Geot/;ermics (i97o) - SPECIALISSUE 2

U. N. Symposiumon the Developmentand Utilization of Geothermal Resources, Pisa ~97o. Vol. 2, Part t

Corrosion Characteristics and Geothermal Power Plant Protection

(Collateral Processes of Abrasion, Erosion and Scaling}
G. ALI.EGRINI * ANt) G. BENVENUTI *

ABSTRACT Before examining the etching and other troubles

Corrosive agents affecting equipment for geothermal and
electrical power generation are surveyed in a short intro-
duction.
For each of them the various physical and chemical
conditions of occurrence are examined, as well as the various
modifications they undergo and the different ways they con-
tribute to the aggression of materials.
Following steam circulation and its transformation into
electrical power, the most conspicuous corrosion phenomena
are outlined. The latter takeplace in steam pipes, thermal and
hydraulic plant equipment, building works and finally in
power, control, manoeuvre and measurement electrical appa-
ratus.
In each case a brief mention is made of existing rela-
tionships between corrosion effects singled out and their re-
spective causes, the varying conditions of steam-producing
fields and different environmental conditions.
With a view to probing deeper into the most significant
aspects of this problem, experimental data are illustrated and
a critical analysis is developed for the interpretation of corro-
sive phenomena accordingly observed.
Knowledge of the mode of action of corrosion is a
preliminary condition for the adoption of the best suited
protection technique."
In some instances a direct action on the corrosion en-
vironment is possible and may basically alter its characteristics
of aggressiveness. In most cases, however, building material
resisting the aggressive attack of the environment, or else
standard protection techniques shall be resorted to.
In this connection, results of successful] experiences are
reported and suggestions are advanced for the solution of
still pending problems.
Introduction
Etching agents, responsible for the complex cor-
rosion processes taking place in geothermal power
plants, are, or directly derive from, chemical compounds
carried by steam in the endogenous fluid. Hence our
research begins with the average composition of the
steam coming from steam jets (Appendix A1).
It is immediately noticed that steam carries a large
quantity of slightly soluble gaseous compounds that,
in the end, are ejected to the surrounding atmosphere
and give the atmosphere the characteristics to be de-
scribed. Other compounds, on the contrary, dissolve
easily and can be found in steam condensate. Among
these compounds the chlorides are especially important;
they occur in quantities too small to affect the average
fluid composition quantitatively, but they are a de-
termining factor in many corrosion processes.
* ENEL, Compartimento di Firenze, Gruppo Perfora-
zioni. I.M., Larderello, Italy.
due to the presence of the typical endogenous fluid com-
ponents, it is useful to describe in short the corrosive
environment as seen in the different parts of the plant
as a consequence of physical and chemical modifica-
tions in the fluid. In this research, w e will follow the
steam route through the plant, schematically represented
in Figure 1.
Description of the e n v i r o n m e n t
In the route from wellhead equipment to turbine,
the natural steam temperature varies from 140 to 260 °C
and its pressure from 2 to 10 ata. It is usually a super-
heated steam containing now and then coridensate phases
due to liquid dragging, to condensation in the pipeline,
or, even, to direct inejction to wash the fluid chemi-
cally. Special drains, or even axial separators in the
case of washing, permit the extraction of the liquid
from the pipeline. These condensate phases contain, in
fact, in a concentration remarkably greater than the
fluid average, the soluble components of the fluid itself
such as H~BO3, NH3, chlorides and sulfates (Appen-
dix A2).
The steam lines convey steam to turbine where the
steam goes in at a temperature ranging from 150 to
220°C and a pressure of 1.9-7.7 ata. Then it comes
out to reach the condensation unit at 9 to 12% humid-
ity under a pressure of 0 . 0 7 - 0 . 1 3 ata.
In the mixture condensation unit the condensation
of steam is carried out in a closed circuit with the
water suitably cooled. The average composition of this
cooling water is reported in Appendix A3. The com-
parison between the analytical data of water upstream
or downstream of the condensation unit shows clearly
the chemical and physical processes occurring during
the circuit of this water.
In the condensation unit, obviously, the water
comes into contact with the fresh steam supplied by
steam jets and is enriched in CO_~ and H_~S. But in the
cooling tower the water meets countercurrents with con-
siderable quantities of air, thus causing a stripping of
CO~ and H~S, an oxidation of the latter with a separa-
tion of elemental sulfur, a partial oxidation in sulfites
and sulfates of existing sulfides and then an enrich-

865
 iI

i =

]O

;Z

1 WELLHEAD EQUmlqENT 9 EXHAUST 17 COOLING TOWER

2 DR~dN 10 CONDENSATION EQUIPMENT 18 PACKING
3 AXIAL SEPARATOR 11 INTERMEDIATE COOLERS 19 STRUCTUREOIr PACKING SUPPORT
4 MANIFOLD 12 BAROMETRIC WELL 20 WATER DISTRIBUTION SISTEM
5 FILTER 13 BAROMETRIC PIPES 21 STACK
6 CABIN 14 TUNNEL 22 SUPPLY CHANNEL
7 TURBINE 15 MAIN PUMP 23 DEICER UNIT
8 COMPRESSOR 16 SUCTION BASIN 24 DIAGONAL COLUMNS

FIG. 1. - - Schematic diagram of endogenous fluid utilization plant.

