Control of Corrosion and Scaling

DRAFT
CONTROL OF CORROSION AND SCALING

IN GEOTHERMAL SYSTEMS
Project coordinated by BRGM (1. Ignatiadis)

BP 6009,45060 Orlans Cedex 2, France
Contract Nos:
JOU2-CT92-0108 and CIPD-CT93-0314
Final Report
Covering the period from
December 1st 1992 to July 31st, 1996
Research funded in part by

THE EUROPEAN COMMISSION
in the framework of the JOULE Programme
Subprogramme ADVANCED FUEL TECHNOLOGIES: EARTH SCIENCES
Date: November 20th. 1996

Control of corrosion and scaling in geothermal systems
PRESENTATION OF THE FINAL REPORT OF THE CONTRACTORS

by 1. IGNATlADlS (coordinator) and A. ABOU AKAR
(BRGMIDRIGGP)
JOULE II Project, contract Nos. JOU2-CT92-0108 and CIPD-CT93-0314

Title: Control of corrosion and scalUig in geothemal systems
FOREWORD
This final report presents the scientific contributions of al1 the partners in the Joule 2 programme,
contract Nos. JOU2-CT92-0108 and CIPD-CT93-0314 (entitled Control of corrosion and scaliig in
geothermal systems). The partners are BRGM, CEBELCOR, CPERI, CPR, and ICEHT, the
research groups that have been involved in the project from the beginning of the programme
(December 1, 1992), and BBPDICM, CAEL, CRIC, ICPE C-60 and ICVL, the groups from
Central and Eastern European countries who joined the project in 1994.
In this report, the research groups put together their work in a unique contribution as an integrated
work. The work done has been classified according to the 6 main themes of the project as defied by
the contractors and European Experts at Udine in July 1994 (corrosion prevention, corrosion
studies, scale formation and modelling, scale prevention, corrosion and scaling in diphasic flow
conditions and corrosion and scaling monitoring). This classification was proposed in order to
facilitate the presentation of this report. Nevertheless, abstract, introduction and conclusion specific
to each contractor were maintained just as it is. Let's specify that some articles can deal with two or
more themes.
This report was presented at the final meeting that takes place in Paris, France, on July 19, 1996, a
day after the 7th biannual meeting and repoa presentation which was held in the same venue as the
fmal meeting.The officia1 end of the programme is July 31, 1996. The outline adopted for this
report is as follows:
Abstract (related to each partner contribution)
A i of the research: context and general objectives, particular objectives of each group
The body of the report, made up of al1 the scientific contributions grouped by themes. This part
describe work performed, results and discussion
Preliminary conclusions (related to each partner contribution)
General conclusion and future developments
References
List of publications and patents related to the project (1993-1996)
Figures
The 10 partners of the programme are:
1. BRGM, Research Division, Department of Geotechnical Engineering and Minera1 Technology

(DRIGGP), Orleans, France
1. Ignatiadis, A. Abou Akar, M. Amalhay, C. Cotiche and H. Lesueur
2. CEBELCOR, Centre Belge de 1'Etude de la Corrosion, Bmssels, Belgium

A. Pourbaix and A. Singh
EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 1

3. Chemical Process Engineering Research Institute (CPERI), Thessaloniki, Greece

A. Karabelas, N. Andritsos, M. Kostoglou, S.V. Paras and N.A. Vlachos
4. Consorzio Pisa Ricerche, Centro TEA (CPR), Pisa, Italy

P. Andreussi, R. Corsi, M. Guidi, L. Marini, G. Mura, A. Paglianti, A. Pasqualeti,
E. Piciocchi, F. Prosperi, F. Sabatelli and E. Viviani.
5 Institute of Chemical Engineering and High Temperature Chemical Processes and the
Department of Chemical Engineering, University of Patras, Greece
P. G. Koutsoukos, N.G. Harmandas and P. Klepetsanis.
6. Bioactive and Biocompatible Polymers Department of the Petm-Poni Institute of

Macromolecular Chemistry (BBPDICM), Iasi, Romania
A. Carpov, G.C. Chitanu, 1. L. Zaharia and A. G. Anghelescu-Dogam.
7. Computer Aided Electrochemistry Laboratory (CAEL) of the "Politechnica" University of

Bucharest, Romania
V. Cotarta, G.H. Juncu, B. Petrescu, F. Stan and F.M.G. Tomescu.
8. Central Research Institute for Chemistry (CRIC), Budapest, Hungary

E. Kalman, 1. Bako, 1. Felhosi, F. H. Karman, 1. Lukoviks, G. Palinkas, G. Patzay, G. Stahl
and J. Telegdi.
9. Electrochemical Technologies and Active Anticorrosive Protection Laboratory of the Research

and Design Institute for Electrical Engineering (ICPE C-60), Bucharest, Romania
1. Lingvay, D. Badea, M. Chefneux, R. Cindea, C. Ionescu, C. Pacala, P. Paraian, C. Rata,
V. Stanciu and F. Stoian.
10. Institute of Chemistry (ICVL), Vilnius, Lithuania.

E. Juzeliunas, M. Samuleviciene, K. Leinartas, D. Vibalyte, A. Sidavicius, P. Miecinskas
and V. Noskovas.
2 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final report

1. ABSTRACT
The BRGM contribution to the European Union CO-financedresearch programme aims to eliminate
the problerns due to corrosion and scaling in low enthalpy geothermal systems in order to ensure
their financial profitability. It focuses on solving real problems encountered during exploitation of
geothermal resources. In this perspective the fields studied are the low enthalpy Dogger aquifer of
the Paris basin. The results can be summarized as follow:
In order to monitor the corrosion rate of carbon steel (used for pipes and casings) and to maintain
the effectiveness of a treatment by a corrosion inhibitor in a given geothermal plant, several
different methods must be used, each having its own limitations, its advantages and disadvantages.
The work done has contributed to the adaptation and the use of three type of methods for
geothermai applications.
The influence of some exploitation conditions on corrosion and scaliig in geothermal wells is
reported. The corrosivity of a geothermal fluid was assessed with respect to various materials at two
flowrates, in the presence and absence of corrosion inhibitor (quatemary ammonium salt).
The behaviour of a carbon steel in the absence and in the presence of various corrosion inhibitors in
partially reconstituted, actual and modified geothermal water is examined in order to optimize their
use in low enthalpy geothermal systems. The influence of some physico-chemicai parameters known
to be determinant in the process of carbon steel corrosion and its inhibition such as s a l i t y ,
hydrogen sulfide concentration and geothermal fluid flowrate in the casings have also been studied
in a naturai geothermal water. The determination of the influence of these physico-chemical
parameters on the effectiveness of an inhibitor, enable us to predict the order of magnitude of the
concentration necessary of inhibitor for an optimum effectiveness as a function of the composition of
the fluid of each well.
Another main part of the work performed is iron sulfide formation and inhibition studies.
Experiments were done in order to better understand its precipitation kinetics. Results of analyses
done at the end of the kinetics experiments and those of the fluids at the production wellhead were
used to identify which iron sulfide controls the solubility of iron and sulfide in the geothermal
environment. Machawite is this iron sulfide, despite the presence of other ones in the deposits.
Electrochemical techniques were used to monitor the behavior of carbon steel during the
crystallization of corrosion deposits in the presence of corrosion inhibitors. By combining the results
with mineralogical analyses of the scale, we have shown that the crystallization of amorphous iron
sulfide into mackinawite is accompanied by an increase in the corrosion rate due to the transfer of
cathodic sites from the surface of the metal to that of the scale.
A comparative study of the effectiveness of various surfactants in inhibiting iron sulfide precipitation
in a natural geothermal environment have been realized. Its objective is to better understand the
mechanisms controllmg the action of these inhibitors and compare their effectiveness to those of
other molecules or formulae which are synthesized and provided by the BBPDICM. In general, al1
the additives tested in this experimental investigation did not prove to have any scaling inhibition
effectiveness with respect to iron sulfide formation.
The behaviour of some non metallic materials in actual and treated geothermal environment have
been characterized. This study shows that knowledge of the behaviour of nonmetallic materiais in
the field of low enthalpy geothermal energy is limited. Scientific results are rare as scientists are
currently concentrating their efforts on the battle against steel casing corrosion. After briefly
describing the context in which these materials are used, this study lits the principal characteristics
of the nonmetallic materials which can be used in geothermal activities and gives the main results
gathered from the Dogger exploitation in the Paris Basin.
On the topic of modelliig corrosion and scalmg phenomena on the walls of steel casing in
geothermal wells a digital mode1 that enables the simulation of these phenomena is proposed.

Considering the complexity of the real phenomena, certain simplivig hypotheses were included in
the model. The amount of mackinawite (the main scale constituant) precipitated is calculated using
the solubility product, Ks or according kinetic considerations. The model also (i) simulates the
precipitation of five other mineral species, (ii) offers the possibility of adjusting the flowrate of the
geothermal water in the well, and (iii) takes into account the presence of a well-bottom treatment
tube (WBTT) when calculating the head loss.
The environmental impact of a perforation in the casing of a well exploiting the water of the Dogger
was studied. When localiied, corrosion can lead to perforations in the casing, thereby increasing the
risk of contamination by geothermal fluids of freshwater aquifers (Albian, Challc) traversed by the
wells. After examination of the various water-migration possibilities with one or two casing
perforations in a production or injection well, the different detection methods for perforations are
discussed in terms of their limitations and accuracy. In al1 case, a logging tool is necessary to
confirm the existence of a perforation and to locate its depth.
The work performed by the CEBELCOR refers to the preparation of potential-pH equilibrium
diagrams, to the effects of oxidants and to the study of corrosion processes and to electrochemical
systems for monitoring corrosion.
The general aim of the work performed by the CPERI is to contribute to a better understandiig of
the complicated phenomena of scale formation and corrosion in geothermal systems. The work deals
specifically with three different areas: the formation and inhibition of deposits, stabiiity of colloidal
systems and two-phase flow characteristics encountered in geothermal installations. The data on iron
(II) sulfide scale formation show that appreciable mass of relatively strongly adhering amorphous
deposits develops only within a narrow pH range. For al1 additives tested, a small inhibition action
was found for the Fe,S system, while for the CaC03 system at intermediate supersaturation ratios
almost complete scale inhibition was obtained. New data are obtained in the so called
"st~atifiedlatomisation"two-phase flow regirne are helpful for the development of generalized
correlations of engineering interest. The latter are aimed at predicting gas phase velocity
distribution, shear stress at the liquidlwall interface, and pressure &op. As regards stability and
coagulation of colloidal dispersions, a new computer code was developed for predicting phenomena
occurring simultaneously along the flow path of a supersaturated geothermal fluid, i.e. particle
nucleation, growth and coagulation as well as particle deposition and wall crystallization. The
system PbS-water (typical of geothermal fluids) was used for case study. Other important
phenomena, relating to colloidal particle coagulation, were also theoretically studied, such as the
effects of particle surface roughness and of its dynamics on repulsive forces resisting coagulation.
The development of a process for eliminating chlorides by washing geothermal s t e m and the
identification of the interactions between diphasic flow conditions and corrosion and scaling are the
main objectives of CPR within the Work Programme.
With respect to these objectives, the activities described in the present report allowed the following
major results to be obtained:
1. Design of a full-scale sbuctured column for s t e m washing. The column will be constructed and
tested in the near future by ENEL at Larderello Geothermal Field.
2. Development of GEA (Geothermal Equilibria Assessment) code. This code allows the computation
of vapour-liquid equilibria in geothennal equipment and represents a significant extension and
completion of the Drop Code developed in the previous programme (JOUG-0005-C).
3. Analysis of field data on the efficiency of chloride abatement in existing facilities. This activiiy has
been canied out in cooperation with ENEL.

4. Development of a dry process for chloride abatement. This process should allow a significant
increase of power production in geothermal plants.
5. Analysis of diphasic flow conditions and in particular, of annular flow in geothermal wells. This
analysis lead to the development of a vertical upward flow version of the HORF (Horizontal Flow)
Code, developed in the previous programme. This code, named VEA (Vertical Annular), has been
used to test the feasibility of s t e m washing operations conducted directly in the well.
The mechanism of iron (II) sulfide precipitation was studied by ICEMTCP using spontaneous
precipitation experiments at temperature, pH and salinity conditions simulating scaling conditions in
geothermal wells in which this type of deposits are found. Spontaneous precipitation occurred only
in solutions supersaturated with respect to amorphous FeS which was the initially forming phase in
acidic solutions (pH 5.5-6.5). In neutral or slightly alkaline solutions mackinawite was formed. The
effect of salinity at 80C was found to iduence both the threshold limit for precipitation and the
nature of the precipitating phase. In high salinity aqueous media in the presence of oxidizing ions
(Cl-, NO3-) the formation of pyrite was favoured. In al1 cases the dependence of the rates of iron
sulfides formation on the relative solution supersaturation yielded a high apparent order (n = 1-9)
suggesting a surface controlled process. The experiments of iron sulfide precipitation done at
geothermal wells showed a similar mechanism. The additives tested faiied to show satisfactory
inhibition with respect to iron sulfide formation except for ATP 6.2 which showed significant
inhibition of the rates of crystallization in natural geothermal brines. The water-soluble additives
tested (commercial and BBPDICM preparations) with the exception of Nomst 491@, showed
however inhibition with respect to calcium carbonate scale formation which for concentrations
ranging from 0.05-10 ppm was between 15-100%. Both AC and DC electrochemical evaluation of
commercial products and compounds prepared by BBPDICM showed that only the former products
Solamine 12g8, Nomst 4918 and Aquaprox MDC 1 3 0 0 ~gave significant reduction of the
corrosion rates of carbon steel in NaCl containing media.
The results conceming the synthesis of maleic copolymers and the derivatives and the activity of
these products as scale and101 corrosion inhibitors investigated by BRGM, ICEIHT, CPERI and
ICPE C-60 are presented by BBPDICM. It was synthesized several maleic anhydride binary or
temary copolymers with methyl methacrylate or N-vinylpyrrolidone as well as salts, monoesters,
monoamides and derivatives containing heterocyclic or aromatic amines. Some maleic copolymers,
especially the ones containing N-vinylpyrrolidone as comonomer exhibited a good ability to inhibit
the calcium carbonate precipitation or even the iron sulfide precipitation. Some of them reduce also
the corrosion of mild steel in some cases but in this regard the results are not yet conclusive. It
could be observed a certain relationship between chemical structure of maleic copolymers and their
effect as scalelcorrosion inhibitors. Some maleic copolymers or their derivatives exhibited at the
same time good properties as scale and corrosion inhibitors. The "ortho effect" stated for
anticorrosion activity of aromatic amines was identified also by the maleic copolymer derivatives of
these products.
The first aim of the work done by the CAEL was to mode1 the corrosion processes in large volumes
(reservoirs) using multigrid and finite element methods, in order to simulate the distribution of
current and potential field, for an optimum position of anode in cathodic protection. The important
aspect are: (i) the influence of the distance between the liquid superior level and the electrode on the
potential distribution and wall current values, (ii) the laboratory study conceming the cathodic
protection of metals (alloys) in geothermal water in the absence of extemal current sources, and (iii)
the corrosion monitoring system based on multi-electrode. The second aim of the work was to
determine the influence of ions (Cl-, HS-), pH, and inhibitors on the corrosion process: a very

