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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

its tendency to
dissociate into
hydrogen ion and
counter ion

H2 Evolution
begins

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 )
2H + 2 H2 (Cathode)

Main anodic and


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
Dissolved O2
on corrosion

of Mild Steel in
Acids Corrosion
Rate ( in./y )

Acid

acetic

H2SO4

0.04
1.2

Under O2 Under H2
0.55
0.006

Ratio

92

0.36

0.03

12

HCl

0.48

0.031

16

HCl

0.39

0.0055

71

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 the


decrease
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


by acidic,chloride-containing
water.

Austenitic S.S pipe that carried sulfuric


acid . Failure was caused by severe
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
casting mould

mould cross section .

Note the irregular


surface contour
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
heat
As low
Fe+++
So,S.steels experience
little attack during brief
pH excursions
exchanger tubes
concentration
handling
acetic
During long
acidic exposure, pits may begin increases
and grow at
ever acid
during
acid
can be more
increasing
rate . Surfaces containing pits , crevices
, and other
cleaning,the
seriously
shielded corroded
areas are more likely to be attacked
by lowpH
conditions
corrosion
rate
of steel
at low than at
rapidly
Occluded
sites allow concentration of acidic increases
materials and
high
temperatures
assist the so called Autocatalytic pitting process
Sulfuric
acid atacids
roomcan be highly sensitive to
Corrosion involving
nonoxidizing
temperature
is handledare more severely
flow.regions of high
flow and turbulence
inquiescent
carbon steel
drums,
attacked than more
regions
when water
concentration
is low,but
Weires, lips,and other
flow obstructions
increase turbulence and
it elbows,tees,
becomes extremely
thus corrosion.Pipe
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 O 2 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
within.(
pH within
active
pitsreadily
may fall
to much lower
As
pH remains
low,corr.
products
dont
precipitate
in the pit
values than bulk water pH )

So,pits
usually
contain
only small amount
of is
corr.
A
striking
feature
of mineralacid
corrosion
the Product,although,
directionality of
areas
surrounding
pits
may
contain
precipitates
formed
by normal
pit
growth.
Because
pits
entrap
metal
ions and acidic
anions
, the
pHprecipitation
process
oxidation
of than
ions leaking
out density
of pits
density of fluid within
canor
beby
much
greater
bulk water
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 the
below
direction
the active
of gravity
corrosion
are favored
sites
Depassivation
by pit leak out
due to density
difference

Pits growth in
the direction of
gravity

Pit morphology varies with acid strength,metallurgy, and many


It
Thus,in
is noted
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
eventually
on metal
develop,even
surface must
when
be localized
cathodic for
attack
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
on C. steel by
H2 CO3.Note
the vivid red
color of
hematite,
indicating high
oxygen Con.

Jagged tree
pattern of
metal loss
caused by
condensing
steam with
high CO2 &
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
with grooving at
bottom of coils.
Carbonic acid
-containing
condensate
attacked

Organic Acids

Note the presence


of orange Fe
oxides and CO3
Also note how
attack starts as
small pits due to
dropwise
condensation

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, O 2 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

Horseshoe-shaped
depressions due to
erosion corrosion

Generally wasted pipe) to the


viewers right ) and new pipe .
Wastage was general near a
pump discharge due to high
flow

Locally wasted region at an inlet pipe .


Note the
severe
attack
at the discharge
Comet
tails
aligned
end of the
pipe
withstraight
flow is a
striking feature of
erosion corrosion

(( Cautions ))
Oxygen pitting and erosioncorrosion frequently
produce damage resembling acid attack

Erosion
corrosion

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
usually
causes
highly localized
areas of
Cavitation produces
spongy,
porousappearing
surfaces,
metal
loss,unlike
acid,which
attacks over a much wider area
strongly
resembling
acid attack

acid corrosion requires


Elimination Stopping
prevention and emergency actions

Prevention
Monitor water pH routinely
inspect acid feed equipment such
as pumps on a regular basis
Isolate & identify possible
sources of inleakage, such as
perforated heat exchangers
or makeup contamination
Eliminate windborne acidgas
contamination of cooling towers
and other water sources
Regularly ( at least monthly )
review all chemical feed and
handling equipment
Clean systems containing acidic
deposits frequently

Emergency
Begin BD or drain system if
possible & Suspend all acid feed
Monitor pH frequently at
appropriate locations

If the pH is less than 3


Block off all acid feed and
Begin maximum allowable
Blowdown immediately
( optional ) add dispersant to
remove soluble iron
( optional )
Raise pH by
adding appropriate caustic
substances
Drain or ensure flow in closed
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


E

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