866
 ment in 02 and N2. The gas held in the condensation The existing temperatures are much lower than are
water comes from the partial solubilization of gases needed for H2S in its gaseous phase to attack iron and
carried in the steam and from the contact with the air create compact films of FeS, whereas they are too high
in the cooling towers. for H2S and CO_, in water solution to cause etching.
The cations in the system come directly from the Nevertheless, solid debris deposits are usually found
fluid (ammonium) or from etching processes in ma- on the valve seats and soon prevent the valves from
terials contacting the fluid (calcium, magnesium, iron); being satisfactorily tight. Small steam leaks in the flanged
and the anions come directly from the fluid (boric, joints or in the stuffing boxes of regulating valves end
carbonic, hydrochloric, hydrosuifurous and silicic)or by rapidly damaging the gasket seats and manifest
from the oxidation processes (sulfuric and sulfurous). themselves by typical white or yellowish efflorescences
This condensation water, though its pH reaches 6.5 of borates (Figure 2). The telescopic joints or bellows
to 7, has such oxidoreducing properties as to cause cor- joints after a short operating time develop leathery
rosion processes similar to those that are obtained in
sulfuric solutions having a very low pH. It is very cor-
rosive for common carbon steels, and since it contains
great quantities of dissolved CO2 it also etches cement-
ing materials having a high percentage of limestone.
The corrosion processes, in the condensation unit,
originate in this way, as do also those in the barometric
well, in the ducts, in the circulation pumps, in the
cooling towers, in the connecting pipelines and in the
gas intermediate coolers.
The noncondensable gas (average analysis shown
in Appendix A4) is discharged outside; hence in the
close proximity of the plants as well as around the
steam drains there are high concentrations of CO2 and
H2S. At times the H2S concentration reaches 10-30
ppm and the CO2 percentage is a thousand times great-
er. In the presence of 02 and atmospheric humidity,
the etching on the common metallic and cement build-
ing materials is marked. Moreover, the hyperbolic cool
ers, owing to an unavoidable dragging of infinitely
small particles of liquid, disperse a continuous saline
rain of condensation water in the immediate environ-
ment, carrying sulfates, sulfides, bicarbonates and bo-
rates mixed with free CO2, 02, H2S and colloidal sul-
fur. This is corrosive for the presence of etching anions
such as S O , - - and also causes equally harmful oxido-
reducing processes. All exposed materials and equip-
ments - - electric cabins, industrial buildings, overhead
lines, protective coatings, structures in general, and in-
struments m undergo corrosion severe enough to en-
FIo. 2. - - Typical whitish efflorescenees du¢ to borates and
danger maintenance and operating efficiency. other salts a#er small steam leaks.

Corrosion, erosion, abrasion and scaling protection

and remedy
STEAM LINES
Etching and scaling by borates and other salts
Generally the chlorides carried by the endogenous
steam do not exceed the maximum limit of 20 ppm
(Appendix AS), and the carbon steel pipelines of com-
mon thickness (6-7 ram) have a reasonably long life.
A general and very slow electrochemical corrosion
is noticed in the pipeline surface. The etching may be
uniform or there may be wide irregular craters or scales
in the condensation areas.
scales that completely prevent sliding; in fact, they are
outdated now in favor of a zigzag construction resting
on supports that allows a free expansion. Sporadic cases
of scaling due to solid debris carried by the fluid were
noticed especially near the wellhead equipment at the
reopening of a steam jet after long period of inactivity.
Now and then, when the fluid carries a certain
quantity of liquid, numerous scales of different thick-
ness and consistency can appear on the pipeline wall,
thus reducing the inner diameter considerably (Figure
3 and Appendix A6). But, luckily, solids or liquids are
not often carried by steam.

867
! hole on the spot and it is necessary to completely re-
FIG. 3. - - Siliceous scaling in a D N 450 steam line connecting
a steam jet very rich in dragged water.
Etching by chlorides
There are however some steam jets, rather rare
(Appendix A5), in which considerable quantities of
chlorides are noticed. The chlorine intake is not con-
stant and some variations can take place not only in
the course of years but also in a few hours or days.
In these instances, the average concentrations are cal-
culated by tens and hundreds of ppm. In the presence
of superheated steam the chlorine etching of iron is
negligible; but in the liquid phases the etching goes on
rapidly. Probably chlorine is carried by steam in the
form of NH4CI and cannot exert its etching action as
long as it is not dissociated. Obviously, in the presence
of the liquid, solubilization and ionization occur im-
mediately: ammonium is probably blocked in the form
of borate and iron is rapidly attacked by the free hydro-
chloric acid. In the commonly used carbon steel pipe-
lines, the prevailing corrosion belongs to the general
electrochemical type and the etching is located just
where there is a production of condensation water: more-
over, the fluid flow tends to bring new metal surfaces
into contact with the etching agent, thus accelerating
the corrosion process up to complete destruction.
Round the hole thus originated, the original pipe-
line thickness is entirely destroyed, sometimes over very.
long stretches. Thus it is often impossible to repair the
868
place the corroded section.
Ni/Cr/Mo AISI 316 type stainless steels were also
used with a completely unfavorable outcome. In fact,
the superficial corrosion of carbon steel with moderate
removal of material gave way to localized etching with
much more rapid destruction: pitting corrosion, stress
corrosion and intergranular or intercrystalline corrosion.
It is common knowledge that pitting corrosion is
a distinctive feature of the presence of halogens. The
etching process takes place as follows: the chlorine anion
destroys locally the protecting film formed by chrome
oxides. Then the surface beneath acts as the anode in
an electrolytic cell whose cathode is the surrounding
passive surface. This explains the localized nature of
the etching process since the emf thus generated pro-
tects the cathodic surface against further etching. The
intensity of the etching generally increases with the rise
in concentration of the corroding agent and with tem-
perature.
In the presence of static stresses of a certain value,
always caused by internal stresses or externally applied
loads, the pitting corrosion changes easily into a stress
corrosion. In fact, as the microcracks get deeper the
stresses at their root concentrate to the extent of exceed-
ing the material yielding-limit: a plastic deformation
occurs and the crack goes on. The mechanical widen-
ing of the crack exposes nonpassivated metallic sur-
faces where the corroding agent operates with an in-
creasing speed, thus magnifying the corrosion process
and resulting in a breakage. Generally, the etching con-
tinues through crystals (transcrystaUine stress corrosion)
facilitated in this by high stresses and work-hardened
material. In other instances, as a consequence of dight
stresses and unsuitable thermal treatments that cause
precipitation of carbides, the corrosion goes on along
the edges of crystals themselves (intercrystalline stress
corrosion). The intensity of stress etching increases with
temperature and stress; it depends also on the oxide-
reducing power of the corroding agent on steel, the pH
values and the alloys present. It is common knowledge,
for instance, that even H2S in water solution with a
pH lower than 4 can cause stress corrosion in type 18/8
steel, whereas stress corrosion does not take place in
type 18/12/2.5.
Furthermore, even stainless steel having a carbon
content greater than 0.04%, as a consequence of un-
controlled heating and cooling such as in weldings, un-
dergoes a precipitation of chrome carbides along the
crystal outline; this reduces the chrome content in aus-
tenite grains and inhibits in those spots the passivation
by the chrome oxides. Such areas are easily attacked
by etching when they are exposed to an acid environ-
ment, for instance to hydrochloric, sulfuric or sulfurous
acid, and an intergranular corrosion occurs. In welding,
for instance, the critical area is over a distance of 4-8
mm from the welding bead.