contradictory behaviour of the steel in contact with brine, which contain H2S and CO2 was
observed. The attack was not uniform corrosion in an electrochemical sense, although it may have
been uniform on a microscopic scale. On the other site an oscillatory domain is identified during Fe
anodic polarisation, which is strongly influenced by some critical values of the parameters
mentionned above. The last aim of the work is to model and simulate the periodic oscillations, that
occur at the anodic polarisation of Fe electrodes in geothermal water with high Cl- content. Another
aspect of this aim is the using of the integral method to calculate the Tafel kinetic corrosion
parameters @,, b,) and corrosion current (I,,,), in the geothermal water.
New simulation algorithm and computer program was developed by CRIC for the equilibrium scale
formation of calcite:
- in water at any desired temperature, pressure. The simulation method based on the Pitzer activity
coefficient calculation.
- in multicomponent (13 ionic species) water at any desired temperature, pressure. The simulation
method based on the Pitzer activity coefficient calculation.
New simulation algorithm and computer program was developed for the equilibrium determination
of the bubble point using gas separation data in thermal water wells at any desired temperature,
pressure. The simulation method is based on the Kocsis method. Were developed an equilibrium
simulation algorithm and a computer program for the determination of the partial pressures of the
dissolved gases (CO2, CH4, and N2 ) and, using detemined CO2 partial pressures, for the
determination of the CaC03 scale formation in Na-K-Mg-Ca-H-Ba-Sr-Cl-Br-S04-OH-HC03-CO3-
CO2-H20 system along the well between the bubble point and the well head. New small scale test
reactor was developed for the investigation of calcite scaliig in water at 20-600C and 1-8 bar. New
pilot plant device was developed to investigate the scaliig processes in various model solutions at
20-800C and 1-4 bar.
The correlation between the molecular structure and corrosion/scaling inhibitor efficiency was
investigated. Chemicals used as corrosion inhibitor were prepared in our laboratory. Based on the
ability of derivatives of natural amino acids to inhibit corrosion and presumed their scale inhibiting
properties experiments were designed to evaluate their effects on corrosion of mild steel and on
scale formation. Various N-acylamino acids were synthetized and their inhibiting capacity was
tested by using potentiostatic method. The inhibiting efficiencies varied between 36 and 61%. The
electronic properties obtained by using the AMI quantum chemical approach, were correlated with
experimental efficiencies and the best multiple correlation coefficient obtained was equal to 0.80.
Due to these prelimiiary results, N-acylamino acids may form charge transfer complexes with the
iron atoms on the metal surface. A stochastic mathematical model was developed for a statistical
description of corrosion process of metals and for inhibition of corrosion by an adsorption
mechanism. Based on the model, the dissolution of metals and the efficiency of inhibitors can be
studied by computer simulation.
The corrosion process and scaling from the geothermal systems of Romania were studied by ICPE-
C60 theoretically and experimentally. Also, it was conceived, designed and tested an equipment with
its specific elements destined for active anticorrosive protection of the extemal sides of the metallic
installations in direct contact with the soi1 as so as of the intemal sides of some bulky equipments in
direct contact with the geothermal fluid.
To choose the adequate inhibitors and their optimal doses (from technical and economical point of
view), the kinetic parameters of the corrosion reactions to the interfaces carbon steel R37lgeothermal
fluid, were detemined from 14 wells. These corrosion rates are influenced by the ionic content of
geothennal fluids, especially of Cl-, S042- and S2-. Maleic polyelectrolytes having different structures
were studied and the conclusion is that they can be utilized as inhibitors with cumulated effect

(corrosion and scaling). The result of these determinations indicates that many studied substances had
a pronounced effect of inhibition. These depending of the lateral groups from the structure of the
polyelectrolytes, operating through the altering of the transfer coefficient a (implicitly the Tafel
slope), or by braking the anodic and101 cathodic reaction of the charge transfer.
It was also studied and conceived an automated system of dosing and injection of the inhibitors
having an optimal concentration (technico-economical) for the geothermal welis. For this purpose, it
was conceived and realized a multifunctional transducer which collects (in situ) fiom the geothermal
water the parameters; corrosion, scale and temperature. The experimental results of this device are
detailed, described for geothermal waters having Ca2+ and HC03-.
The results of iron and carbon steel corrosion investigations in geothermal fluids Vidmantai 1 and
Vidmantai 2 (Lithuania) are summarized by the ICVL. The fluid content was determined by means
of atomic-absorption spectroscopy, ion chromatography and other analytical methods. Corrosion
rates were estirnated taking volkammetric measurements. Cathodic and anodic Tafel slopes, the
polarisation resistance and the corrosion rate were determined in the fluid as functions of electrode
rotation, the immersion t h e , temperature and the amount of chloride. This has been done in
naturally aerated solutions as well as in the N2 and CO2 atmosphere. Formation of oxide-layer on
carbon steel during the corrosion process have been studied. X-ray photoelectron spectroscopy and
surface etching with ionized argon were used for this purpose. The influence of oxide layer on
kinetics of corrosion process was discussed. The results of iron corrosion investigations by
electrochemical quartz crystal micro-gravimetry (EQCM) are also reported. The EQCM data were
analysed in terms of oxide layer formation, precipitation of scarcely soluble compounds on the
electrode, and iron corrosive dissolution. The investigations in synthesised solutions were conducted
as well.

TABLE OF CONTENTS
1. Introduction .Aim of the research .....................................................
2 . Work performed. results and discussion ..............................................

2.1. Corrosion prevention .......................................................................
2.2. Corrosion studies ............................................................................
2.3. Scale formation and modelling ............................................................
2.4. Scale prevention .............................................................................
2.5. Corrosion and scalig in diphasic flow conditions ....................................
2.6. Corrosion and scaiiig monitoring ........................................................
3. Preliminary conclusions ..................................................................
4 . General conclusion and future objectives .............................................
5 . References ..................................................................................
6 . List of publications related to the project (1993-1996) .............................
7 . Annexes: (figures) .........................................................................
8 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 .final report

1. INTRODUCTION - AIM OF THE RESEARCH
The aim of the programme is to resolve the problems caused by corrosion and scaliig in the
exploitation of low and high enthalpy geothermal systems. The increased costs resulting from these
problems decrease the profitability of the projects and, in certain cases, can be inimical to the
development of the uses of geothemal energy. The geothermal plants most concerned are those
currently operating in the Paris Basin in France, at Larderello in Italy, in Greece, and those in the
planning stage in these and other countries. The mechanisms of corrosion and the formation of scale
encountered are similar, even when the geothermal fluids have different physico-chemical
characteristics. Very few European research centres are currently working on these highly specific
and complex aspects of corrosion in deoxygenated media in France, Italy and Greece. Since the
energetic (or economic) value of the resource is low, it is necessary to develop processes that are
both very efficient and inexpensive.
The immediate objectives of the programme are to detemine the conditions under which corrosion
takes place and which lead to the formation and growth of scale (iron sulfide, calcium carbonate,
silica, lead sulfide), and to develop predictive models. This will lead to the design of processes for
industrial application to control corrosion and scaliig, using corrosion and crystal growth inhibitors,
vapour-cleaning systems and treatment of condensates before injection. The work programme is
carried out by the following groups:
Bureau de Recherches Gologiques et Minires, Direction de la Recherche, Research Division,
Dpartement Gomatriaux et Goprocds, Department of Geotechnical Engineering and
Minera1 Technology, (BRGM, Dr. 1. Ignatiadis, Coordinator) Orleans, France;
Centre Belge de 1'Etude de la Corrosion (CEBELCOR, Dr. Pourbaix) Bmsseis, Belgium;
Chemical Process Engineering Research Institute (CPERI, Prof. A. Karabelas) Thessaloniki,
Greece;
Consorzio Pisa Ricerche, Centro TEA (CPR, Prof. P. Andreussi) Pisa, Italy, and
Institute of Chemical Engineering and High Temperature Chemical Processes (ICEIHTCP, Prof.
P. Koutsoukos) Patras, Greece.
The possibilities for developing the use of geothermal energy in other European countries (Hungary,
Romania, Lithuania, etc.) led us to propose an extension of the programme to allow the association
of new research partners. This extention was prompted by the European Union programme for
"Cooperation in Science and Technology with Central and Eastern European Countries, 1993". The
additional work programme is carried out by the following groups:
Bioactive and Biocompatible Polymers Department of the Petni-Poni Institute of Macro-
molecular Chemistry (BBPDICM, Prof. A. Carpov), Iasi, Romnia,
Computer Aided Electrochemistry Laboratory (CAEL, Dr. V. Cotarta) of the "Politechnica"
University of Bucharest, Romania,
Central Research Institute for Chemistry (CRIC, Prof. E. Kalrnan), Budapest, Hungary,
Electrochemical Technologies and Active Anticorrosive Protection Laboratory of the Research
and Design Institute for Electrical Engineering (ICPE C-60, Dr. 1. Lingvay), Bucharest,
Romania,
Institute of Chemistry (ICVL, Dr. E. Juzeliunas), Vilnius, Lithuania.
The aims and deliverables for the laboratories of the European Union are defined in the initial work
programme. The general objectives, particular objectives and deliverables for laboratories in Central
and Eastern European countries are defined in the additional and specific work programme.

BRGM
The BRGM contribution to the European Cornmunity co-financed research programme Joule
contract noJOU2-CT92-0108 aims to eliminate the problems due to corrosion and scaling in the
exploitation of low enthalpy geothermal systems in order to ensure their financial profitability. It
focuses on solving real problems encountered during exploitation of geothermal resources. In this
perspective the fields studied are the low enthalpy Dogger aquifer of the Paris basin (41 doublets in
operation representing a thermal power of more than 350 MW). The research programme aims on
the one hand, on the theoretical level, to develop understanding of the reaction mechanisms which
control corrosion (of carbon steel) and scaling, and on the other hand, on the technological level, it
aims to improve the solutions currently employed and to develop new, less costly and101 more
reliable solutions. This contribution deals with the following topics:
(i) development of the metrology associated with the monitoring of corrosion and scalig,
(ii) selection of the most efficient products for inhibiting corrosion or crystal growth with a view to
their optimal use withii current and future operations,
(iii)establishment of the kinetics of the formation and growth of the scale most frequently
encountered, with the development of appropriate numerical simulation codes. The calculation
code will enable modelling of corrosion-scaling phenomena in low enthalpy geothermal systems,
(iv) establishment of a general methodology for detecting and assessing perforations in casings of
wells exploiting geothermal waters,
(v) study of corrosion and scaling phenomena in diphasic flow conditions.
CEBELCOR
The feeling of CEBELCOR is that his previous work on the E-pH diagrams has provided a much
stronger confidence in the data and in the resulting diagrams, and an detailed consciousness on what
is still uncertain (stoichiometric coefficients, data for some iron sulfides, metastability, aging). E-pH
equilibrium diagrams are a solid support to the interpretation of field data and of lab experiments.
The limitations of these diagrams due to kinetic aspects have been clarified and appear as marginal:
field observations, lab experiments and measurements in other disciplines (oil and gas, marine)
show that most of the reactions of these systems S-H20 and Fe-S-H20 are rather reversible, at least
much more than generally considered before. The experiments conducted in double-cells clearly
indicate the activity of local corrosion cells. These cells may become interesting sensors for the
study or detection of corrosion in H2S media. The results of the lab tests have shown the importance
of catalysis of electrochemical reactions that have a l i i t e d driving force. This has opened a field
for research that is not yet completed. The work of Cebelcor is concemed with.
(i) influence of oxidants and corrosion process in both S and Cl environments (also localised
corrosion and corrosion under deposits),
(ii) E p H diagrams for Fe-S-H20 systems,
(iii) development of electrochemical systems for the determination of corrosion modes and rates.
CPEIU
The formation of hard and tenacious scales in both the surface and the subsurface equipment, as
well as the corrosion of metallic surfaces have inevitably severe adverse consequences on the
operation and the economics of a geothennal installation. The general objectives of the present
research programme are, first, to expand our knowledge of the mechanisms which control scaling
and corrosion phenomena and, second, to improve the currently employed techniques or to develop
new ones in an effort to alleviate these problems. The particular objectives of thii part of the
project, as outlined in the original work programme, are:
(i) to elucidate the mechanisms of sulfide scale formation (notably of iron sulfide),
(ii) to assess the efficiency of organic additives to inhibit scale deposition.
10 EEC-DG Xll-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

(iii) to study theoretically the coagulation process and use the results in modelling efforts. More
precisely, to realise a computer code capable of predicting the evolution along the pipe of the
colloidal particle distribution and of deposit formation,
(iv) to study the local characteristics of two-phase flows affecting corrosion and scaling phenomena,
CPR
The main objective of the present programme is the analysis and solution of corrosion problems
created by the presence of hydrochloric acid in superheated geothermal steam. Part of the
programme represents the continuation of a previous EU funded programme (JOUG-0005-C). In
particular, this is the case for the following items:
(i) design of a structured packing column for steam washing,
(ii) development of a computer code for the assessment of vapour-liquid equilibrium in geothennal
systems,
(iii) analysis of field data relative to chloride abatement.
New objectives of the present programme are the following:
(iv) development of a dry process for steam washiig,
(v) analysis of diphasic flow conditions in geothermal wells and of their relevance with respect to
corrosion problems.
Not al1 these objectives were stated in details in the original work programme, and also, it was
expected to perfonn an experimental activity with regard to point (v) which has not been possible
due to the larger priorities and more consistent fund allocation received by the other parts of the
programme. Major deliverables completed in the course of the project can be grouped as follows:
(i) wet processes for HCl abatement,
(ii) dry Process for HC1 abatement,
(iii) computation of vapour-liquid equilibria in geothermal equipment.
ICEIHTCP
The problems of corrosion and scaling, often coupled, constitute a serious impediment in the
utiliiation of geothermal energy which is based i n handliig geothermal fluids of various chemical
compositions. The process of scale formation is a heterogeneous process including various steps as
development of supersaturation, diffusion of the growth units of the salts forming through the bulk
fluid onto the heterogeneous surface (e.g. pipe walls or valves or suspended particles), followed by
surface diffusion to the active sites, dehydration and finally integration into the growing crystal. The
slowest of the above stages is the rate determinmg step. It is therefore necessary, for each salt
forming, to understand the mechanism of formation by studying the conditions (e.g. temperature,
ionic strength, supersaturation etc.) and measuring the kinetics of precipitation. Analysis of the
kinetics results leads to conclusions regardiig the mechanism of scale formation and to suggestions
as to how to reduce these phenomena. Phase characterization is another important issue since a
number of iron sulfides are known and may be formed in geothermal fluids. Scale formation is very
often related with corrosion of metallic parts which are in contact with the aqueous media.
Corrosion is another severe problem which seems to affect seriously the installations of geothennal
energy utilization. Carbon steel is a material commonly used in the geothermal installations because
it is inexpensive and of interest for its mechanical characteristics. Unfortunately, carbon steel is
sensitive to corrosion in the geothermal environment. Geothermal waters are characterized by the
relatively high fluid temperature and salinity, which in addition to the presence of H2S and CO2
compose a very corrosive aqueous environment. The objectives of the ICEIHT group in the frame
of this project are the following:
(i) construction and development of a computer based automatic titrator system for the
investigation of iron sulfide formation in aqueous systems at 25"C,

