler Note the presence
with grooving at of orange Fe
bottom of coils. oxides and CO3
Carbonic acid - Also note how
containing attack starts as
condensate small pits due to
attacked dropwise
condensation

Organic Acids organic acid strength tends to increase as

molecular weight decrease

Hence , low molecular weight organics such as formic acid are

quite corrosive relative to longer chain acids

Additionally, as in carbonic acid corrosion, oxygen tends to increase

corrosiveness of many organic acid solutions on carbon steels

Pits ( if formed ) tend to be shallower , rounder , and less

severely undercut than surfaces attacked by strong acids
 Wasted surfaces are typically rough to jagged, but they become
smoother and more undulating as acid strength, O2 concentration,
and potentially corrosive metal ion concentration decrease

Carbon steel corroded by

Flow effects may be pronounced.highturbulence areas can become
organic acid on a cast iron
preferred
pipe elbowattack sites and erosioncorrosion are important

Locally wasted region at an inlet pipe .

Horseshoe-shaped Note the severe
Comet attack
tails at the discharge
aligned
depressions due to end of with
the straight
flow is apipe
erosion corrosion striking feature of
erosion corrosion

Generally wasted pipe )to the

viewers right ) and new pipe .
Wastage was general near a
pump discharge due to high flow
 (( Cautions )) Erosion
corrosion
Oxygen pitting and erosioncorrosion frequently
produce damage resembling acid attack

Oxygen pitting can be differentiated from acid

corrosion by analyzing corrosion products &
deposits & by carefully examining pit geometry

On nonS.S,oxygen pits have less undercut interiors than acid

pits & usually lined with reddishbrown corrosion products

corrosion products formed by O2 corrosion are much thicker

& more difficult to remove than those found in acid pits

Pitting caused by oxygen corrosion

Pitting on stainless steels is associated with acid conditions

pH outside the pit may be mildly acidic or not acidic at all
that develop within pits by autocatalytic processes

However,cavitation
Cavitation producesusually causes
spongy, highly localized
porousappearing areas of
surfaces,
metal loss,unlike
strongly acid,which
resembling attacks over a much wider area
acid attack
Elimination Stopping acid corrosion requires
prevention and emergency actions
Prevention Emergency
Monitor water pH routinely Begin BD or drain system if
possible & Suspend all acid feed
inspect acid feed equipment such
as pumps on a regular basis Monitor pH frequently at
appropriate locations
Isolate & identify possible
sources of inleakage, such as If the pH is less than 3
perforated heat exchangers or Block off all acid feed and
makeup contamination Begin maximum allowable
Blowdown immediately
Eliminate windborne acidgas
contamination of cooling towers ( optional ) add dispersant
and other water sources to remove soluble iron

Regularly ( at least monthly ) ( optional ) Raise pH by adding

review all chemical feed and appropriate caustic substances
handling equipment

Clean systems containing acidic Drain or ensure flow in closed

deposits frequently systems or in stagnant areas
 CONCLUSION
Corrosion is not yet completely understood, despite an enormus
amount of research over the last century and concentrated study
during the past twenty five years

Corrosion can be controlled if it is detected and diagnosed in time,

but unfortunately there is no universal remedy

There are at least a dozen form of corrosion which are affected

in different ways by metallurgical structure, composition, and
mechanical factors

The identification of cooling water system corrosion problem

begins with a knowledge of how to recognize such problem .
Knowing where particular forms of damage might occur, What
damage looks like, how critical factors influence attack and
most importantly, how such problem can be eliminated

Acid corrosion is usually caused by an upset.kind of the acid and the

kind of metal attacked have the largest consideration in control and
eliminate such type of attack in a cooling water system .
ALUMINUM COMPANY OF EGYPT
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