FIo. 4. m Corrosion in a stainless steel bell'ows: m u l t i p l e trans-
verse a n d longitudinal breaks can be seen.
From what has been said previously about the
three types of corrosion, it is clear that the attempts to
use stainless steel on the endogenous fluid were not
successful. The prevalence of one of the three corrosion
types over the others obviously depends on the type
of steel and the installation conditions, but it is evident
that the conditions for etching do exist, and it can de-
velop and endanger in a short time the steam line opera-
tion. Some examples are given here.
At the wellhead equipment of VC5 steam jet, whose
characteristics are reported in Appendix 2, a bend in
AISI 316 was attempted; within a few months a mixed
pitting-stress etching took place, making the bend un-
usable. In 1968 on the manifold Lago-Monterotondo,
in the strip involving the Mancino well that was also
rich in sulfates and chlorides, carbon steel bellows
absorbers installed in 1959 were replaced with stainless
steel pipelines, used to lead the endogenous steam to
pletely destroyed during the 8 to 9 years' operation by
progressive electrochemical corrosion, the latter were
attacked within only 2-6 months by evident pitting and
stress corrosions (Figures 4, 5, 6).
Other breaches by intergranular corrosion were
often noticed in weldings of AISI 504 or 316 stainless
steel pipelines, used to lead the endogenous steam to
the turbine pumps; these cracks, too, often occurred
after a fairly short operating time.
i
Fro. 5. ~ Detail o] b e l l o w s w a v e w i t h breaks.
Since an etch-proof material to withstand chloride
has not been found, a system of protection by varying
the corroding environmental conditions was worked out
some time ago. Since 1956, the washing of steam has
been attempted by introducing in the pipeline water
or alkaline solutions that retain the acid-soluble com-
ponents of steam and then'-separating the liquid down-
steam in axial separators. At first, the washing was carri-
ed out with water, measured in the most accurate way
possible to avoid a dangerous and uneconomical steam
degradation, but the concentrated liquid which was col-
lected in the separators had a very low pH and was
excessively corrosive. Then inejctions of diluted soda
solutions were tried. At first, the washing liquid was
recycled to increase the concentration for.subsequent
use in chemical borax factories, but at these concentra-
tions tough scaling of borates mixed with sulfates and
sulfides occurred. The pipelines were clogged and some-
times the induction valves to the turbines and the blades
themselves experienced clogging and scaling.
Furthermore, if the inejected liquid was not entire-
ly separated after a short pipeline length, considerable
corrosion and erosion occurred in the steam line where
the liquid was dragged.
Nevertheless, our present knowledge leads us to
assert that the alkaline washing of steam is the ,only
suitable remedy for etching in steam jets with con-
869
FiG. 6. - - Microphotograph x 190 o~ the cracked area o/ the
bellows in Figure 5. Numerous cracks due to fragilization
of the material can be seen.
siderable chloride content, provided that the following
principles are adopted:
u the washing must to carried out at the well-
head 'of the affected hole with a diluted alkaline solu-
tion and a quantity of soda lower than the total anions
contained on an average in the supplied steam; this
prevents the formation of poorly soluble sodium borates
- - ' t h e liquid delivery must be always lower than
the flow necessary to saturate the steam, and the liquid
must be entirely separated in efficient separators after
the minimal circulation for mixing was been achieved.
Unfortunately, from the technological point of
view, the solution of this problem is very complex,
considering that washing units are needed where there
is not any operating staff, in areas that are difficult to
reach and in steam jets whose composition and delivery
vary within certain limits.
THERMAL AND H Y D R A U L I C M A C H I N E R Y
Whereas in the old secondary steam cycle the most
important corrosion processes occurred in the heat ex-
changers, in the direct cycle now used, the etching
occurs in the thermal machinery directly utilizing the
endogenous fluid. Since the steam of the various wells
870
FIG. 7. - -Corrosion in a turbine rotor: a well localized etched
area can be seen.
placed around a plant is collected and conveyed to the
general manifolds feeding the plant, it is evident that
average etching characteristics of the steam when enter-
ing the turbine depends on the complex holes.
The problem of choosing the material for the
machinery is then complicated, in addition to the nor-
mal strong mechanical stresses, also by the need to cope
with chemical substances under particularly dangerous
conditions of temperature and humidity. Besides the
erosion due to a high-speed fluid, there is corrosion
imputable to chlorides, sulfides and sulfates and abra-
sion caused by finely dispersed solid substances. Adding
to this the scaling processes, we obtain a complete
panorama of the factors that threaten the efficiency of
the plant.
Scaling can occur anywhere in the turbine. The
components are always the same: iron sulfide, clay,
ammonium, calcium and alkaline metal salts of boric,
sulfuric, hydrochloric and carbonic acid. As a rule, iron
sulfide prevails in the first rows of blades, whereas
later rows shows partially hydrated ammonium borates,
silica and various silicates. These scales are up to 5 mm
thick and show a crystal consistency and structure
that suggest an actual separation by supersaturation
crystallization. Since it is impossible to prevent their
formation, practical methods are used to diminish their
Fro. 8. ~ Detail of corrosion in a turbine rotor. There is con-
siderable etching near the blading, with removal o/ ma.
terial, whereas the blades show only slight scales.
danger such as, for instance, the spaced injection of
heavy diesel oils into the turbine to make the scales
softer and easy to remove.
In the case of corrosion, on the other hand, pos-
itive results have been obtained in the choosing of
materials. For instance, after rejecting the brass original-
ly used for blades in the indirect cycle, a stainless
chrome-nickel steel (X 12 C N 188) was unsuccessfully
tried but showed frequent breachcs from intergranular
corrosion, due to the N H ~ and H:S etching on nickel.
Chrome steels with a martensitic or scmiferritic struc-
ture such as XI0 C13, X15 C13, X20 C N 18 and XI6
C N 19 are n o w being used; thc high chrome content
of these steels gives the alloy effective passivation against
cching agents, besides its suitable characteristics of stress
resistance. The blades thus made have reached econom-
ically satisfactory values in terms of hours operation,
and probably other improvements will be achieved in
the future. Erosion is noticed only in the last blade
rows where some sporadic pitting also occurred.
Some perplexity still exists as to the behavior of
the materials employed in the construction of the re-
maining parts of a turbine: type 1 8 M V 5 alloy steels
are usually used for rotors, whereas stators and casing
arc made of cast iron in the low-pressure parts and of
graded steel in the high-pressure or back-pressure units.
Fro. 9. -- Corrosion in a turbine casing. The etching is loca-
lized in a limited area with considerable removal oJ ma-
terial in the body, whereas the blades are sound.
Chlorides are the main etching agent; the corrosion is
superficial and occurs where there is a production of
condensation water. Etching and removal of the iron
is facilitated also by erosion processes (Figures 7, 8, 9).
As a rule, cast iron had a greater resistance than steel.
The behavior of stainless steel is still unknown, but
a test has been planned. Since in the absence of con-
densation water the corrosion does not take place, the
utilization or proper drains, if possible, is recommended.
The condensation unit, as was noted, has only a
slightly acid medium but its oxidoreducing properties
are harmful for many building materials. The spots
where the etching goes on with greatest intensity are
those that are hit by the sprays, because here the cor-
rosion product is continuosly removed thus laying bare
new materials and the areas surrounding the level of
the liquid.
The c o m m o n carbon steel undergoes a fairly rapid
and general corrosion, since it is easy to depolarize.
Besides the formation of ferrous hydrate and its sub-
sequent oxidation to ferric hydrate, there is also a
production of iron oxide and sulfide tubercles with
traces of precipitated sulfur because of the presence
of H2S and oxidizing substances.
The cast iron employed in the construction of the
condenser of the first smaller units resisted this environ-
871