(ii) investigation of spontaneous iron sulfide scale formation (and particle size distribution) in
supersa-turated aqueous solutions at 25C and 80C under sustained (only for 25C) and
variable solution supersaturation. The effect of pH, ionic strength and presence of foreign ions
will be studied,
(i) study of the inhibiting properties of various organic additives on iron sulfide scale formation at
80C in high salinity supersaturated solutions in the laboratory and in real geothermal fluid,
(iv) inhibition of calcium carbonate scale formation by water soluble polymers prepared by
BBPDICM and by commercially available corrosion inhibitors;
(v) preparation of synthetic pyrite crystals from amorphous FeS suspensions and study of
amorphous FeS particle transformation to pyrite,
(vi) electrochemical investigations of the corrosion of carbon steel in Cl- and HS- containing media,
and of the anti-corrosive properties of the additives prepared by BBPDICM and already used
commercial corrosion inhibitors in Cl- containing media.
BBPDICM
The BBPDICM contribution was the obtaining of new maleic copolymers and maleic copolymer
derivatives, the objectives of the research programme were:
(i) to develop new types of scale inhibitors for geothermal waters, eventually corrosion inhibitors.
(ii) to study the correlation between the chemical structure, composition and physico-chemical
properties of polyelectrolytes and their inhibiting effect on the precipitation of carbonates or
other insoluble salts that produce scale in geothermal systems.
CAEL
The anti-corrosion protection of large volume tanks where electrolyte solutions are stored still
constitutes an important element inluencing the cost of such units. The anti-corrosion can be
realised by applying different methods. The inner wall surface can be diversely coated, corrosion
inhibitors can be added to the electrolyte itself, and fmally, electrochemical protection can be used:
cathodic protection without or with extemal current source, and anodic protection. The high Cl'
contents in the chemical composition of geothermal water and its temperature drastically l i t the
efficiency of protection methods. The cathodic protection with extemal current source supposes
solving a field problem in an electrically conductive medium, described by Laplace's equation. The
cathodic protection of steel structures using dummy anodes with no extemal current source is a
common corrosion protection procedure used in ship buildimg. The aims of this study was:
(i) to model the corrosion processes in large volumes using multigrid and fuiite element methods,
in order to simulate the distribution of current and potential field, for an optimum position of
anode in cathodic protection. The corrosion monitoring system was based on multi-electrode.
(ii) to determine the iduence of Cl-, HS-, pH and inhibitors on the corrosion process (corrosion
rate, uniform corrosion, pitting corrosion, formation, porosity and breakdown of scale).
(iii) to model and simule the periodic oscillations, that occur at the anodic polarisation of Fe
electrodes in geothermal water with high Cl- content and to calculate the kinetic corrosion
parameters ba, bc and Icor, in the geothermal water.
CRIC
The aim of the programme is to resolve the problems caused by corrosion and scaling in the
exploitation of low and high enthalpy geothermal systems. In low temperature systems, often
referred to as "hydrothermal" or "direct use", scaling apparently plays a less important role. It is
well known that Hungary has the second biggest resource in the world of low enthalpy hot water
and this type of energy should be used in the near future to a higher degree. The research

programme which aimed the understanding of the corrosion and scale controlling mechanisms in
geothermal field was:
(i) to develop mathematical models for:
- inhibition of mineral scaling and metal corrosion in geothermal wells;
- scaling mode1 which includes equilibrium thermodynamic relationships, temperature,
pressure, water composition;
- stochastic description of metal corrosion including adsorption kinetics of inhibitor molecules;
(ii) to establish of empirical relationships between kinetic and thermodynamical parameters of the
processes based on laboratory experiments;
(iii) to develope new type of anti scale and anti corrosion agents for use in geothermal systems
based on systematic studies of correlations between the reactivity and structure for newly
synthetized molecules;
ICPE-CO0
The purpose of this programme is both the theoretical study of the corrosion mechanism and of scale
forming in geothermal systems with various physical and chemical characteristics and to test
technical solutions for scales decreasing and elmination.
The geothermal systems in exploitation in Romania consists principally of: (i) drilling well -at
different depths- catching source, (ii) vessel, degassing tank, usually positioned next to the well, (iii)
transport pipes to user, (iv) users equipments, principally heat exchangers, (v) pipes for the
transport of the exhausted geothermal water from user to soi1 reinsertion well, (vi) buffer vessel for
exhausted geothermal water, and (vii) reinsertion well. The principal areas affected by
electrochemical corrosion are the wells (outsidelinside), the transport pipes (outsidelinside), the
inside of regulation and flowrate measurement units, the degassing vessel inside, the heat
exchanger, etc...Conceming the scales forming the most exposed areas are: the head of catchiig
well (to 100-150 m depth), the transport pipes and the heat exchangers. The objectives are:
(i) to design, build and test a prototype for active cathodic protection with potentiostatic control
for exterior corrosion metallground) of collecting/transport pipes,
(ii) to determinate the kinetic parameters of corrosion in geothermal systems exploited in Romania,
and elsewhere if requested;
(iii) to develop corrosion inhibitor (possibly includiig crystal growth properties, accordingly to the
proposa1 of Pr. A. Carpov from BBPDICM), the effectiveness of the inhibitor will be
d e t e ~ i n e dby ICPE-C6O or by other partners.
ICVL
The task of ICVL group in the frame of the programme was the corrosion investigations of iron and
carbon steel in geothermal fluid of the West Lithuania aquifers. The fluids are from Cambrian
aquifer and has temperature of about 800C. The next task of the work was an investigation of oxide-
layer formation on carbon steel and on iron taking place during the corrosion process in the
geothermal environment. X-ray photoelectron spectroscopy (XPS) simultaneously with the etchimg
of samples surfaces with ionised argon as well as electrochemical quartz crystal microgravimetry
(EQCM) were used for this purpose. The attention was focused on:
(i) Tafel slopes, polarization resistance and corrosion rates of iron and carbon steel in the
geothermal environment of Vidmantai 1 and Vidmantai 2,
(ii) influence of the liquid flow rate on the parameters mentioned above by means of a rotating disc
electrode,
(iii) influence on the corrosion rate of temperature, exposure time, chloride, CO2 and air
atmosphere,
(iv) influence of the above factors on interphase layer formation.

Control of corrosion and scaling in geothermal sysrems
2. WORK PERFORMED, RESULTS AND DISCUSSION
2.1. Corrosion prevention
BRGM
The behaviour of a carbon steel in the absence and in the presence of various corrosion inhibitors in
partially reconstituted, actual and modified geothermal water is examineci in order to optimize their
use in low enthalpy geothermal systems. The influence of some physico-chemical parameters known
to be determinant in the process of carbon steel corrosion and its inhibition such as salinity,
hydrogen sulfide concentration and geothermal fluid flowrate in the casings have also been studied
in a natural geothermal water. The determination of the influence of these physico-chemical
parameters on the effectiveness of an inhibitor, enable us to predict the order of magnitude of the
concentration necessary of inhibitor for an optimum effectiveness as a function of the composition of
the fluid of each well. It would thus be possible to ensure that the inhibitor is sufficiently effective at
economically supportable concentrations. Finally, we evaluate the adsorption-desorption kinetics of
inhibitors in order to see whether or not its action is immediate or not and to determine how long
the inhibitor remains effective after treaiment has ceased.
In reconstituted geothermai water, the inhibitors were tested using various stationary and
transitory electrochemical techniques and a precise experimental protocol (Amalhay, 1994; Arfaoui,
1995; Amalhay and Ignatiadis, 1994b; Ignatiadis and Amalhay, 1995). By combining and
comparing results gathered using theses techniques, we were able to determine the mechanisms
goveming the action of the inhibitors and determine their effectiveness. It was clear that scale plays
a preponderant role in the evolution of the corrosion.
In actuai geothermal water, a fwst comparative study (long-term) of the carbon steel corrosion
rate in untreated and treated geothermal waters using coupons have been realized (Ignatiadis et al.,
1995). This study allows us to verify and extrapolate the results obtained during short- and medium-
term periods of immersion by electrochemical tests and to provide more precise information on
actual carbon steel behaviour and on how inhibitors work. Gravimetric tests carried out on
corrosion coupons immersed 65 days in an untreated geothermal fluid from Melun 1'Almont enabled
us to estimate the average corrosion rate to be 1.21 mmlyear. The corrosion is not absolutely
uniform and is very great because of the presence of scale on coupons and of the absence of
treatment with inhibitor. Gravimetric tests carried out concurrently at the Villeneuve La Garenne
(non treated fluid) and la Courneuve Nord (treated fluid) sites enabled us to show that inhibitors act
by slowing down crystal growth. The corrosion rate was more than 10 times lower in a treated fluid
than in a non treated fluid. These in situ tests enabled us to validate results gathered using
electrochemical methods concerning not only the evolution of the morphology of the scale as a
function of time and of the injection of corrosion inhibitor, but also the effectiveness of the
inhibitor. A second comparative study of the effectiveness of various additives in inhibiting carbon
steel corrosion in a natural geothermal water by using rapid electrochemical tests have been realized
(Amalhay 1994; Amalhay et al., 1994d; Cotiche 1994; Amalhay and Ignatiadis, 1995a, 1995~).In
order to rapidly determine the mode of action and the effectiveness of some corrosion inhibitors in
reducing corrosion rate, we developped and carried out a series of rapid and successive tests using
stationary and transitory electrochemical techniques. These techniques consist in electrochemical
monitoring, for short periods of around three and a half hours, of the response of carbon steel
electrodes. The electrodes are immersed from the start in a natural geothermal water treated with 10
mg/l of each inhibitor. these compounds cannot be recommended for use as scale formation
inhibitors. Several compounds are recommended for use as corrosion inhibitor at low concentrations
(economically feasible). In the natural fluid, scale plays a preponderant role in the evolution of the

corrosion, where the study of the cathodic slopes of the Tafel lines, shows that the cathodic reaction
probably occurs entirely on the scale and controls the kinetics of the corrosion reactions. Without
treatment, the large decrease in the corrosion rate of steel which was seen during the first 20 hours
of immersion is due to the formation of amorphous iron sulfide which temporarily protects the
metal.
In modied geothermal waters, fwstly was studied the iduence on the electrochemical behaviour
of carbon steel of the immersion t h e , the rotating speed and the concentration of corrosion inhibitor
in a degassed geothermal solution, where only the Cl- play a preponderant role (Amalhay and
Ignatiadis, 1994a; Amalhay et al., 1995a). The results prove that the temporal evolution of the
corrosion of steel is essentially linked to the physico-chemical properties of the layer of scale.
Secondly, electrochemical measurements were done to determine the corrosion rate of the carbon
steel in a natural geothermal water as a function of immersion time, electrode rotating speed,
flowrate, HS-, Cl- and inhibitor content in the water (Amalhay, 1994; Amalhay et al., 1994e;
Amalhay and Ignatiadis, 1996a). HS- causes significant changes in the electrochemical behaviour of
carbon steel as indicated by an increase in corrosion potential and current. During the first 6 hours
of immersion, we distinguished three stages of carbon steel behaviour in water with various HS-
contents. When inhibitor is added, the diffusion of HS- towards the metallic surface, and thus the
cathodic reaction which takes place on the scale, seem to be limited, but the inhibitor nevertheless
infiuences the anodic reaction as there is an increase in the corrosion potential and a notable
decrease in the corrosion rate. The behaviour of the metal can again be separated into three stages.
An increase in Cl- content from 0.2 to 0.5 M causes a slight increase in corrosion potential for three
different flowrates (13.5, 21, 30 1.h-1) with and without inhibitor. Without inhibitor, the flowrate
seems to primarily affect the stationary electrode. With inhibitor, corrosion potential and anodic
Tafel constants increase with increasing flowrate at 0.2 and 0.5 M NaCl. The increase in flowrate
therefore facilitates the anodic action of the inhibitor, probably by reducing the thickness of the
scale and thereby facilitating access to the metallic surface.
Electrochemical techniques were used to monitor the behavior of carbon steel during the
crystallization of conosion deposits. Corrosion inhibitors were tested at different concentrations on
site in order to compare their effectiveness in reducing the corrosion rate (Amalhay and Ignatiadis,
1995b). By combining results of electrochemical measurements and mineralogical analyses of the
scale, we have shown that the crystallization of amorphous iron sulfide into mackinawite is
accompanied by an increase in the corrosion rate due to the transfer of cathodic sites from the
surface of the metal to that of the scale (Ignatiadis and Amalhay, 1996a, 1996b; Amaihay and
Ignatiadis, 1996b). Al1 of the inhibitors tested significantly reduce the corrosion rate of carbon steel
and delay the crystallisation of mackinawite from amorphous iron sulfide.
The behaviour of some non metallic materials in actual and treated geothermal environment
have been characterized (Corton, 1994, Lesueur, 1994). This study shows that knowledge of the
behaviour of nonmetallic materials in the field of low enthalpy geothermal energy is limited, for
example, to the analysis of nonmetallic elements already installed on wells or to the "views" of
companies providing services in the field of geothermal energy. Scientific results are rare as
scientists are currently concentrating their efforts on the battle against steel casing corrosion. After
briefly describing the context in which these materials are used, this study lists the principal
characteristics of the nonmetallic materials which can be used in geothermal activities and gives the
main results gathered from the Dogger exploitation in the Paris Basin.
CPR
The design of a structured packhg column for steam washing was a continuation of the previous
programme (JOUG-0005-C) and has been made on the basis of a set of specific data relative to HC1

Conrrol of corrosion and scaling in geothermal sysrems
absorption in alkali solutions. The process operates at relatively low s t e m velocity (< 7 mis), and
consequently low droplet entrainment. The large interfacial surface needed for HCl absorption was
provided by the stmctured packing. On the basis of this work, a full scale washiig column has been
designed and will be constmcted and tested in the near future at Larderello field. Specific support
from EC under THERMIE programme was obtained for this project.
The results of the conventional washing processes adopted at Larderello field have been published in
the open literature by Paglianti et al., (1996) and represent a useful tool for any possible
improvement of these processes in particular for analysis of steam washing equipment. On the
basis of the results obtained it is possible to evaluate the contribution to s t e m washiig due to the
different apparatuses present in the plant, liquid injection section, mixer, primary separator,
demister.
This activity conceming the dry abatement of HCl has started with a thermodynamic analysis of
gas-solid reactions between HC1 and various possible solid sorbents. On the basis of the results
obtained, the kinetics of the chemical reaction between HCl and sodium bicarbonate and carbonate
has been studied in a differential reactor. The kinetic study demonstrated the feasibility of dry
sorption of HC1 and allowed the p r e l i i a r y design of the main reactor. The cost of this abatement
method is such that its installation would allow consistent savings in the energy losses due to s t e m
desuperheating. However, it is recommended that the process be analysed in a pilot plant reactor
before any field applications.
ICEIHTCP
Experimental details of electrochemical measurements
The electrochemical investigation of carbon steel corrosion in NaCl containing aqueous media was
done in the presence and absence of sulfide ions and in the presence of additives to be tested.
Testing of additives regarding their corrosion inhibiting properties was also done in real geothermal
water. Electrochemical investigation included DC (open circuit potential (OCP) measurement vs.
time and Potentiodynarnic scans (Log(1) vs. Applied potential)) and AC (impedance spectroscopy:
measurements of impedance vs. frequency) measurements. The following water-soluble compounds
were examined with respect to their potential as corrosion inhibitors for carbon steel:
1. Organophosphoms compounds: ENTMP,NTMP and HEDP,
2. Commercial products: Solamine 129, Nomst 491 and Aquaprox MDC 1300.
3. Polymeric additives (prepared by BBPDICM) and,
4. Organic compounds: Picric Acid, Sodium Oxalate, Sodium Benzoate and p-~ydrbxyBenzoic
Acid.
Presence of atmospheric oxygen and sulfides in the working solutions proved to enhance the
corrosion of carbon steel. Presence of amorphous FeS leads to protection against corrosion due to a
non porous solid layer that adheres on the carbon steel surface.
Concerning corrosion inhibition, only the commercial products showed a satisfactory behavior.
Solamine 129 showed the best behavior in sodium chloride aqueous media and in real geothermal
fluid. Al1 the other additives tested either they did not affect the corrosion of carbon steel, or they
enhanced the corrosion process.
BBPDICM
(see scale prevention)
CAEL
For the CAEL group, the objective was to mode1 the corrosion processes in large volumes
(resewoirs) using multigrid and f&te element methods, in order to simulate the distribution of

the bulky equipments-in contact with the geothermal electrolyle to be achieved through cathodic
current injection potentiostatically controlled. The design has at basis a theoretical calculation of the
current and potentiel distributions at the metal surface. The calculation is absolutely necessary for
the correct dimensioning of each element of the system. According with the obtained data, it was
designed each element: anode placement, anode diensioning, electronic schemes of the
potentiostatic rectifier, placement and conception of the reference electrode. Two potentiostatic
equipments destined for anticorrosive protection of outside structures as so as for the inside
structures of the bulky equipments too, specifically for the geothermal systems. The proposed
system ensure the active anticorrosive protection systems throught current injection potentiostatically
controlled. The injection is realised versus active anodes which can be inert and101 consurnable,
specialized. The important elements- (specialiied sensors) were concepted and made for a long
working period in the specific mediums for which they were created. The proposed equipments and
systems follow to be tested both in situ of the geothermal systems in operating, and in the ICPE
S.A. specialized laboratories for the fiability test. As result of the tests in laboratory the tested
equipments respects the national prescriptions (STAS) and the international ones (CE1 and ISO), and
also the specific parameters for functioning given by project. For the operating geothermal systems
these equipments continue to work and there is no technical problem with them so far. It was
studied the possibilities of application of the active anticorrosive protection in some metallic
subassemblies from geothermal systems. Thus, there were identified: (i) the extemal sides of the
metallic structures which are in direct contact with the soil; (ii) the interna1 sides of some bulky
equipments. These parts can be protected through the injection of cathodic current method. The
system proposed by us for these surfaces is a complex one, with automatic injection of current in
closed-loop, controlled by the output signal given by an adequate sensor. The equipments achieved
were tested in laboratory and we have obtained good results. We also continue to test these
equipments on a geothermal system from Romania-Bihor district. At this moment we are working to
elaborate the documentation of these equipments according to international prescriptions ISO-9000.
Another part of the work done deals with the shidy of the anticorrosive efficiency of some
polyelectrolytes with anti-scaling effect, synthesized by BBPDICM. It becomes necessary to
conceive new inhibilors with cumulative effect (corrosion and scaliig) and to determine of the
optimal conditions for dosing these inhibitors. Experiments were realized for 21 maleic
polyelectrolytes:
a) It was studied the effect of 13 polyelectrolytes at 0.1-30 ppm addition in synthetic geothermal
water at 60C in order to select a commercial cheaply formula, with a cumulated effect of the
corrosion and the scale inhibition. From the analyses of the experimental results it is estirnated that a
part of the studied polyelectrolytes solutions presents a pronounced inhibitory effect. These solutions
can present a practical interest for a simultaneous inhibition both of steel corrosion and of scaling.
Another part of the presented formula have a reduced anticorrosive efficiency or even nul.
b) It was studied the effect of some polyelectrolytes (copolymers of maleic acid with
triethanolamine) at 0.1-30 ppm addition in synthetic geothermal water at 50C, with the sarne
objective as in a). The corrosion inhibition effect was sudied with polarization curves. The results
are: (i) the AV.128.72 polyelectrolyte in large domains of concentration decreases the corrosion rate
in geothermal waters (1116) and has a mixed effect: reduce both the partial anodic and cathodic
current, (ii) the AV.127.71 polyelectrolyte presents a smaller inhibition effect and influences only
the partial anodic process.
c) The inhibition of corrosion effect was tested for carbon steel R 37 in synthetic geothermal water
at 60C with some polyelectrolytes - copolymers of maleic acid, N-vinilpyrolidone with piperazine

and its derivatives. The tests were realized through the methods of steady state polarization curves
and impedance spectroscopy in a.c.-impedance analyses. By analyzing the data it results that:
- the polyelectrolytes copolymers of maleic acid and N-vinilpirolidone with piperazine and its
derivates, are mixed inhibitors if their structures have lateral aminic groups. In absence of lateral
amino groups the polyelectrolytes reduce the rate of pure charge transfer only for the cathodic
reactions;
- the tested electrolytes have a fast effect so only 1 hour after the addition of inhibitors the corrosion
rate is reduced about 2 to 4 times;
- maximum inhibition effect is achieved with APAEP-1 which has a combined action.
d) The study of geothermal water corrosiveness with polyelectrolyte addition: copolymers of maleic
acid with aromatical amines: it can be observed that many polyelectrolytes present the antiscaling
effect and the inhibition of corrosion too. Through the determination of the acting mechanism, in
correlation with the stmctural formula and the composition of the polyelectrolytes, we consider that
it can be conceived new structures of polyelectrolytes with a great anticorrosive effect.
The corrosion reaction from the interface metallsynthetic geothermal water were studied in the
presence and absence of 21 different maleic polyelectrolytes. Most of them have a great
anticorrosive effect. Il was establiihed that in concordance with the molecular structure and the
content of functional groups, the polyelectrolytes acting anodic, cathodic or mixed either through
the braking of the charge transfert or the modification of the transfer coefficient. A maximum
anticorrosive effect was obtained with the polyelectrolytes having mix action respectively of those
which operate both kinetically and adsorption (alter the transfer coefficient).
2.2. Corrosion studies
BRGM
(see corrosion prevention)
CEBELCOR
Potential-pH equiiibrium diagrams for the system S-H20 were prepared for temperatures from O
to 150C. Consistent thermodynamic data were obtained from Shock (1988), Shock and Helgeson
(1988) for these temperatures. The data were reviewed in comparison with earlier data from other
sources, and an extensive publication was prepared using the data selected (Pourbaix and Pourbaix,
1990; 1992). This publication includes equilibrium diagrams for the system S-H20 at 25, 50, 100
and 150C, for a total dissolved sulfur concentration of 1 molell, considering sulfur, sulfides,
thiosulfates, tetrathionates and sulfites on the one hand, and hydrosulfites, sulfites and dithionates on
the other hand. Al1 calculations for 0C and for other sulfur concentrations are also repoaed. A
theoretical analysis of the effect of access of oxygen is also presented.
Equilibrium diagrams for the system S-H20 for sulfur concentrations of 0.1 and 0.001 molell,
corresponding to solutions in equilibrium with partial pressures of H2S of about 1 and 0.01 bar
respectively, were calculated (Singh and Pourbaix, 1996a). Diagrams were calculated for the
system Fe-S-H20 at 25"C, for these two sulfur concentrations. Equations are given for other sulfur
concentrations. Two data are missing for higher temperatures: the free energies of formation of
mackinawite FeS0,943 and of sulfide S2-. As soon as such data are available, an additional
publication will be prepared with equilibrium diagrams up to 150 or 200C.
From this work (Singh and Pourbaix, 1996a), mackinawite appears as metastable versus pyrrhotite.
Mackinawite may be obtained by reduction of ferrous ion, while pyrrhotite may be formed by

oxidation of ferrous ion. The lower the dissolved sulfur concentration, the larger the corrosion
region where Fe2+ is stable. The area of stability of magnetite is small when maghemite is
considered as the hydrated ferric oxide, and is even smaller or non-existent when hematite or
goethite are considered. Other iron sulfides (troilite, greigite) were not considered in this work,
because the prime interest in geothermy is on pyrrhotite and mackinawite. The E-pH equilibrium
diagrams are useful for the interpretation of laboratory experiments and of field data.
Another part of the work done deals with the effect of trace amounts of oxidants on the corrosion
of C-steel in H2S environment. The theoretical analysis (Pourbaix and Pourbaix, 1990; 1992)
suggests that, if the oxidation of H2S solutions leads to thiosulfate or tetrathionate, there will be a
pH decrease, while if the oxidation leads to elemental sulfur, there will be no pH change. Quantified
examples are given for solutions in equilibrium with 1 bar H2S and with occasional or permanent
exposure to a partial pressure of 0.01 bar Oz. Experiments were conducted to indicate the redox
potential and pH of H2S solutions exposed to either air (po2 = 0.2 bar) or H2S (pHzs = 1 bar). The
tests were made in NaCl 0.35M, representative of the Dogger geothermal water. Gold and platinum
were used as redox electrode. Typical results are shown in figure 1 (annex). The correspondence
between the Eredoxchanges and the pH changes is shown in figure 2 (annex). The potentials and
pH, when plotted in a E-pH diagram for the system S-H20 (Singh and Pourbaix, 1996a),
correspond to the oxidation of H2S into elemental S for the small plateau at O mVshe of figure 1,
+
and then to the oxidation of H2S into SzO3-- for the rest of the plateau around 100 mVshe (fig. 1
and 2). These data suggest that both reactions (oxidation of H2S to S and to S2O3-- can indeed
proceed and that acidification can occur when the latter takes place.
Concerning the study of the corrosion process in sulfide and chloride environment, the approach
was to conduct corrosion experiments combined with electrochemical measurements in order to
interpret the results and identify the reactions taking place. Experiments were conducted also in a
double-compartment corrosion cell, to simulate several factors that could induce localised corrosion:
crevice, scratching, depletion in H2S (Singh and Pourbaix, 1996b). The methods were found
satisfactory, although collection of corrosion products for analysis was not easily feasible. The
major conclusions of this study are:
- the electrochemical conditions for iron and carbon steel in H2S saturated solutions lie well below
the water-hydrogen equilibrium potential, in a region of stability of iron sulfide, not far from a
corrosion area;
- rnackinawite, pyrrhotite, and perhaps troilite can form in these conditions. Pyrite is not stable,
unless slight aeration;
- a slight acidification can significantly increase the corrosion, for a given sulfide concentration;
- the presence of chioride has apparently no influence on the electrochemical conditions of plain
iron surface in H2S solutions;
- however, hydrolysis of ferrous iron in the presence of chioride could produce some acidification,
with increased corrosion as a result. This mechanism may be iiiited to the initiation step. During
the propagation step, anodic surfaces see a higher pH;
- in the complete absence of oxygen, the driving force between cathodic and anodic surfaces is
small;
- still, anodic corrosion current densities are high when the anode is the H2S depleted surface. This
tends to support the idea that H2S depletion is part of the mechanism of localised corrosion in
sulfide solutions;
- the transformation of ferrous ions into pyrrhotite is an oxidation reaction, while the
transformation of ferrous ions into mackinawite is a reduction reaction. This may suggest that
pyrrhotite could preferably form by precipitation of dissolved ferrous ions when a reduction

Control of corrosion and scaling-in geothermal systems
reaction is available and that mackinawite could preferably form when an oxidation reaction is
available. Application of this for the control of deposits in geothermy could be investigated;
- the rate of the cathodic reaction (mainly hydrogen evolution) is probably much influenced by the
sulfur compound present: pyrite, troilite, the non-stoichiometric iron sulfides or elemental sulfur.
Measurement of the kinetics is accessible through experimental techniques derived from the
methods used here;
- it is probable that large current densities are due to the fact that some species act as catalysts for
the corrosion reaction or for the hydrogen evolution reaction. Catalysts for non reversible
reactions are reversible redox systems of which the equilibrium potential is between the
equilibrium potential of the reduction reaction and the equilibrium potential of the oxidation
reaction. Two types of catalysts must be considered in geothermal systems: non stoichiometric
iron sulfides, and bacteria;
- non stoichiometric iron sulfides are present in geothennai wells: pyrrhotite FeSl+, and
mack'iawite FeSI,. In given conditions (sulfide concentration, pH), the redox system
mackinawite-pyrrhotite or the transformation of mackinawite with different values of x may act
as a catalyst for the corrosion of iron with reduction of water into hydrogen;
- the same concept may be extended to the action of bacteria: thanks to specific enzymes, bacteria
are reversible systems and they act as catalysts for reactions of which the equilibrium potential of
the oxidation partial reaction and the equilibrium potential of the reduction partial reduction are
lower and higher than the range of potential in which the bacteria can grow;
- inhibition of corrosion in geothermal conditions is govemed by the electrochemistry of the
system: the conditions in operation correspond to the formation of iron sulfides (possibly
pyrrhotite and mackinawite), with a possible general corrosion because the region of stability of
Fe2+ is not far from the actual conditions, and with a possible corrosion under deposits. F i i g
amines are effective to control H2S corrosion, especially in the absence of deposits. A
combination of acid treatment to prevent deposits and of f W i g amines is sometimes used in the
oil and gas indusm. Another possibility is to increase pH with neutraluig inhibitors;
ICErnCP
see corrosion prevention
CAEL
The objective was to study the corrosion processes due to the presence of HS- and Cl- anions. A
very contradictory behaviour of the steel in contact with brine, which contain H2S and CO2 was
observed. The attack was not uniform corrosion in an electrochemical sense, although it may have
been uniform on a rnicroscopic scale. In any case an important conclusion for practical applications,
since in constmction of tube for geothermal water transport, is that it must be assumed that H2S can
increase the severity of corrosion, even when present in small amounts. It was attempting to
conclude that the lack of reproducibility and the high corrosion rates indicated by the polarisation
resistance resulted from defects in these films. On the other site an osciilatory domain is identified
during Fe anodic polarisation, which is strongly influenced by some critical parameter values: Cl-,
HS-, inhibitor concentration and pH value. A scanning rate over 1 mVlsec in lmear voltamrnetry
can by-pass the oscillatory domain. From this point of view, the current oscillations on Fe
electrodes in geothermal water of high Cl- and HS- anion contents can be considered as a non-
stationary process.
The other deliverable was focused on the determination of the kinetic parameters of corrosion in
the range of oscillating current. Modelling and simulating the periodic oscillations, that occur at
the anodic polarisation of Fe electrodes in geothermal water with high Cl- content are the aims of
this study. One supposes that the occurrence of the oscillations is due to the kinetic steps only. The

mathematical mode1 consists of a two-diensionai ODE system. Non-Langmuir isotherm was found
to be essential for producing the lirnit cycle. Oniy local fit between experiment and theory is
obtained. Another aspect of this work is the using of the integral method to calculate the kinetic
corrosion parameters b,, b, and I,,,, in the geothermal water. The mathematical theory of a two-
parameter method, based on an integral formula, for analysing polarisation curves is applied and the
roots of the non-linear system of two equations are solved. The experimental applications concerns
the behaviour of ARMCO iron in geothermal water with sulfur and CO2 contents.
ICPE-C6O
The purpose of this work is the study of the corrosion mechanism a t the metdgeothermai water
interface, the experimental determination of the corrosion rate, respective of the kinetic parameters
of the iron dissolution electrochemical process, data which are absolutely necessary for the design of
the mechanical assemblies and for choosing the proper inhibitor.
For the detennination of the corrosion risk and also of the proper inhibitors to preventing it, the
corrosivity of fourteen geothermal fluids from Bihor basin - Romania were investigated through the
method of steady state polarisation curves. The tests were made for five different temperatures in
the range of 30 to 90C. Ten types of geothermal waters having chlorosodic character, with diverse
contents of Ca+ and HC03-, waters at which the contents of S04" is smaller than 17 mg11 were
investigated through the method of steady state polarization curves; and four geothermal waters with
a great content of S042- andlor S2-. The results are:
- in chlorosodic geothermal waters, with a low content of S042-, the corrosion rate is primarily
determined by the concentration of Cl-;
- lg j o = f(lg [Cl-]) is a liiear function (deduced from the graphic representation), but there are two
different zones, respectively for Cl- concentration lower and higher than 15 mgll; each of these
zones having its own type of mechanism;
- for these waters the corrosion rate, in the range of 30 to 95"C, is decreasing with the increasing of
the temperature;
- in geothermal waters which have content of S04" and101 S2-, the control of the reaction is pure
kinetical, the l i t stage being the pure charge transfer. Differently of the geothemal waters from
the first category, at these ones the corrosion rate is increasing with the increasing of temperature.
ICVL
The unique geothermal anomaly in Lithuania and its vicinity is situated in the area of the West
Latvia, the West Lithuania and the Kaliigrad Region of Russia. The West-Lithuanian Geothermal
Anomaly (WLGA) is the most intensive and has the biggest area. The average temperature gradient
in the WLGA is ascertained as 40-5O0C/lan, while it is usually oniy 20-3O0C/km in the surroundiig
regions. Klaipeda, Silute, Palanga, Gargzdai and several smaller towns are situated in this region
and can be considered as the potential users of the geothermal energy for district heating and other
applications. The two most promising aquifers in the geothermal fields have been discovered during
the geological exploration and geothermal interpretation. The first aquifer is located at the depth of
700-1100 m in the MiddleILower Devonian geological formation and is characterised by low
temperature (30-40C). Aquifers, situated in the MiddleILower Cambrian geological formations at
the depth of 1700-2200 m., are more suitable for geothermal utilisation. A temperature range of 60-
95C has been measured in these aquifers. The isotherm of 80 and 60C covers respectively an area
of 2400 and 6000 Id. Despite sufficiently generous investigations dealing with utilisation of
geothermal energy in Lithuania, no corrosion investigations in geothermal environment have been
carried out until recently. These investigations were conducted in the current work. To better
understand the corrosion behaviour of iron, it is very important to study the oxide layer formation as
a function of various factors. XPS and EQCM were used for this purpose in the work presented.