Fla. lU. - - Corrosion in an A I S I 304 electrowelded pipe. The
large craters and pittings around the nonattacked welding
bead are due to contact with water of the cooling towers.
ment well. Also the sheet iron-lead terneplate shows
good corrosion resistance, but it is subjected to the
mechanical erosion of water jets on lead and it has to
be protected in these critical spots with AISI 316
sheets. AISI 316 has shown.up to now a perfect cor-
rosion resistance under these conditions, whereas in 304
type intergranular and electrochemical corrosion have
been noticed in some instances even on the weldings
of electrically welded pipelines (Figure 10), However,
the construction of the whole unit in AISI 316 has
not been, up to the present, an economically feasible
solution. On the water spraying units, made of different
kinds of east iron, the corrosion does not occur, but
tough sulfurous scales are noticed, that tend to clog
these units and must be eliminated by sandblasting.
What has been said here concerns not only the
condenser but also the barometric pipeline, gas and
water pipelines in the different compression stages, and
the intermediate coolers and their barometric piping.
In the barometric piping the spots most attacked
are those in the tunnel at water level where also stain-
less steel shows signs of corrosion craters, but it is
sufficient to lay on a thicker coating to ensure their
long life.
872
In the compressor, the corrosion does not cause
important trouble, but scales of the type seen in tur-
bines, composed of FeS, sulfates, borates, silica and
sulfur are noticed also here.
Sulfur can be found in a great quantity in gas in-
termediate coolers of the packed type; it is an inflam-
mable deposit that tends to clog progressively the whole
passage area of the gas and necessitates frequent re-
placement of filling rings. However, in these instances
the scales on the compressor body and rotors are less
widespread.
Cast iron, terneplates and stainless steel in the
main water circuit have resistance properties similar
to the ones already mentioned for the condensation
unit. Obviously the same environment exists.
Therefore, the main pump shaft, wear ring and
bushes are made of chrome-nickel steel; the propeller
of chrome steel and the bearings of chrome steel with
Dewa metal; the water inlet piping and the return
piping from the cooling tower, made at first of cast
iron, are at present coated or made entirely of AISI
316. Aluminium and its alloys have given good results
on their resistance to corrosion from water circulation.
Peraluman alloy with a 3.5% magnesium content is
likely to be much used since it shows excellent mechan-
ical properties as well as a suitable corrosion resist-
ance.
Buildings in the plant hydraulic eireu/t
The buildings comprise the barometric well, the
suction basin, the tunnel, and the cooling tower. It is
necessary to make a distinction between the parts placed
under the level of the liquid and the upper parts.
The former are exposed to the solubilized chemical
compounds we have mentioned, whereas the latter are
evidently at~ected by the action of gases given off by
the liquid, which are transformed because of the unu-
sual humidity and aeration.
T U N N E L S , W E L L S , BASINS
Tunnels are built with a first head-to-head ring
of bricks and a second ring against the earth of con-
crete, or concrete (simple or reinforced) with protec-
tive plastering. The plastering is generally accomplish-
ed by simple or reinforced gun rendering.
Part above the liquid
The most serious etching conditions are in the part
exposed to gas, that is the vault and the water line
where the etching product is continuously removed by
new erosion, thus preparing new areas for the etching
itself. In some parts of the vault where there is in-
sufficient aeration and dilution of sulfurous gases, a
catalytic oxidation of sulfides to sulfates and sulfites
takes place and the sulfuric ion attacks the calcium
of cements with a speed proportional to their per-
meability.
Flo. 11. - - Corrosion in a brick tunnel with nonseasoned
reinJorced gun rendering. The part under the level o/ the
liquid blackened by sulJides is in a good state: the upper
part is much corroded and the metallic reinJorcemenl is
seriously damaged.
This process, which is the most conspicuous, is
accompanied in a more moderate manner by processes
of deliming by carbonation and formation of sulfides.
The etching begins in the calcium contained as free
lime, then in the calcium carbonate or bicarbonate,
and finally in the calcium bound to silica and belong-
ing to the mineral cement components. Processes of
double exchange between ammonium, iron and calcium
salts also occur and determine the course of etching
reactions.
This results in a thin paste formed of CaSO~.2H20
grains or crystals dispersed in a chaotic heap of va-
rious salts, boric acid, sand and silica.
In the case of reinforced concrete or concrete
gunned with a metal mesh, when the etching salts,
penetrating through the superficial layer, reach the
iron of the reinforcement, they cause the formation of
oxides, sulfides, and various iron salts that, since they
take up a volume considerably greater than the original
iron, cause visible gaps in the protecting layer of ce-
ment. At this point the corrosion of the iron now laid
bare goes on more rapidly, and it can jeopardize in a
short time the stability of the structures.
On the contrary, in the case of a brick tunnel,
the junctures are the first to be attacked, also resulting
in loss of stability.
Fro. 12. - - Corrosion in a well seasoned rein/orced concrete
tunnel. The most attacked area is in the suction basin
vault. The iron rein/orcement is laid bare and damaged.
For instance, in the tunnel of the Serrazzano plant,
built with bricks, it was noticed after almost 10 years
of operation that the bricks were attacked over some
centimeters and the juncture cohesion was destroyed;
the use of a reinforced gun rendering was then decided
upon and because of the urgency was installed without
a suitable seasoning time. On inspection after one year
of operation, a complete destruction of gun rendering and
metallic reinforcement was noticed in the least aerated
parts. Even the bricks below were crumbling over some
millimeters and presented an acid reaction (Appendix
7 and Figure 11). Under these conditions, the whole
setting-hardening system of the cement was destroyed,
and the original gun rendering was transformed into
a group of calcium, iron and ammonium salts dispers-
ed in a silicious medium to the detriment of the sili-
cates and silicoaluminates that under normal condi-
tions represent the resistant structure of the cement.
On the contrary, in Larderello plant 3, where the tun-
nel seasoning was complete before starting, after 20
years' operation a strong etching was noticed only in
an area near the plugs of air-exhausters and at the
surface level of the liquid on the pillars and the side
wall (Appendix A 8 and Figures 12, 13, 14, 15).
873
FIo. 13. ~ Ceiling of the least attacked area in the tunnel of Fro. 14. -- Pillar of the same tunnel in the pump room, after
Figure 12. Note the soundness of the building work with chipping. Note the deep hole hollowed out at the water
the exception of the water level line. level line.