Working electrodes for voltammetric measurements were made of pure iron (ARMCO, 99.9) and of
carbon steel Ct 3 which is widely used for manufacturing the pipes. The iron and steel sarnple were
pressed into Teflon jackets and had the geometric area of 1 cm2. The rotating disc electrode was
prepared in the same manner. The reference electrode was a KC1 saturated calomel one (SCE)
placed into separate vesse1 and connected with the investigating solution through the electrochemical
key fdled with the same solution.
The measurements were taken in a special glass ceIl for electrochemical investigations. The ce11
made it possible to thermostat the solution and to have a necessary atmosphere. Voltammetric
dependencies were obtained under conditions of pulse and stationary potentiostatic polarisation as
well as at a liiear potential sweep. The distribution of the elements in the steel surface layers was
investigated by X-ray photoelectron spectroscopy (XPS) and a special electrochemical ce11 was
designed for EQCM measurements.
To simulate the hydrodynamic conditions in a pipe, the rotating disc electrode was used. It is well
known that liquid moves parallel to the electrode surface in the layers close to them when the
electrode rotation is applied, so the geothermal fluid flow in the pipes may be simulated. Besides,
the influence of difision processes on corrosion kinetics may be studied as well. The corrosion
behaviour of iron and carbon steel was studied (under laboratory conditions) in the geothermal fluids
of Iridmntai 1 and Vidmntai 2 . The following conclusions may to be drawn accordiig to the data
obtained:
- the corrosion rate decreases with the immersion time of iron in the solution;
-the cathodic Tafel slopes and corrosion current densities are much higher when the rotation of
electrode is applied;
-the anodic Tafel slopes vary not much as a function of immersion t h e and electrode rotation
frequency and has the value in the range of about 80 - 100 mV;
-the positive open circuit potential shift, i.e. intensifyiig of cathode process proceeds when
electrode rotation is switched on;
- deaeration of the solution leads to decrease in the corrosion rate. To the greatest degree this is
noticeable in the first hour of immersion and especially when electrode rotation is applied. After
two hours immersion the decrease in the corrosion current in deaerated solution is insignificant.
The corrosion current density depends from the electrode rotation in deaerated fluid the same as in
the aerated one;
- the rises of temperature from 20 to 80C cause decrease in corrosion rate of about 1.5 - 3 times
depending on the immersion time. Much pronounced decrease was determined in an unstirred
solution in which the same rising of temperature results in increase of jc about 10 times;
-saturation of geothermal fluid with CO2 causes a slight rise of corrosion rate after 1 h of
immersion in the solution;
- corrosion process inhibition is obsewed when increasing the chloride concentration in the sulfate
solution (pH 3) to the value like in the real geothermal fluid (100 g/l). The lower concentrations of
chloride, viz. 10 and 50 g/l, hiiders the process only at the beginning of immersion;
- the approximate value of the limiting corrosion rate in the naturally aerated system under study has
been calculated. This value was equal to 1.52 mA/cm2.
The formation of oxide layer on iron surface was studied by XPS using surface etchimg with ionised
argon. The formation of the layer at initial stages of corrosion was investigated by EQCM.
Following conclusions can be drown:
- the thickness of oxide layer growth with the exposure time in the solution. The thickness is very
similar in the cases of aerated, deaerated and CO2-saturated solutions;
- the rise of the temperature from 20 to 80C causes developing of more thick layer;
24 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final repori

-the electrode mass growth was detected by EQCM in the first stages of corrosion. The effect was
attributed to the surface blocking by scarcely soluble compounds. The interphase layer should be
sufficient compact otherwise it could not affect a q u m oscillation frequency;
- the most thick layer at the beginning of corrosion develops in the naturally aerated solution. The
layer developed in the CO2 saturated fluid is significant t h i i e r ;
- the corrosion rate calculated from mass gain data at the initial stages of corrosion is extremely high
for the naturally aerated solutions. Three main reasons can be presumed to explain such a result: i)
an high initial electrode activity; ii) a thii depletion layer with pH gradient at the first stages,
consequently, high reduction rate of depolarisers; iii) a precipitation of solution components
simultaneously with corrosion products precipitation.
2.3. Scale formation and modelling
BRGM
Experiments were done in order to better understand iron sulfide precipitation kinetics
(Peyrot, 1993; Ignatiadis, 1993a, 1993b; Peyrot et al., 1995). Results of analyses done at the end of
the kinetics experiments and those of the fluids at the production wellhead were used to identify
which iron sulfide controls the solubility of iron and sulfide in the geothermal environment
(Ignatiadis and Peyrot, 1994). Mackinawite is this iron sulfide, despite the presence of pyrite,
pyrrhotite, greigite and marcasite in the deposits on filters. The origin of the iron (from both the
resemoir and corrosion) and of the dissolved sulfides (from both the resemoir and current bacterial
activiy), and the influence of these species on scaling processes are discussed (Amalhay et al.,
1994b, 1994c, 1995b; Ignatiadis, 1994a; Gauthier and Ignatiadis, 1994; Ignatiadis et al., 1996,
1997). A model of scaling regulation (control) is proposed, suggesting that the formation of scale is
controlled by the diffusion of anions (sulfide, hydrocarbonate, chloride) through the scale (Amalhay
et al., 1994b, 1994c, 1995b).
Concerning the development of the MODEP computation code, the aim was to propose a digital
model that enables the simulation of corrosion and scaling phenomena on steel casing walls (Abou
Akar and Ignatiadis, 1994, 1995). Considering the complexity of the real phenomena, certain
simpliQimg hypotheses were included in the model (Abou Akar, 1994a, 1994b; Abou Akar and
Ignatiadis, 1994, 1995). The simulation of casing corrosion is based on application of the Volmer-
Heyrovski reactive mechanism. The calculations take into account Fick's diffusion laws, the
variation of the thickness of the diffusion layer due to scale growth, and the porosity of the scale
(assumed initially to be made up of mackinawite Fel+,S, the main scale constituant) (Abou Akar
and Boens 1995a, 1995b, 1996; Boens, 1995). The amount of mackinawite precipitated is calculated
using the solubility product, K, or accordiig to kinetic considerations. The model simulates also the
precipitation of other minera1 species (commonly encountered in scale in geothermal wells in the
Paris basin, i.e. pyrrhotite Fe,.,S, siderite FeC03, goethite FeOOH, calcite CaC03 and amorphous
silica SiOz) according to thermodynamic considerations and offers the possibility of adjusting the
flowrate of the geothermal water in the well and takes into account the presence of a well-bottom
treatment tube (WBTT) when calculating the head loss (Abou Akar et al., 1996). The transfer onto
PC of the VAX Fortran code (Abou Akar et al., 1995b, 1996; Battaglia, 1995) has a numerous
advantages: a faster computation speed, autonomous operation, demonstration possibilities outside
the office, and a direct link with graphic packages. Simulation of the behaviour of geothermal fluids
using the MODEP code has enabled the study of the evolution of the major parameters as a function
of the exploitation duration and well depth. The results has revealed (Abou Akar and Boens, 1995a,
1995b, 1996; Abou Akar et al., 1996):
EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final repori 25

- the establishment of different kinetic regimes as a function of diffusion length;

- the calculation of chemical species concentrations on casing walls;
- that the well is subjected to high corrosion at the beginning of its life. Inhibitor treatments must
therefore be applied as soon as water flows through the well;
- that because of the simulation method chosen (increasing thickness of protector scale), the
corrosion rate falls rapidly with time at the beginning of simulation. This reduction in corrosion
becomes less marked when the scale is sufficiently thick. In addition, corrosion rates calculated are
similar to those experimentally measured;
- a good correlation between the evolution of iron content (fluid vein and wall) and that of pH and
sulfide content, and also between the evolution of casing diameter and production flowrate;
- the effect that the slightest variation in pH has on evolution of the corrosion rate of the casing.
This is a simple model and certain phenomena are not taken into account. Nevertheless, this model
could be improved by taking into consideration the reduction of chemical species other than
H+such as HS- and HC03-. However, cemin phenomena are difficult to model:
- the possible precipitation or redissolution within the pores of the scale, which leads to a variation
in porosity with time;
- the appearance of additional cathodic sites, where the protons would be reduced (the electrons
produced during oxidation of iron can move around in the scale as it is conductive). It is no longer
sufficient to only study the metal surface. The scale must be subdivided into thin layers (choice of
the thickness of the layers, calculation of the total intensiiy of the corrosion current). The
numerous problems to be overcome increase the calculation time considerably.
Certain phenomena are very diicult to model, such as the frequency of corrosion pitting at a given
point of the casing. At the most, quantification of the influence of certain physical parameters on the
probability of the appearance of pitting corrosion can be attempted. Even the proposed version of
the code isn't capable of simulating the totality of real phenomena, it can nevertheless be used to
calculate trends that result from variations in the major parameters of the aquifer and101 the casing.
Results will be compared with corrosion measurements in the near future to provide an indication of
the gap with reality and to enable calibration.
CEBELCOR
See corrosion studies
CPERI
Iron Sulfide Scaie Formation
A detailed description of the experimental set-up and procedures is given in Andritsos and Karabelas
(1991). The pH of the fmal solution was controlled by injecting reagent grade nitric acid into the
ferrous Stream. The test section consists of four to six tubular segments, each accomodating two
replaceable pairs of semiannular coupons, forming a pipe section with a uniform inner diameter of
13 mm. The test coupons were made of 316L stainless steel, titanium and teflon, materials used in
geothermal applications. Crystalline reagent grade ferrous ammonium sulfate and sodium suphide
were used for the preparation of the ferrous and sulfide solutions, respectively. The crystal structure
of the deposits was established by X-ray diffraction and the morphology of the deposits was
examined by SEM. The particle size and the morphology of buk precipitated FexS particles were
examined by dynamic light scattering (DLS) respectively in a Brookhaven Instruments Co. unit and
by SEM.
As has been observed with other sulfide systems, the deposited mass increases linearly with time in
the pH range where measurable deposits are formed, at least for the period of these tests (3-5

hours). Appreciable deposition for a certain set of experimental conditions (constant concentration,
temperature and velocity) occurs withii a fairly narrow range of pH values (Andritsos and
Karabelas, 1995). At pH values less than 5.8 the mass of the deposits is extremely small and cannot
be weighed. With increasing pH the deposition rate increases rather sharply and then declines after
reaching a maximum at a value of pH between 6.2 and 6.5. Qualitatively, this behaviour is similar
to what is observed in other sulfide systems such as PbS (Andritsos and Karabelas, 1991). For scale
formation to occur, a critical value of the supersaturation ratio, Sc, should be exceeded, a
characteristic common to other sulfide systems (PbS and CdS). With increasing supersaturation
above Sc, the measured deposition rate rises significantly reaching a maximum value. At even
greater S values, spontaneous bulk precipitation occurs instantly with mixing of the two reagent
streams. In fact, Ricard (1989) reports that for the FeS system in the pH range of 7 to 9, bulk
precipitation is almost complete within 0.26 s after mixiig the reagent streams. The sulfide particles
formed in the bulk (with size of order 100 nm) could be deposited on the pipe surface, but simple
calculations with accepted correlations (e.g. those suggested by Papavergos and Hedley, 1984) show
that the convective transport rate of the particles is two orders of magnitude smaller than that of
individual ions. The black colour of the deposits at pH < 6.7 turns reddish-brown after several hours
of air exposure. XRD examination of both black and reddish-brown deposits did not reveal any
crystalline phase other than elemental sulfur (a-S). Analysis of the deposits by EDS has shown
qualitatively that the major constituents of the deposits were iron and sulfur. In most cases,
however, more sulfur than iron was detected on an atomic basis. The above observation is further
supported by three other observations: (1) The concentration of iron measured in filtrates (using 25-
nm membranes) corresponds to 30-50% of the initial [FeIt. (2) Runs with a ratio [SItl[Felt of about
two shows that the deposition rate is quite close to that for equimolar concentrations.
Morphologically, at short tirnes isolated amo~phoussemi-spherical particles are observed on any
substrate. Their size is less than 200 nm. With t h e , a rather finniy adhering layer forms. Ricard
(1989) suggested that in the precipitation of FeSx the first precipitate has a Fe(SH)z composition,
forming through a fast and a slow process. It is not unliiely that the bubble-like protmsions seen on
the sulfide layers are due to the release of H2S. This observation, combined with the above
mentioned ratio Fe:S- 1:2, strongly supporLs the suggestion of Ricard for the Fe,S formation
mechanism. An increase of the temperature of the liquid increases significantly the deposit
formation rate. The estimated activation energy (-23 Wlmol) is relatively close to that expected for
a diffusion-controlled process, i.e. -20 Wlmol (Mullii, 1993). The deposition rate increases with
increasing flow velocity, suggesting that the formation of deposits may be controlled by the
convective mass transport of the scale-building ions from the fluid bulk to the substrate. However,
at higher velocities it seems that the deposition rate remains constant with increasing velocity.
Although no definite explanation can be offered at the moment for this behaviour, it is probable that
at higher velocities the deposition process is controlled by a surface reaction mechanism.
Cornputer Simulation of Scale Formation and of Coiioidal Parcie Coagulation
Simulation of Particle size Distribution and Scaling Along a Pipeline
The simulation of precipitation and scale formation in pipe flow of sparingly soluble salts, developed
in this programme (Kostoglou et al., 1995), is shown to produce physically realistic results. State of
the art models are used to represent the individual processes involved (nucleation, particle growth,
coagulation) and no arbitrary parameters are introduced. To cope with unavailable data, the PbS
surface energy is estimated by means of turbidity data obtained for the specific system in a parallel
experimental activity. Regarding the formulation, a rather comprehensive population balance is
employed for the solid phase (PbS) in connection with mass balance for the ionic species. The
predictions are quite encouraging, reproducing the bell-shaped deposition versus pH curves obtained
in the laboratory. The peak value of the deposition rate is also predicted quite satisfactorily.
Additionally, the computations display trends of particle size distributions, affected by the

Control o f corrosion and scaling in geothermal systerns
interaction of various mechanisms, which are physically realistic, in a quantitative and qualitative
sense. On the basis of the above results, it appears that by employing this simulation scheme one can
scale up with confidence to larger pipe sizes and different tow rates encountered in geothermal
plants. Also the model can be easily extended to other similar systems of sparingly soluble salts.
Effect of Roughness on Repulsive Forces between Colloidal Particles
Particular attention is paid in this project to colloidal particle coagulation, which (if enhanced)
greatly affects both scaling and brine treatment processes due to particle size enlargement. To
irnprove physical understandiig as well as modeling particle coagulation and particulate fouling, a
theoretical siudy was completed on the effect of particle surface microroughness on electrostatic
repulsive forces between particles. The latter represent a major force resisting particle coagulation.
A simple model of rough surfaces is proposed, which allows computation of the repulsive energy of
interaction as well as an estimation of the tangential forces developing between these surfaces. The
influence of some key model parameters (such as roughness parameters, distance between surfaces
and electrical double layer thickness) on the repulsion energy are examined. The results of the
simple model can be generaliied at least qualitatively, for arbitrary rough surfaces.
Effect of Suvace Dynamics on Repulsive Forces
This part of the study is concerned with surface dynamics of colloidal particles when they approach
each other, which is of sig~ficancein relation to colloidal particle stability and coagulation. More
specifically work is summarized on double layer repulsive forces between colloidal surfaces
approaching each other with finite velocity. The classical theory of colloidal interactions tacitly
assumes that the approach velocity is either infhitely small or infinitely large. In this work the
above assumption is relaxed and the theory is extended for intermediate values of the approach
velocity. Two models of the colloidal surface are considered; Stem layer and dissociation of surface
groups. For the linear problem (small surface potential) closed form expressions have been
developed for the repulsion force. Numerical results are presented which tend to agree qualitatively
with experimental observations.
ICEIHTCP
For the investigation of iron sulfide formation in aqueous systems at 25'C, a computer based
automatic titrator system was constmcted. This unit based on a 386DX IBM compatible PC was
developed for the control of experimental variables. The master variable chosen for monitoring the
process of FeS precipitation was the solution pH. Specific software was wntten for monitoring pH
and maintaining it constant at a preset value. This was realized through an appropriate expansion
card which provided capability of PC-pH meter communication and control of an external stepper
motor for driving a pair of mechanically coupled syringes. Data from each experiment is recorded
on the disk for further treatment.
Precipitatr'on Experiments
The spontaneous precipitation expenments in supersaturated aqueous solutions were done in a 200
ml, double walled glass reactor thermostated at 25C. The supersaturated working solutions were
prepared by mixiig equal volumes of solutions of the ions composing the salt studied. Experiments
were done at both variable and constant supersaturation for iron sulfide and calcium carbonate, in
the presence and absence of inert electrolytes and101 additives to be tested as potential precipitation
inhibitors. Seeded growth experiments were also done for the calcium carbonate system. The
additives tested @repared by BBPDICM), were salts of maleic anhydrite copolymers with various
groups as N-Vinyl Pyrrolidone, Vinyl Acetate, Styrene and Methyl Methacrylate, with code names
AP 28.52.1, AP 28.2, AS 11.2 and AV 142.1. Commercial additive codes were Solamine 129,
Aquaprox MDC 1300 and Nomst 491.
28 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374- final report

The spontaneous iron suljde scale formation in supersaturated aqueous solutions ut high
temperature was investigated. A high temperature high pressure benchtop reactor (Parr Instruments)
was used for this type of experiments at 8OoC, having an effective volume of 300 ml. Al1
experiments were done at variable solution supersahiration in the absence and presence of various
foreign ions and water soluble polymers to be tested as crystallization inhibitors. Experiments were
also done under real conditions in the geothennal site of Melun YAlmont (Paris, France), for testing
of the various additives. Particle size evolution measurements were done under the same
experimental conditions at both 25 and 80C, by transferring unfiltered aliquots of the work'ig
solution in a laser particle counter during the precipitation experiments.
The driving force for the precipitation of a solid phase is the difference between the chemical
potentials in the supersaturated solution, p,, and at equilibrium, b,
respectively:
Av=b-~s
Kietics data from experiments were fitted to the semi-empirical equation
R, = k,o "'
where Rp is the measured rate of precipitation, kg the reaction constant, m the apparent order of
precipitation and CJ the relative supersaturation with respect to the solid phase fonning defied as
Inhibition effectiveness tests were carried out at a fned supersaturation level so that the rates
measured could be directly compared. The relative inhibition was defined as
R.I.% = (Ro -.%O x IO0
%, Ri are the precipitation rates measured in absence and in presence of additive respectively.
Iron sulfide precipitation was found to occur spontaneously in supersaturated aqueous solutions. The
point where precipitation starts depends on the pH, temperature and saliity of the supersaturated
solution. At low temperature (25C) only iron monosulfides can be directly precipitated, regardless
of the solution salinity. In neutral or slightly alkaliie solutions the phase forming is mackinawite. In
slightly acidic solutions amorphous FeS precipitates. At elevated temperature (80C) under low
salinity conditions the spontaneously precipitating phase is amorphous FeS. In slightly acidic, s a l i e
solutions supersaturated with respect to amorphous FeS, the same phase was found fonning while at
lower supersaturations pyrite precipitates. Precipitation of pyrite is enhanced by the presence of
oxidiuing ions such as Cl- and NO3-. The highest precipitation rates were observed in NaCl
solutions. From the kinetic analysis it may be assumed that in al1 cases iron sulfide precipitation is a
surface controlled process. It was also found that iron sulfide particles exhibit enhanced aggregation
during precipitation in aqueous solutions. Synthetic pyrite can be produced via the thermo-
dynamically unstable precursor solid phase amorphous FeS, by ripening at elevated temperature for
extended time periods. The product was found to consist of uniformly sized (lpm) sphemiiitic
crystallites, having a specific surface area of 6 ml g-'.
Testing of various polymer compounds as potential scalig inhibitors gave ambiguous results. While
in laboratory experiments many of them exhibited inhibition properties, in on-site experiments only
ATP 6.2 @repared by BBPDICM) gave satisfying results.
Polymeric additives (BBPDICM products), derivatives of maleic anhydrite showed very good
behavior in most cases as scale inhibitors in the calcium carbonate system. Reduction up to 100% in
the crystallization rates was obtained at very low additive concentrations especially for seeded
growth experiments, indicating blocking of the active growth sites by copolymer molecules. Among

the commercial products tested only AQUAPROX MDC 1300 was found to be effective at very low
concentrations. Solamine 129 and Norust 491 did not exhibit an equal effectiveness.
CRIC
in Hungarian geothermal wells the scaling is mainly due to calcite precipitation and a suitable
description and modeiiig of these rather complicated scaling processes have an economical
importance. Computer-assisted calculations are increasingly used in the prediction of scaliig and
corrosion (Haarberg, 1989; Plummer and Busenberg, 1982; Hamie, 1984). A great advantage is the
ability to simulate the effects of changes in brine variables, such as temperature and composition,
and the probable result on scaling and corrosion. It is necessary to estimate scaling and corrosion
rates at various points in a geothermal power plant. Input data are based on the brine chemistry and
flow and the computational model provides the following parameters: flow rate, temperature and
velocity at certain distance from the bottom of the production well through the plant to the waste
injection system.
in our research we started a step by step construction of a simulating tool to describe these
processes. The first step in this development is the equiiibrium description of the scaling of calcite
and the other important scaling components and the determination of the bubble point. We have
developed an equilibrium model algorithm and program of 15 component by the simplification of
the Haarberg model (1989) in order to describe the equilibrium solubility of calcium carbonate,
calcium sulfate, barium sulfate and strontium sulfate thermal water system under various carbon
dioxide pressure, temperature and concentration of the 15 components. Formulating a model for an
aqueous electrolyte system the following set of equations is to be solved:
material balances
electroneutrality balances
phase equilibria equations
reaction equilibria equations
For the Na-K-Mg-Ca-H-Ba-Sr-Cl-Br-S04-OH-HC03-CO3-O-O system the following equations
are valid:
The vapour-liquid equilibrium for the CO2
. the carbon dioxide hydrolysis

the HC03- dissociation
the H20 dissociation
the calcium, barium and strontium solubility
. the electroneutrality balance

the total allcdinity
the mass balances for carbon dioxide and as well for the calcium, barium, strontium and sulfate
ions
The carbonate system at a fmed CO2 partial pressure (or fmed pH) can be described by the five
equilibrium equations of the CO2-H20-Ca2+ system. However the fixed CO2-partial pressure model
has serious limitations: the CO2-pressure maybe unknown and during the possible precipitation or
dissolution the carbonate equilibrium system changes, which results in alteration of the CO2-partial
pressure. To elimmate these limitations the mass balance for CO2 may be used. To solving the given
equilibrium problem we used the strategy developed by Haarberg (1989). Fust we solved the
equations of the carbonate system, by calculating the equilibrium state before precipitation or
dissolution and by determining some solid phase which could be included or taken out. The
equilibrium composition after precipitation or dissolution is fially calculated.
This set of equations may be solved by the method of Haarberg (1989) by combining and reducing
into two equations in two unknowns. The resulting non-iimear equations can then be solved for m,,

and for m H o l by a regular Newton-Raphson solver in two variables. The solution of this system
using activities instead of concentration requires an iteration algorithm. The input data may be the
total alkalinity-CO2 pressure, or the total alkalinity-pH values. We constmcted a solution algorithm
and a prograrn for both the mT-pCol and for the mT-pH input cases.
From the calcite dissolution equations (for a CaC03-CO2-H20 system) it is quite clear that removal
of CO2 from the solution into a steam phase during flashing leads to calcite supersaturation even
though the concomitant temperature drop itself leads increase in calcite saturation. Smce most
reservoir fluids are close to saturation with calcite, carbonate scaling the precipitation is possible for
al1 geothermal wells inside the well between the bubble point depth and the production casing. The
solubility of calcium carbonate minerals in aqueous solution at any particnlar temperature increases
with increasing partial pressure of CO2. Boiling leads to strong reduction in CO2 partial pressure
due to effective transfer of CO2 into the steam phase. The presence of other gases in the geothermal
fluid, especially if they are less soluble in water then CO2 will enhance degassing of the CO2 during
boilimg .
In the next step we combined this algorithm with the earlier developed multicomponent equilibrium
solubility algorithm. The basic idea of this combination is the fact that scaling starts only above the
bubble point, so we have to describe the precipitation and dissolution processes betweeu the bubble
point depth and the well head. Using the available gas separation and chemical analysis data for a
given well one can determine the bubble point pressure (and the partial pressures of the three gas
components). Moving in the direction upward of the well head it is possible to determine the new
gas pressures, temperature the liquidlgas phase ratio at this new depth value. In our simulation
mode1 we used a method similar to the Kocsis method [Kocsis, 19761 for the determination of the
equilibrium gas pressures and temperature between the bubble point and well head depths.
The small laboratory reactor was constmcted in order to make pre-investigations before constmction
of a semi-plant scale equipment. It was necessary to determine the residence times which are needed
to reach the equilibrium. This small reactor is also suitable for static experiments conceming the
investigations of precipitation-dissolution processes of the main scale developer CaC03 and other
compounds.
2.4. Scale prevention
BRGM
A comparative study of the effectiveness of various surfactants in inhibiting iron sulfide
precipitation in a natural geothennal environment have been realiied (Harmandas et al., 1996).
The objective of this study is to try to understand bener the mechanisms controlling the action of
these inhibitors and compare their effectiveness to those of other molecules or fonnulae which have
not been marketed and are synthesized and provided by the group of Prof. A. Carpov (BBPDICM,
Iasi, Romania). In general, al1 the additives tested in this experimental investigation did not prove to
have any scaliig inhibition effectiveness. Yet, we can see that in some cases, some of the
compounds accelerated the formation of iron sulfide precipitate. Considering that the concentration
used (5 mg/l) was in the s m e order of magnitude as Fez+ concentration, these compounds cannot
be recommended for use as scale formation inhibitors.
CPERI
The scale inhibition studies were conducted in the previously described set-up with the addition of a
second test section following the first one. The inhibitor solution was introduced after the first test

attained with the same maleic copolymer. BBPDICM think that is the first step to obtain a
multifunctional agent for geothermal water treatment.
ICPE-CO0
(see corrosion prevention)
2.5. Corrosion and scaling in diphasic flow conditions
BRGM
The study of corrosion and scaling in diphasic flow conditions was undertaken on an artesian
production well of the Chelles geothermal station (France), which was operating without treatment
with additives injected at the bottom of the well (Abou Akx, 1993; Abou Akar and Lafforgue,
1994). Corrosion at the surface has been under study at this location for several years. In 1992, an
auxiliary injection tube was put down the well to a depth of 150 metres. Fitted with coupon-holders,
corrosion coupons were placed at three depths: 150 m (monophase zone), 60 m (bubbling point) and
4 m (biphase zone). Measurement of the rate of corrosion shows a slight increase with the degassing
of the fluid. Examination of polished sections with a metallographic microscope shows that the
products of corrosion are made up of iron oxides and oxy-hydroxides containing a mackinawite
residue. These products initially take the form of the coupon and at the surface growth of iron
sulfides with mainly pyrrhotite can be obsewed, in places associated with carbonates or diluted in a
siliceous matrix. It has not been possible to demonstrate any correlation between this deposition on
one hand (nature and proportion) and on the other, the transition from the monophase to the
biphase zone.
CPERI
The velocity measurements were carried out in a horizontal flow loop (using Laser Doppler
Anemometry, LDA), where air-water two-phase flow developed in a 50.8 mm i.d. pipe (Paras and
Karabelas, 1991). Regardiig the she'ar stress experiments, measurements were carried out at nearly
atmospheric pressure, in a newly constmcted horizontal flow loop, where two-phase flow developed
in a 24 mm i.d Plexiglas tube with a 5 m long straight section. Liquid-to-wall shear stress, at various
pipe circumferential locations was measured using the electrodifusion technique. A schematic
layout of the flow loop, as well as the description of the electrochemical technique are presented in
more detail elsewhere (Vlachos et al, 1996). This setup is of smaller scale than the existing 50.8
mm i.d. pipe loop in order to better control the conditions of the electrochemical system and to
reduce the volume of the photo-sensitive liquid inventory and of the possibly required nitrogen gas.
At relatively small liquid flow rates (compared to s t e m or gas ihroughput), and for gas velocity
above 10m/s, the so-called "stratifiedlatomisation" flow (da) regime prevails. The main features of
this regime are the appearance of disturbance waves, with a characteristic frequency 1-10 Hz, the
liquid droplets entrained in the gas phase and the drastic change of the average gaslliquid interface
profile from flat to concave. Conclusions are reported for the gas phase flow field and for the liquid
layer characteristics.
The new LDA data in the gas phase of sla flow are assessed in connection with already reported
data of wavy liquid layer characteristics obtained in the same experimental set-up, under the same
conditions, and found to be consistent. The tirne average velocity profiles on the vertical symmetry
plane display a maximum generally below the middle (or center) of the gas space coordinate y/(D-
hW). On the contrary, the axial velocity profiles on the horizontal symmetry plane (Le. 90" to the
vertical) clearly exhibit a "moustache" shape, with a local minimum at the pipe center, and two
-
EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 final report 33
(symmetrically spaced) maxima. These trends are in general agreement with those observed in the
data by Dykhno et al (1994), strongly suggesting the presence of secondary flow currents.
Regardmg the structure of such secondary currents, the new data seem to be in agreement with the
observations made by Flores et al (1995), i.e. of two large counter-rotating vortices with respect to
the vertical symmetry plane. Well-hown forms of the turbulent velocity profile seem to be quite
satisfactory for correlating the data, not only at the pipe top but also in the lower strata of gas phase
if the equivalent roughness of the wavy interface is properly taken into account. The infiuence of
large waves is quite significant near the gaslliquid interface, as expected. An interesting fmding of
this study (obtained from the velocity spectra) is that the influence of large waves may extend up to
-
the pipe top (even at distance from the wall y lmm), probably through the secondary motion in the
gas core.
Special attention is paid to the lateral distribution of the liquid-to-wall shear stress by making
measurements at various circumferential locations. An important result regarding the local time-
averaged shear stress is that a significant lateral variation exists, associated with the decreasing
liquid film thichess, away from the bottom of the pipe. Only in the case of relatively low
superficial velocities (UG<15m/s), the mean shear stress is roughly constant up to 45", where an
adequate liquid film exists. Beyond that lateral position, shear stress tends to decrease as the film
thickness decreases to reach, at the angle q of the triple-point (solid/gas/liquid), the value of the gas-
to-wall shear stress. By taking into account the correct shape of the gaslliquid interface and having
the ability to calculate accurately a circurnferentially averaged shear stress value, improved
estimates of the interfacial friction factor fi are obtained. To estimate fi, film thichess, pressure
drop and shear stress measurements (or respective correlations) are required. For the computational
procedure the gas-liquid interface is considered to be concave, and not flat for reasons pointed out
earlier. The complete procedure is described elsewhere (Vlachos et al., 1996).
CPR
The GEA ( G e o t h e d Eqdibn Assessment) Code represents a consistent extension and
completion of the DROP code developed to determine the liquid composition at dew point of
geothermal steam. The GEA code is able to predict the equilibrium composition found in the heat
exchange equipment of a geothermal power plant and in particular in the Direct Contact Condenser
- Cooling Tower system. The code also considers the oxidation of H,S due to dissolved oxygen and
for this reason can be extremely useful in order to determine the effect of HC1 in the H2S
partitioning between non-condensable gases and the circulating liquid.
Direct injection of an alkaline solution in the well (stem washing in the weii) allows, in principle,
protection of well casing in al1 the cases in which a corrosive condensate may form in the well. The
theoretical investigation conducted in this part of the project demonstrated the feasibility of this
process, in particular with regard to the phenomenon of well flooding and the identification of the
liquid flowrate which allows good protection of pipe wall at an acceptable increase of pressure
losses. In order to determine the pressure losses and the flow structure in the well with respect to
liquid partition between the wall layer and the entrained droplets, a new model has been developed
in order to evaluate liquid deposition at the wall. This model, along with other correlations
developed in the past in this laboratory or available in the open literature is the central block of the
vertical annular flow version of the HORF code named VEA (Vertical Annular). The HORF code
has been developed in the past to predict the flow structure in the transportation in long pipelines of
geothermal fluids. The model devloped in the present research was proven to predict accurately the
measurements of liquid entrainment rates, liquid deposition rates and pressure drops available in the
literature. The resuits obtained with respect ;O the irocess of steam &whing in the well suggest that
also in this case a direct application of this technique is feasible.