Part below the liquid packing, the diagonal columns, the supply channels,
the cantilever roof and the stack itself. Again, the parts
Below the level of the liquid the etching is al-
below the liquid level do not suffer a strong attack,
ways moderate. It is caused mainly by the dissolved
especially since a slimy sulfur deposit protects the ce-
CO~ that superficially delimes the cement, transform-
ment from contact with water. But all the structures
ing insoluble carbonates into soluble bicarbonates. This
above show much deliming by bicarbonation, etching
is, luckily, a slow process, although its speed can in-
in iron, and erosion of the corroded parts.
crease when the concrete is permeable and rich in cal-
This process is the more evident as the concrete is
careous components. In this instance, the deliming can
richer in limestone. Therefore, when the crushed stone
be accompanied, in a more moderate manner, by etch-
is constituted of calcium carbonate, the cement work
ing reactions of CO2 and B~Oa on silicate and silico-
shows within a short time some hollows in the spots
aluminates to transform them into carbonates, bicar-
where there were limestone grains and the binder frame
bonates and soluble borates; the dissolved HaS and
that remains is considerably weakened (Figure 16).
NH, HS react with the ferrous ion to from iron sulfide
If the reinforcement is attacked too, the recom-
that gives a typical black coloring to the immersed
mendation made for tunnels applies; the corrosion
part of the tunnel.
should be immediately stopped to ensure the stability
Also the dissolved ammonium sulfate can attack
of the structure.
concrete calcium and magnesium salts if the concrete
Strong corrosion by decarbonation as well as by
is not suitably seasoned. Thus it is very important to
sulfuric etching of calcium salts has been seen in the
ensure a proper seasoning, but this is not always achiev-
stacks. For instance, in the No. 3 cooler of Larderello
able in maintenance procedure.
plant 3, after 20 years operation, the upper part of
the stack was found to be seriously damaged (about
COOLING TOWF..RS 15-16 m under the cornice, Figures 17, 18).
Also the cooling towers can be attacked by cor- Besides horizontal breaches about 60 cm apart,
rosion process like the ones that take place in tunnels. that is at the casting joints, also vertical breaches iso-
All parts are affected: the supporting structure of the lating entire structural panels were noticed.