2.6. Corrosion and scaling monitoring
BRGM
In order to monitor the corrosion rate of carbon steel (used for pipes and casings) and to
maintain the effectiveness of a treatment by a corrosion inhibitor in a given geothermal plant,
several different methods must be used, each having its own limitations, its advantages and
disadvantages. The work done has contributed to the adaptation and the use of three types of
methods for geothermal applications (Ignatiadis et al., 1994a, 1994b, 1994c, 1994d). The results
obtained by al1 of these methods enable us to evaluate corrosion rates in cells (with partially
reconstiiuted or actual geothermal water), in pipes and casings in geothermal plants. To determine
the decrease in casing thickness by measurement of the iron flux emanating from the production
well, it is necessary to know the iron content of the reservoir fluid and the amount of scale deposited
by the rising fluid on the well walls. The physico-chemical fluid data gathered at production
wellheads and from the Well Bottom Treatment Tubes (WBTTs) or from the down hole sampler
PRINPIMO (Lesueur et al., 1996) allow the calculation of corrosion rates. Measurements of weight
loss of metal coupons immersed in the fluid at the surface for various lengths of time are converted
into thichess loss. Measurement of the polarisation resistance of a metal sample immersed in the
fluid makes it possible to determine the aggressivity of the fluid (generalised corrosion) with respect
to the sample. Work towards the design and test of an on-line probe has been carried out. The use
of a suitable electrochemical equipment, allow us to determine the type of corrosion observed in the
presence of an inhibitor and on the influence of certain chemical components of the fluid on the
corrosion.
The influence of some exploitation conditions on corrosion and scaling in geothermal wells is
reported (Amalhay et al., 1994a; Ignatiadis et al., 1997). The corrosivity of a geothermal fluid was
assessed with respect to various materials at two flowrates, 0.3 and 3 m/s, in the presence and
absence of an corrosion inhibitor (quatemary ammonium salt type). The procedure for measuring
corrosion rates included both weight loss and electrochemical methods. The scale produced under
the same conditions was characterized by classical chemical analysis, X-ray diffractometry,
scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). The
experiments show that carbon steel samples suffer fairly general corrosion. The corrosion rate and
scale thichess decrease as a function of the fluid flowrate. The inhibitor considerably reduces both
corrosion rate and scale thickness (Amalhay and Ignatiadis, 1993; Amalhay et al., 1994a; Ignatiadis
et al., 1997). Concentration of chloride ions at the metallscale interface in the presence of the
inhibitor is considerably reduced compared to that measured in absence of inhibitor. Mineralogical
analysis showed that the scale is composed of more than 70% iron sulfides (mainly as mackinawite)
and that the S/Fe ratio in the scale increases as a function of length of exposure. In an attempt to
understand the mechanisms of formation of iron suIfide scale, we used several techniques to analyze
scale formed on samples of carbon steel immerged in geothermal water for relatively long periods of
t h e . SEM studies of polished sections of carbon steel after long immersion times showed that the
scale is made up of two distinct layers having different compositions. The inner layer is made up
primarily of iron oxi-hydroxide (FeO-OH), of iron hydro-oxichloride and of iron chloride. This
layer is thii and adheres well to the metal. Small heterogeneities of iron sulfides and iron carbonates
are sometimes present in this first layer. The outer layer is much thicker-up to, or even more than,
1millimetre thick. This layer is formed essentially of a mixture of iron sulfides. This layer is soft,
brittle and does not adhere well to the metal. When the hydrogen sulfide content is low, the scale
has this two-layer structure, but the inner layer of iron hydroxide is very thick and in the outer
layer, the iron sulfides are made up mainly of pyrite. The lower the hydrogen sulfide concentration
of the fluid, the richer the scale formed on the carbon steel coupons coming from the various

CAEL
Specific tools (two specialised softwares) to be used for experimental measurements or interpretation
of experimental data were developed: (i) a program (TAFEL II) for computation of corrosion rate
and polarisation resistance by using the integral method (distributed to the Greek's partner of the
contract); (ii) another program (LEAC) for experimental data acquisition, to assist the matrix
electrode system via a multiplexing hardware system. It allows the measurement of the current
distribution andlor open circuit electrode potential.
The matrix electrode (multi-electrode) is an extension of usual single-electrode electrochemical
systems. It is particularly suited for corrosion monitoring in actual or micro-pilot systems. This
matrix electrode:
can be used in studying the infiuence of flowing corrosion inhibitors over plane electrodes;
is a very flexible system, since it is computer assisted;
can be integrated in so called virtual instruments and can be operated in the frame of object type
graphical programs;
reduces the measuring errors currently present in surface manufacturing by virtue of its very
matrix structure;
can be used in electrochemical system with or without extemal current source;
is a monitoring system and as such it cannot be used properly in investigating surface phenomena
associated with the first polarisation cycle;
The system can be easily developed and oriented toward different data acquisition boards since a
large part of it (electrode, multiplexor, software) is designed by LEAC;
A muitiplexer board was designed to connect the matrix electrode to the data acquisition card. The
set of electric information produced by the matrix electrode is received by the data acquisition
system (BP 100 board) via the multiplexor system. The electrical information is presented either
directly or suitably amplified to the A/D board, where the continuously varying data are converted
into digital (discrete varying) data, which is in tum presented to the PC computing system. This
process is controlled by a dedicated software package LEAC which exchanges information with the
matrix electrode. The experimental date can be either processed in real time or stored in view of
subsequent processing using commercial software packages compatible with ASCII data files. The
post-processing used in our study of corrosion processes was done on the ORIGIN software
package.
ICPE-CO0
The possibity for automatic dosing (in closed-loop) of the inhibitors in geothemal systems was
examined. Geothennal well operators are interested in correctly dosing the corrosion and101 scaling
inhibitors in such quantities, so to obtained the best result for the technical and economical
parameters. The quantity of inhibitor requested depends of some physico-chemical parameters,
which are variable intime. It is better to dose the inhibitor in a controlled automatised process. This
means that finally if there is not enough inhibitor, the purpose of dimiishiig both the scale and the
corrosion is not fulfilled, or if it is too much the cost is to high. Conceming the work performed:
a) It has been studied the constmction of the actuator for automatically dosing the inhibilor. In order
to obtain the best technico-economical effect for the inhibitor dosage, the electrical motor must be of
a special design and type, so to provide constant speed at constant torque, in large range of speed
(1110 ratio). The purnp driven by the electrical motor must be of a high pressure value (300 atm)
and controlled debit function of the motor speed.
b) it has been studied, conceived, designed and executed a multifunctional transducer device capable
to collect information about scaliig and corrosion rate and temperature and to transform these
parameters in electric signals. In order to use this information it has been conceived an intelligent
EEC-DG XII-Joule Programme-contracf Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 37

system that collects, transmits, processes the information and decides the dosage of the inhibitor by
means of an actuator. By monitoring these parameters we can obtain the automatic dosage required
for the geothemal water.
c) It was experimentally demonstrated the possibility of monitoring the scaling rate by measuring the
impedance of some special designed electrodes. It was designed, built and tested the proper device.
Considering the ideas presented previously, the multifunctional transducer can give at its output a
signal which is substantial sufficient to control an automatic injection system of inhibitor.
It was studied the automatic dosing possibiliiy in optimal quantities (from technico-economical point
of view) of the inhibitors in geothermal systems. So it was designed an automatic system controlled
by computer through the electrical signal given by a multifunctional sensor for corrosion, scale and
temperature. This signal controls the actuator (the assembly motor-purnp) which inject the inhibitor
inside the geothermal well. Also, it is realized and tested a multifunctional transducer. From its
experimentations it results that for the carbonates scales, the impedance variation at 100 Hz of the
transducer is about 200 n / m d , respectively 0.2 Q/pm.
38 EEC-DG XI/-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report

3. PRELlMlNARY CONCLUSIONS
BRGM
The objectives of the BRGM were to eliminate the problems due to corrosion and scaliig in the
exploitation of low enthalpy geothennal systems in order to ensure their financial profitability. The
research programme aimed on the one hand, on the theoretical level, to develop understanding of
the reaction mechanisms which control corrosion (of carbon steel) and scaling, and on the other
hand, on the technological level, it aimed to improve the solutions currently employed and to
develop new, less costly andlor more reliable solutions. The work carried out in the framework of
this project allow us to:
Develop a metrology associated with the monitoring of corrosion and scalmg;
Select the most efficient products for inhibiting corrosion or crystal growth with a view to their
optimal use within current and future operations;
Establish the kinetics of the formation and growth of the scale most frequently encountered, with
the development of appropriate numerical simulation codes. The calculation code enable
modelling of corrosion-deposition phenomena in low enthalpy geothermal systems;
Establish a general methodology for detecting and assessing perforations in casings of wells
exploiting geothermal waters.
Seven main studies were carried out: (i) to monitor, study and model the corrosion and scaling
phenomena, and (ii) to determine the optimal conditions for the elmination of the causes of
corrosion and scaling:
1) In order to monitor the corrosion rate of carbon steel, several methods have been used and
adapted for geothermal applications: chernical analysis, weight loss of coupons and measurement
of the polarisation resistance. Each of these methods have its own limitations, its advantages and
disadvantages.
2) The influence of some exploitation conditions (iibitor, flowrate, material) on corrosion and
scaling in geothermal wells have been examined: the corrosion rate and scale thickness decrease
as a function of the fluid flowrate. The inhibitor considerably reduces both corrosion rate and
scale thickness. The scale is composed of -70% iron sulfides (mainly as mackinawite).
3) The behaviour of a carbon steel in the absence and in the presence of various corrosion inhibitors
in reconstituted, actual and modified geothermal water in order to optimize their use in low
enthalpy geothermal systems has been studied. The influence of some physico-chemical
parameters such as saliity, hydrogen sulfide concentration and flowrate have also been studied.
This enable us to adjust (for each fluid composition) the concentration of the inhibitor for an
optimum effectiveness.
4) Experiments were done to understand iron sulfide precipitation kinetics. Mackinawite is the one
which controls the solubility of iron and sulfide in the geothermal environment. A model of
scaling regulation is proposed, suggesting that the formation of scale is controlled by the
diffusion of anions through the scale. Crystalliiation of amorphous iron sulfide into mackinawite
is accompanied by an increase in the corrosion rate. Al1 of the inhibitors tested, except those
prepared by BBPDICM, significantly reduce the corrosion rate of carbon steel and delay the
crystaiiiiation of mackinawite from amorphous iron sulfide. A comparative study of the
effectiveness of various surfactants in inhibiting iron sulfide precipitation have been realized. In
general, al1 the additives tested did not prove to have any scaling inhibition effectiveness.
5) The behaviour of some nonmetallic materiab in actual and treated geothermal environment have
been characterized. After briefly describing the context in which these materials are used, this
study lists the principal characteristics of the nonmetallic materials which can be used in
geothermal activities and gives the main results gathered from the Dogger exploitation in the
Paris Basin.
EEC-DG XII-Joule Programme-contract Nos JOUZ-CT92-0108 and CIPD-CT93-0314 - final report 39

6 ) A digital model (MODEP) that enables the modelling of corrosion and scaling phenomena on the
casing walls is proposed. Simulation of corrosion is based on the Volmer-Heyrovski reactive
mechanism and takes acconnt Fick's diffusion laws, the diffusion layer and the scale porosity.
The model (i) simulates the precipitation of mackiiawite and other mineral species, (ii) adjusts
the flowrate in the well, and (iii) takes into account the presence of a well-bottom treatrnent tube.
Although the MODEP code has never claimed to be capable of simulating the totality of real
phenomena, it can nevertheless be used to calculate trends that result from variations in the major
parameters of the aquifer and101 the casing.
7) The environmental impact of a perforation in the casing of a well exploiting the water of the
Dogger was examined. When localized, corrosion can lead to perforations in the casing, thereby
increasing the risk of contamination by geothermal fluids of freshwater aquifers traversed by the
wells. After examination of the various water-migration possibilities with one or two casing
perforations in a production or injection well, the different detection methods for perforations are
discnssed in terms of their limitations and accuracy.
These results were presented at the partners periodic meetings to which CEC experts are invited and
in seven biannual reports. BRGM annual reports and some study reports have been sent to experts
in order to spread the information. Several publications in international meetings have been made.
CEBELCOR
E p H equilibrium diagram contribute to the correct understandimg of the reactions that are possible
and of those that must not be considered, in given conditions of pH, potential, sulfur and iron
concentrations. They provide also a trustable guide for extrapolation and prediction of phenomena in
modified conditions. They clearly show the combinations of anodic and cathodic reactions that rnust
be considered simultaneonsly. The nature of possible corrosion products is indicated also, and this is
a support to the analysis of deposits and scale. Again, diagrams suggest modifications of operating
conditions that would decrease the amount of deposits formed. Of course, specific inhibitors for
crystal growth need other siudies, conducted by other groups. The use of two-compartment
corrosion cells appears promising for the detection of corrosion processes, includ'mg localised
corrosion. The principle of these cells has been described.
Three draft papers have resulted from this research programme: one is almost ready for being
submitted, probably to Corrosion Science. Data for mackinawite at higher temperature would
strongly add to the interest of this paper. A second draft paper (on experimental work) is now being
cornplemented by addition of surface and deposits analysis and would then be an interesting
contribution to corrosion in sulfide media. When these papers will be ready, they will be presented
also in corrosion congresses. It is important to indicate that this programme induced a close
collaboration between BRGM, Cebelcor and Dr. Amaihay, throngh a post doc position of the latter
at Cebelcor, within the "Research in Bmssels" programme of the "Rgion de Bmxelles-Capitale".
CPERI
Three main studies were carried out: (i) iron snlfide scale formation, (ii) two phase flow, and (iii)
simulation of particle size distribution and scaliig along a pipeline.
The data show that deposits form essentially oniy within a narrow pH range, which is associated
with the solubility of the amorphous Fe,S. At relatively large supersaturation ratios precipitation in
the bulk solution occnrs immediately after mixing of the two reagent streams, thus depleting the
solution of ions needed for wall crystallization. One may conclude that a small reduction of pH of
the brine can be beneficial, not oniy by converting a supersaiurated solution to an undersaturated
one, but also by decreasing the supersaturation ratio below its critical value. On the other hand, a
small increase of pH can alter the spontaneous precipitation propensity of a brine, promoting
instantaneons bulk precipitation. The relatively small size of the precipitated particles may suggest

the use of a flocculating agent in the clarification system. The experimental work regardimg scale
inhibition deals with the effects of several additives on the scale formation of Fe,S and CaC03
systems. A small inhibition action was found for the iron sulfide system at an additive concentration
of 10 mgll. On the other hand, for intermediate CaC03 supersaturation ratios almost complete scale
inhibition was obtained with al1 additives, while at higher ratios crystal distortion occurred, resulting
in weakly cohesive deposits, but not in a significant reduction of the scale formation rate.
At relatively small liquid flow rates (compared to s t e m or gas throughput), and for gas velocity
above 10m/s, the sa-called "stratified/atomization" flow regime prevails. The main features of this
regime are the appearance of disturbance waves, with a characteristic frequency 1-10 Hz, the liquid
droplets entrained in the gas phase and the drastic change of the average gaslliquid interface profile
from flat ta concave.
The simulation of precipitation and scale formation in pipe flow of sparingly soluble salts, presented
here, is shown to produce physically realistic results. State of the art models are used to represent
the individual processes involved (nucleation, particle growth, coagulation) and no arbitrary
parameters are introduced. The predictions are quite encouraging, reproducing the bell-shaped
deposition versus pH curves obtained in the laboratory. The peak value of the deposition rate is also
predicted quite satisfactorily. Additionally, the computations display trends of particle size
distributions, affected by the interaction of various mechanisms. Particular attention is paid in this
project ta colloidal particle coagulation, which (if enhaced) greatly affects both scdmg and brine
treatment processes due ta particle size enlargement. A theoretical study was completed on the
effect of particle surface microroughness on electrostatic repulsive forces between particles. A
simple mode1 of rough surfaces is proposed, which allows computation of the repulsive energy of
interaction as well as an estimation of the tangential forces developing between these surfaces.
CPR
Al1 the activities carried out in the course of the present research programme arrived ta a firm
conclusion and the major results obtained can be used for a more efficient and clean exploitation of
geothermal energy. Future work can obviously be dedicated ta an improved lmowledge of the
processes and methods investigated in this project, but present results can be immediately
transferred to field operations.
ICEIHTCP
Iran sulfide precipitation is a process controlled by a surface diffusion mechanism regardless of the
environment in which it occurs. The finally forming phase depends on various physicochemical
parameters in the working solution. Metastable phases form initially, converting gradually to stable
ones.
Polymeric products were tested but showed little effectiveness regardiig inhibition of iron sulfide
formation, especially under real conditions, while for the calcium carbonate system they even
caused complete inhibition of precipitation.
Corrosion of carbon steel specimens occurs rapidly in aerated saline solutions. Corrosion is also
enhanced in the presence of sulfides while it is retarded by the presence of amorphous iron
monosulfide in the working solution. Commercial products used in French geothermal wells
exhibited good inhibiting properties regarding corrosion, but maleic anhydrite copolymers gave poor
results.
It has ta be pointed out that in both cases of solid formation and corrosion, the fuial additive testing
should be done with experiments at the specific geothermal site they are going to be used in order ta
draw decisive results.