874
F1o. 15. - - Detail o] cast iron barometric drains of the inter-
mediate coolers of the gas compressors. Scale and deposit
can be seen in the part immersed in the liquid.
The breaks had penetrated to the point of corro-
ding the reinforcen~nt iron, so that it was necessary to
restore a continuity by welding before repairing the
concrete.
REMEDIES
In view of the importance of etching processes,
many attempts have meen made to combat it. For a
new construction the following measures are needed:
Coat the reinforcement with a suitably thick
layer (4 cm approximately) of concrete to inhibit the
infiltration of corroding gases and prevent etching on
iron.
Let the casting season as long as possible in
order to complete the setting and hardening before ex-
posing to etching agents.
Use suitable components to shorten the setting
time. Therefore sand and siliceous crushed stone should
be used instead of limy stones, and quick-setting ce-
ments of the pozzuolana and alumina type. Further-
more, concretes should be prepared by studying the
most suitable particle size.
It is recommendable to perfect the surface fin-
ishing by a good gun rendering and do whatever pos-
sible to lessen erosion by water. A final protective
Flo. 16. - - Example of concrete deliming. Pillar supporting
the packing of a cooling tower cast with crushed stone
rich in limestone.
coating is extremely useful, above all in maintenance
operations, but is hard to achieve.
Many attempts have been made in this respect,
but their outcome was often unsatisfactory (Appendix
A9). A suitable coating should combine the following
characteristics: resistance to CO~ and acid gases, re-
sistance to erosion, resistance to aging l~y exposure to
sun and air, perfect adhesion to the cement (same
coefficient of expansion). A coating meeting all these
requirements has not been found.
PACKINGS, DEICER U N ITS AND WATER DISTRIBUTION
S Y S TEMS
To conclude the examination of this part of the
plant, the packings, deicer units and water distribution
systems of Cooling towers will be discussed briefly.
The distribution systems were made at first of sand-
stone or asbestos cement material; but sandstone was
not suitable owing to its low elasticity and brittleness,
and asbestos cement was corroded by the CO2 action
that solubilized and destroyed the hydraulic binder
by deliming it.
The P.V.C. (polyvinylehloride), now commonly
used, though it gives satisfactory results, undergoes the
aging common to many polymers, accelerated by the
contact with water and gases.
875
 Fro. 17. -- Cracks in the stack o/ a cooling tower.
The packing is usually made of fir wood that be-
haves very well; furthermore, the sulfur patina cov-
ering it inhibits any form of bacterial life, thus no
formation of algae occurs. The deicer units, finally,
were made at first of iron or P.V.C., but the iron units
were destroyed by rapid electrochemical corrosion, and
the P.V.C. units became very fragile at low tempera-
tures. At present, deicer units have been rebuilt with
Peraluman; its behavior has been entirely satisfactory
up to now.
Lines, transformers, and other equipment exposed
to atmosphere
As has been pointed out, the atmosphere surround-
ing geothermal power plants exerts an etching action
on many building materials and protective coatings•
The action is strong within a distance of 200 meters
from the cooling towers, average within a distance of
200-500 meters, and harmless beyond these distances.
The high concentration of H~S and CO.~ in special
conditions of oxidation and humidity, the continuous
rain of condensation water which attacks exposed sur-
faces by its oxidoreducing processes, make it difficult
to select building materials or take measures for eco-
nomical maintenance.
The chemical processes involved are briefly the
following:
876
FIG. 18. -- Cracks in the stack ol a cooling tower.
I) Formation of sulfides. The exposed surface of
copper or silver alloys, the pigments containing heavy
metals (Fe, Cu, Pb, etc.) and even the Fe hydroxide
produced by the corrosion of ferrous materials are trans-
fornied into their respective sulfides by the the. H~S
in the environment. There is typical browning of col-
oured surface.
2) Fragilization and aging of organic substances.
The chemical double bond is much more often broken
in this environment. This phenomenon plays a deter-
mining role in the destruction of some protective coat-
ings and synthetic paints.
3) Inhibition of the ~ calamine ~ removal process.
(,~ Calamine >7 as used here refers to ferrous and ferric
oxide which forms during operation). A good protective
coating of ferrous material is commonly obtained af-
ter removing the calamine produced when iron is ex-
posed to atmospheric agents. The surface is the suit-
able for adhesion and is not undermined afterward by
other oxidation processes. But in the atmosphere of geo-
thermal power plants, as soon as the calamine is re-
moved the surface below is already seriously attacked.
The new coating cannot ~ take ~> securely, since the
already existing etching processes continue and en-
danger its life.
 4) Corrosion of metallic coats. This is due to the
conden.~ation rain dragged by the cooling towers. If
environmental conditions allow the water to evaporate
rapidly, a sticky saline deposit occurs and protects the
surface below as a scaling: but when a saline solution
remains in contact with the coating, the electrochemi-
cal corrosion progresses rapidly. It is characterized by
localized pitting especially when the anodic areas are
limited in comparison with the cathodic areas. The sur-
faces begin to get opaque, then they are covered with
blisters having slight rust haloes and, finally, the orig-
inal protection is entirely destroyed.

5) Impossibility of a correct painting cycle. As in

the case of calamine removal that is compromised by
a simultaneous etching, a complete painting cycle with
the application of many protective coats is jeopardized
by the fact that during the application destructive pro-
cesses imputable to the atmosphere as well as to the
condensation rain inevitably occur. The paint may be
relatively inert to the etching agent; in this case a very
slight deposit occurs which does no damage other than
to the setting of the following coats. Or the layer below
may be attacked by the etching agent (especially un-
dersurfaces containing lead or iron that are particu-
larly sensitive to hydrogen sulfide). In this instance
the characteristics of the undersurface are affected im-
mediately. In either case the paint cycle cannot meet
the resis.tance requirements from the very beginning.
6) Acceleration of etching by differential aeration.
The thickness of the protective coating is not perfectly
homogenous. The thinner areas suffer greater penetra-
tion of atmospheric oxygen to the iron below. There-
fore, an increase.in potential occurs in these spots, and
they acquire a cathodic character in comparison with
the thicker areas. Thus, in such areas corroding pro-
cesses being with the formation of blisters and the
breaking of the protecting film. These processes are
facilitated by the geothermal power plants.
7) Decomposition of concrete due to the deliming
and corroding action of the CO: and the acid compo-
nents of the condensation water. This has been discuss-
ed in connection with the building works in the hy-
draulic circuit.
From all of this, it follows that one can anticipate
serious corrosion of the geothermal plant exposed to
the atmosphere. As regards the power machinery and
equipment, a strong etching on metal surfaces of alI
kinds will be noticed. For example, transformer ra-
diators are seriously damaged by corrosion in the spots
where the condensation water deposits. Special meas-
ures are taken in order to protect the dangerous parts
against this rain.
Iron horses and frameworks, though frequently
varnished, are constantly attacked (Figures 19, 20).
F~c. 19. -- Corrosion in metallic Jrameworks and supports o/
cabins exposed to the action of the condensation rain.
The isolating switch lever controls, switch levers
and control boxes, metallic structures of all kinds re-
quire an expensive maintenance.
Overhead conductors made of Aldrey alloy show
superficial etching of the cable wires; in fact, the for-
mation of oxides and hydrated basic salts of aluminum
takes place, increasing the volume and causing subse-
quent deformation.
A short time after painting, the iron poles of elec-
tric lines near plant show some pitting and superfi.
cial corrosion with scales on the side exposed to the
rain. The power connections made of copper are ex-
posed to a sulfide formation and finally become brittle.
The corroding action becomes really harmful for
protective and control circuits, for measuring circuits,
remote controls, and instruments in general. In such
instances the circuit uses small-section conductors that
are rapidly worn out by corrosion, Furthermore, in the
field of low currents the connections must ensure ef-
ficiency, but superficial sulfuration always occurs in
the materials usually employed in such equipment and
makes efficiency impossible.
To eliminate the drawbacks that have been listed,
two solutions were considered: 1) the use of suitable
protection, or 2) the utilization of etch-proof building
materials.

877

Flo. 20. - - Corrosion in metallic /rameworks and supports ot
cabins exposed to the action o/ the condensation rain.
PAINTING A N D PROTECTIVE COATINGS
A large range of products and materials has been
tested, but up to the present time no completely sat-
isfactory results have been obtained. The oil paints,
once universally used, give good results inside the ma-
chinery building, but outside even a four-coat varnish-
ing cycle does not last longer than two years. Progres-
sive browning is noticed due to the formation of lead
sulfide or other heavy metal oxides contained in the
pigment. The speed of discoloration depends on the
pigment composition and its average characteristics.
Epoxy paints, especially when applied after a correct
surface scraping, have a longer life than oil paints,
but they age too. Unsatisfactory results were obtained
also with oleosynthetic, acrylic, vinyl, phenolic, ctdoro-
rubber, polyester and polyurethanic paints.
Better results were achieved in the painting of
machines at temperature of about 200°C with sili-
cone paints. Promising results, but not well texted yet,
were obtained with cycles of a coat of zinc plate dis-
persed in a synthetic medium and two coats of paint
containing chlororubber on carefully prepared surfaces.
In general, a painting cycle, to hold out longer
against etching, should consist of:
the most accurate preparation possible of the
undersurface by sandblasting or scraping;
878
the utilization of primers not containing heavy
metals and synthetic final coats with the shortest ap-
plying and drying time.
Among the most commonly used protective sub-
stances, it is useful to mention vaseline for power con-
nection and synthetic spray varnishes for cleaning and
coating the controls.
SELECTION OF BUILDING MATERIALS
On the ground of what has been said before,
when economically possible, the common carbon steel
should not be used. For stands, doorways and poles
it would be better to use reinforced centrifugated con-
crete, with a good surface finishing.
As to frameworks, supports, handrails, stairways,
gangways, metallic structures in general, good results
were obtained with Peraluman. Peraluman control le-
vers for switches also had a long life.
Under the action of the condensation water of the
cooling towers the Peraluman surface becomes opaque
with small white pittings, hut the process seems to stop
there, with no sign of strong corrosion. Grounding
wires of individual equipment can be made of copper
protected with a plastic sheathing: but the ground mesh
and grounding terminals should be made of iron rod
and be suitably oversize to resist corrosions.
Copper or copper alloy conductors should not be
used unless for large-section bars or tongs which are
affected very slowly by sulfuration. In general, alumi-
num and its alloys are preferable since they resist cor-
rosion by natural passivation in a neutral or slightly
acid environment. Stainless steel is recommended for
bolts since carbon steel as well as galvanized iron are
rapidly oxidized. The connections for low-current
equipment should be pressurized or gold-plated.
In conclusion, it can be stated that in all appara-
tus exposed to the atmosphere in geothermal power
plants, whereas it is impossible to ensure positive re-
suits by protecting materials with the commonly used
coatings, it is nevertheless possible to eliminate dan-
gerous corrosion by careful selection of building ma-
terials.
Appendix
A1 - COMPOSITION OF THE ENDOGENOUS FLUID
Average composition of the endogenous fluid (boraci-
ferous zone)
(in g/kg fluid)
H20 951.010
COz 47.546
H~S 0.546
Gaseous residuals
(CH,, Hz, N2) 0.526
HsBOs 0.218
0.15~.
NH3
Average gas/steam ratio in NI of gas/kg of condensation
water =~ about 30.
Average composition of gas in the fluid, percent by A3 - COMPOSITION OF cONDENSATION WATER OF THE
volume ENDOGENOUS FLUID
CO2 94.120
H2S 1.594 Average analysis of sampled condensation water
Hz 2.298 of the endogenous fluid
CH4 1.206
N2 0.782
D o w n s t r e a m from U p s t r e a m from
condenser condenser
These average compositions vary somewhat from
one steam jet to another as well as from one geother- Gas c o n t e n t (cma/l) 50 - 110 40 - 100
mal field to the next. For instance, in the geothermal
field of Piancastagnaio in the <~Amiata ~ area the aver- Percentage composition
o/ gas:
age gas/steam ratio exceeds 120 N1/kg. Other chan-
ges are noticed over a period of some years: however, CO2 75 - 90 65 - 80
all the observed modifications keep within such limits 02 0.20 - 0.40 0.30 - 0.60
that they do not contribute to the general corrosion H2S 0.30 - 0.9 0.1 - 0.30
Nz, H=, CH, 9 - 22 18 - 30
processes, at least insofar as the listed components are
concerned. Percentage composition
o/ liquid:
The following compounds and elements are al-
ways found in a quantity measurable in ppm: HsBO3 0.3 - 1.00 0.3 - 1.00
NH3 T o t a l 0.15 - 0.25 0.15 - 0.P5
SiO.o, Na, K, Fe, and rare gases (He, Ne, A) S0¢---- 0 . 0 5 . 0.1 0.1 - 0.15
Cl traces traces
Some steam jets have a chlorine content, usually SiO2 traces - 0.002 traces . 0.002
lower than 20 ppm, but sometimes up to 100 p p m Fe~Os + A l ~ ) s t ra c e s traces
CaO 0.005 - 0.015 0.005 - 0.015
(AS). In other steam jets a liquid dragging can occur; MgO 0.0005 - 0.0015 0.0005 - 0.0015
it is usually slight but in some instances tens of cubic pH 6.5 - 7 6.5 - 7
meters per hour. In general, these steam jets are ex-
cluded from the system of steam lines (for instance, The condensation water of the endogenous fluid,
in the area of Travale the liquid delivery reaches about above all in the cooler basin, is opalescent owing to
100 mS/h). Where these draggings take place, the liq- dispersed sulfur in its colloidal phase. It has also a
uid contains the components mentioned in the Table reducing action on N / 1 0 0 solution of I:.
and their concentrations can considerably modify the During the summer periods of greater evaporation
etching characteristics of the fluid when the dragged and thus of less increase in the general balance of wat-
quantity of liquid is high. er, the saline content increases considerably.

Components that
are found in the Na + K+ Ca ++ Mg ++ Cl'- SO¢--- HBO~"- SiOa
dragged liquid
ppm min. 1-0 10 10 I 10 70 70 10
• max. 2500 250 300 8 800 1000 5500 450
J average 500 150 50 3 250 300 -- 100

Finally, the liquid always contains solid clay de- A4 - C O M P O S I T I O N OF COMPRESSOR ]~XHAUST GAS
bris in the form of dispersed powder and, very rarely,
stones or pebbles of a fairly big size. Composition of the gas exhausted from compres-
sors, after separation of humidity.
A2 - ENRICHMENT OF SOLUBLE COMPONENTS IN THE
FLUID CONDENSATE ( p e r c e n t by v o l u m e )
CO~ 77 - 93
An example of enrichment of soluble components H2S 0.5 - 2
in the condensate collected in a steam line by special Residual + air 6 - 21
drains is tabulated here, for well VC3 (geothermal field The residual is essentially constituted of H2 and
of Lago). Pressure about 7.0 arm, temperature 250°C. CH, in approximately the ratio in which these ele-
The well has no dragging. ments are found in the endogenous fluid. On an aver-

Endogenous Condensate Condensate Condensate

fluid at the Ist drain at the 2nd drain at the 3rd drain
(In parts per million)
HaBOa I 19 2750 5690 7850
C1-- 103 273 550 2020
Fe ÷ + present present abundant very abundant
pH -- 3.7 3 3

879
G e o t h e r m a l field No. w e l l s No. w e l l s c a r r y i n g Cl-- (in p p m )

from 1 from 6 from 11 from 16 ove r 20 Total Max. v a l u e

to 5 to 10 to 15 to 20 ppm

Lard eretlo 92 27 7 1 I 2 38 31
Castelnuovo 31 5 -- -- -- -- 5 3
Serrazzan o 19 7 2 I -- m 10 12
Sasso l0 6 m __ __ -- 6 3
Monterotondo 9 2 1 m 3 5
Lago 17 4 2 2 -- 2 10 100
Lagoni Rossi 10 3 m ~ 1 4 27

Total 188 54 12 4 I 5 76

age, the residual forms 25% of the residual + air Before installing the separator, abundant scales
mixture. were noticed on the pipeline wall thus reducing the
pipe cross section. The analysis of scales showed a
A5 - CHLORIDE DISTRIBUTION IN THE GEOTHERMAL SiO2 content of about 97%.
FIELD W E L L S
The table above includes only steam jets that form
part of the exploitation system in the boraciferous area. A7 - ANALYTICAL DATA CONCERNING CORROSION PRO-
The analytical values concern only the C1- contained C E S S E S ON I N S U F F I C I E N T L Y SEASONED BUILDING
in steam, without considering the C1- possibly carded WORKS IN THE HYDRAULIC C I R C U I T
in the dragged water.
Example of corrosion processes on insufficiently
A6 - T Y P I C A L PROCESSES IN STEAM IETS WIT H DRAG- seasoned building works in the hydraulic circuit of
GED WATERS the tunnel of Serrazzano plant (Table below).
Zuccantine steam jet (Lago geothermal field).
Pressure 8.5 arm, approximate temperature 170°C, de-
livery 50 t/h, dragged water 20 m3/h. A8 - ANALYTICAL DATA CONCERNING CORROSION PRO-
The steam jet is exploited by introducing it, af- C E S S E S ON SUITABLY SEASONED BUILDING WORKS
ter separating the liquid in a separator, in the high IN THE HYDRAULIC C I R C U I T

pressure manifold of Lago plant. The dragged water Example of corrosion processes on suitably sea-
contains the following impurities within the concen- soned building works in the hydraulic circuit of the
tration limits listed: tunnel of Larderello plant 3 (following page).
(ppm)
Ca + ÷ 13 - 14
SiO~ 278 - 447
el-- 400 - 500 A9 - T E S T S OF PROTECTIVE COATS IN HYDRAULIC CIR-
SO,---- 300 - 500
Na + 350 - 450 C U I T BUILDING WORKS
K+ 200 - 250
H3BO~ 700- 1400 Tests were made with painting cycles and coatings.

S a m p l e d r a w n from (percentages) Plastering Nonattacked

A n a l y t i c a l data Plastering corroded Bricks u n d e r the c o r r o d e d at plastering under
on the v a u l t corroded plastering the w a t e r l i n e the level of the
on the v a u l t level liquid

Silica + residual 67.34 77.88 25.72 77.51

Fe2Os + AlzO3 6.11 1.79 4.17 4.94
CaO 8.86 2.25 36.95 14.94
SO( 13.88 1.00 29.22 1.00
CO~. absent a bs e nt a bs e nt 1.2
H~BO3 present ~ ~ absent
p H at w e l l h e a d I - 1.5 2 1.5 - 2
pH in w a t e r s o l u t i o n 2.5 ~ 2.5 - 3 about 10

880
 Sample drawn from (percentages)
Analytical data Tunnel vault highly Tunnel vault less Wall under the
corroded areas corroded areas level of the liquid

Silica + residual 70.79 84.11 92.14

Fe2Os + A1203 0.90 0.54 1.12
CaO 18.44 7.80 1.12
SO, 44.83 8.30 traces
CCh traces present present
HaBOs ) ) traces
N.B. - The reinforced concrete under the vault samples was attacked, whereas the concrete under the wall sample was sound.

Paints
The bituminous and derivative products gave un-
favorable results owing to early aging in the surfaces
exposed to atmospheric agents and erosion in the sur-
faces affected by the water jets.
Better results were obtained with the same pro-
duets applied with mineral fiber reinforcements.
Other tests were carried out with epoxy and po-
lyC/nyl synthetic paints but with poor results. The
epoxy paints, though they have excellent adhesion and
good resistance to abrasion, appeared fragile and sub-
ject aging by the sun. The polyvinyl paints, on the con-
trary, did not show sufficient adhesion to cement. And
finally, paints made of inorganic substances (silicates)
appeared to be not suitable for this purpose since they
are easily removed by erosion processes.

Coatings
The products made with synthetic resins and ae-
rated silica gave unsatisfactory results for two rea-
sons: a different thermal expansion coefficient in com-
parison with concrete and poor adhesion, resulting in
separation and subsequent penetration of water to
complete the destructive action (Figure 21). Coatings
of polyester resins reinforced with glass fiber are being
tried.
In the most corroded areas, coatings made of
AISI 316 sheets anchored to the iron reinforcement of Ftc. 21. - - Example o] unsuitable protective coating lacking
adhesion to support and accompanying disintegration by
concrete were also tried. the water.

881