BBPDICM
BBPDICM appreciates that this research must be continued because maleic copolymers are not only
usefui for geothennal waters but also in other industrial domains or in environmental protection.
BBPDICM intends to contact the Programme EUREKA, if this programme is still interested in
geothermal studies, with the aim to test our products in different countries interested in the
exploitation of geothermal water containing calcium and magnesium bicarbonates. In the same time
the collaboration with ICEIHT Patras will be continued in the future on a biiateral basis. The
laboratory synthesis of its products could be scaled up in the small or medium sized production units
without great diff~cultiesin Romania or abroad. The maleic polyelectrolytes are versatile products.
They can be applied in a large number of research domains in the following programmes:
- environment - as water and waste water treatment or sludge, etc,
- agriculture - as soi1 conditioners, etc,
- industrial technologies - as filtration aids, etc,
- biomedicine - as formulation aids for dmg delivery systems, inhibitors for calcification of artificial
organs or implants.
Concerning his intentions to publish, BBPDICM thinks that the following results could be published,
of course with the agreement and in collaboration with our colleagues:
- inhibition of FeS precipitation with maleic polyelectrolytes (this effect is not yet cited in literature),
- inhibition of CaC03 precipitation in geothennal systems with various maleic polyelectrolytes (new
products with a such effect),
- review papers conceming polymeric antiscalants and anticorrosion agents,
- piperazine derivatives of maleic copolymers as corrosion inhibitors,
- aromatic amine derivatives of maleic copolymers as corrosion inhibitors,
- romanian patent applications regard'ig the synthesis of various derivatives of maleic copolymers,
- european patent applications (with the help of Our colleagues and EU) concerning inhibition of FeS
precipitation or inhibition of corrosion with maleic polyelectrolytes.
CAEL
For the CAEL group, the work performed in this programme allowed the following points:
purchase of research equipment, computing equipment and associated software at the current
European level;
international contacts with suitable partners in the area of corrosion and scaling;
marketing studies regarding the implementation of anti-corrosion protection and anti-scaling
methods in geothermal wells of the Bihor-Romania area;
preparation of two papers to be published, the first concerning the cathodic protection of tanks
with external current source and the second dealiig with the validation of an integral method of
computing the corrosion rate.
CRIC
An equilibrium model and a related computer programme was developed to simulate the solubility
of calcite in water. The first model is based on the simultaneous resolution of the material balances,
electroneutrality, phase equilibria and reaction equilibria equations via Newton-Raphson method.
Using this model one can calculate the equilibrium concentration values for the Ca2+, H+, OH-,
HC03-, CO3" ions, and the H ~ C O as ~ *well as the pH, the alkalinity and the total carbonate at any
temperature and CO2 pressure using the Davies and Pitzer activity calculation methods. A small
laboratory scale reactor was developed first to test the predictions and for the future experiments.
The predicted results fitted well the data measured and given in the literature. The developed model
is a suitable basis for the simulation of solubilities of multicomponent geothermal and thermal water
including the Na-K-Mg-Ca-H-Ba-Sr-Cl-Br-S04-OH-HC03-CO3-CO2-H20 system.

An equilibrium model and a related computer code was developed in the second step by modifying
the Haarberg model maarberg, 19891 to simulate the equilibrium scale formation in thermal water.
The model is based on the simultaneous solution of the material balances, electroneutrality, phase
equilibria and reaction equilibria equations via Newton-Raphson method. Using the model one can
calculate the equilibrium concentration values for the Ca2+, Ba2+, Sr2+, Mg2+, H+, Na+, K+,
OH-, Cl-, B r , HCOy, C032-, S042- ions, and the H2C03* as well as the pH, the alkalinity and the
total carbonate at any temperature and CO2 pressure using the Davies and Pitzer activity calculation
methods. The predicted results fitted the literature data well. The developed model is a suitable basis
for the simulation of multicomponent geothermal and thermal water solubilities includiig the Na-K-
Mg-Ca-H-Ba-Sr-Cl-Br-S04-OH-HC03-CO3-CO2-HO system.
An equilibrium simulation algorithm and a computer program were developed for the determination
of the bubble point pressures in a thermal or geothermal well. The developed program computes the
bubble point using the measured gas separation and other data. The computed bubble point depth
and pressures were compared with the measured values and a suitable coincidence was found.
N-substituted (acylated, hydroxymethylated, carboxymethylated) amino acids reduced the corrosion
mild steel up to 85% in test water. The presence of a more hydrophobie moiety enhanced the
acylamino acid's corrosion inhibition activity.' N-carboxymethylated amino acids are effective scale
control agents and may reduce the corrosion inhibition at the same t h e . This property of inhibitors
could be a consequence of the electronwithdrawing properties and inductive effects. Actually,
inhibitory efficiency depends upon a combination of intramolecular, steric and electronic activities.
SFM images gave a detailed information on the surface morphology due to the corrosion with or
without inhibitors.
Our prelimiry results indicate the imporance of the ELUMO. Efficiency increases with
decreasing values of ELUMO. The results seem to indicate, that charge transfer from the metal
surface to the inhibitor takes place during the adsorption. The continuation of this investigations is in
progress. Comparing simulated and experimentally deterniined fractional coverages a very simple
model was found for interaction adsorbed species in order to make a distinguition between the
adsorption mechanisms of Langmuir and Frumkin type.
The results got by CRIC were already included at several international conferences by the
coworkers and the publication of the results has also been started. The accumulated results will also
be distributed among Hungarian specialists dealing with geothermal systems. The CRIC is going to
organize the industrial production of newly developed chemicals and introduce the new product at
Hungarian geothermal wells.
ICPECOO
It was studied the possibilities to control the corrosion and scaling in romanian geothermal systems.
Regarding the problem of corrosion Our research takes in consideration both the method of active
protection, through the injection of cathodic current in potentiostatic regirne and that of the
corrosion inhibitors. From our works has resulted that the method of active protection is suitable in
good technico-economical conditions only for the protection of extemal sides of the system
(metallground interface) and also, of the intemal sides of some bulky equipments (metallgeothemal
fluid interface) as: degassing tanks, buffer vessel, etc.. .
Are presented the aspects regarding the conception-electrical and electrochemical diiensioning of a
active anticotrosive protection systems (current distribution, the positioning of injection anodes,
etc.) and also their constmction and their functional test. To h o w the exactly corrosiveness of the
geothermal water respectively of its origin, were determined the kinetical parameters of the
corrosion reactions to the R 37 steel/geothermal fluid interface from 14 representative wells which
operating in correlation with the mineralogical structure of these.

The conclusions of these works show that in geothermal fluid without S2- and with a small content
of S042-, the corrosion is determined primarily by the concentration of Cl-. For these geothermal
waters, in the range of temperature 30-95"C, the corrosion is increasing with the temperature
decreasing so, the damages caused by them are more important on the "cool" side of the equipments
(the output of the heat exchanger, the recirculation pipes, buffer vessels, etc...). In the geothermal
fluids having a small content of Cl- and an important one of S2- and S042- the corrosion is
determined by these concentrations and increases with temperature increasing. The most corrosive
geothermal fluids are those which have a high content of Cl-, SOd2-respectively S2-.
To have a simultaneous supervision of corrosion and scaling, it was studied the anticorrosive action
of some maleic polyelectrolytes having a wellknown antiscaling effect. Thus, it was determined the
corrosion for carbon steel R37 in direct contact wilh synthetic geothermal water in the presence and
also the absence of some polyelectrolyte additions (0.1-30 ppm) which have different structure.
From Our determinations was resulted that dependig of their structure and composition the maleic
polyelectrolytes can present a pronounced inhibition effect. They act through the braking of the
charge transfer reactions (anodics and101 cathodics) and through the modifying of the transfer
coefficient a.
From our determination it results that the maximum inhibition effect of the corrosion and scaling
too, is usually obtained for an optimal concentration of inhibitor, concentration with depend both the
geothermal temperature and chemical composition. In this context it was conceived an automatic
system (controlled in closed loop by a computer) of injection and dosing dependig of the
momentary values of the corrosion, scaling and temperature. In the system conceived by us the
adjustments is executed taking in consideration the above mentionned parameters detected by a
multifunctional transducer designed, built and tested by us. From these determinations the
conclusion is that the carbonate scale resulting from the geothermai fluid of the well no 4159 -
Oradea has the resistivity of about 120 Qm, so the impedance variation (to a signal at 100 Hz) of the
transducer is about 0.20 R/pm - signal which is enough big to be processed in the automatic system
proposed.
ICVL
Corrosion of iron and carbon steel in the geothermal fluids of Vidmntai 1 and Vidmntai 2 was
studied under laboratory conditions. The following conclusions can be made:
- the corrosion rate decreases with the immersion time of iron in the solution;
- the corrosion current density is much'higher when the rotation of electrode is applied;
- deaeration of the solution leads to decrease in the corrosion rate, especially when electrode
rotation is applied. After two hours immersion the decrease in the corrosion current in deaerated
solution is insig~ficant;
-the rises of temperature from 20 to 80C cause decrease in corrosion rate depending on the
immersion t h e . Much pronounced decrease was determined in an unstirred solution;
-saturation of geothermal fluid with CO2 causes a slight rise of corrosion rate after 1 h of
immersion;
- corrosion process inhibition is observed when increasing the chloride concentration in the sulfate
solution (pH 3) to the value l i e in the real geothermal fluid (100 g/l);
- the corrosion rate in the naturally aerated system reached a limited value (- 1.52 mA/cm2);
Conceming the formation of oxide layer on iron surface, the following conclusions can be drown:
- the thickness of oxide layer growth with the exposure time in the solution. The thichess is very
similar in the cases of aerated, deaerated and COTsaturated solutions;
- the rise of the temperature from 20 to 80C causes developing of more thick layer;
- the most thick layer at the beginning of corrosion develops in the naturally aerated solution. The
layer developed in the CO2 saturated fluid is sig~ficantthiier.

4. GENERAL CONCLUSION AND FUTURE OBJECTIVES
The work carried out for the project has provided us with a better understandiig of the corrosion-
scaliig that has taken place and represents a marked progress in each of the six following topics:
corrosion prevention, corrosion studies, scale formation and modelling, scale prevention, corrosion
and scaliig in diphasic flow conditions and corrosion and scaling monitoring.
The prevention of corrosion in low-enthalpy geothermal systems was the main concern of the
contracting parties in this project: much of the study was devoted to testing the effectiveness of
corrosion inKibitors, their conditions of use and their adaptation to geothermal fluids with different
physico-chemical characteristics. A wide range of inhibitors, both commercially avaiiable and
synthesized by certain partners, were exchanged between the contracting parties and tested under
geothermal field conditions as well as in the laboratory. The electrochemical approach
(measurement of impedance and polarization resistance) was the main tool adopted for these studies.
The prevention of corrosion is also expressed by other studies as the cathodic protection and anodic
protection of the surface distribution network. Monitoring the effectiveness of the inhibitor treatment
by adapting existing methods to geothermal fluids, as discussed in the chapter on "corrosion scaling
and monitoring", enables the early detection of anomalies so that they can be remedied. Some of the
methodologies, such as mild acidification (injecting an acidhhibitor mixture down the well in order
to dissolve the scaling), inhibitor concentration and injection frequency, are now applied to certain
geothermal operations in the Paris Basin. Non-metallic materials were also considered, and a study
was made of their behavior under geothermal conditions. Where high enthalpy is concemed, studies
continued on the process of s t e m washing (for HCl abatement); this was begun under the Joule 1
contract; on the basis of this work, a full scale washing column has been designed and will be
constmcted and tested in the near future at the Larderello field. The feasibility of a dry process (dry
abatement of HC1) was also examined and a reactor for this study is now being designed.
Corrosion studies (reaction mechanisms, effect of fluid composition, etc.) were the second most
important element of the project. The work was based on constmcting Eh-pH equilibrium diagrams
of the S-H20 and Fe-S-H20 systems. The presence of trace amounts of oxidiziig agents and
chloride ions, and their effect on corrosion and on the formation, nature and development of
scaling, were also studied when drawing up these diagrams. Studies in reconstituted, real and
modified geothermal media (both with and without the presence of an inhibitor) have made it
possible to (a) assess the effect of different parameters (pH, Oz, CO2, H2S, T, salinity, flowrate,
effective protection of corrosion products, etc.) on the variation of the corrosion rate, and (b)
determine the kinetic parameters of the corrosion reaction.
The third objective concerned the study and modeiiig of scaling. Scaliig experiments were run,
both in the presence and absence of an inhibitor, in reconstituted and real (and modified) geothermal
media in order to study the formation rate, size, morphology and composition of scaling in relation
to the principal physico-chemical parameters of the fluid. This study led to the formulation of a
mechanism for their growth and effective protection relative to theu steel support. New calculation
codes, suitable for both high and low enthalpy, were written for modeliig the scaling phenomena.
The MODEP code (dedicated to low enthalpy) proposed in the F i a 1 Report of the Joule 1 project
has been greatly improved. Today it includes Fick's laws of distribution, kinetic and thermodynamic
criteria and the precipitation of several mineral species. In addition to the formation of scaliig, the
MODEP code also simulates the corrosion of casings (a deliverable that was not initially planned,
but which turned out to be required for the studies). Further improvement of this mode1 is the basis
of a proposa1 to the European Union as part of the INCO COPERNICUS work programme in 1996.
A second code simulates the coagulation of colloidal PbS particles in the fluid vein (nucleation,
growth, distribution) and the eventual formation of scaling on the casing wall. The dynamics of the
EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314- final report 45

particles, their roughness and their mutual repulsive forces are al1 taken into consideration by the
model. A fia1 model simulates the precipitation and deposition of CaC03 on the walls of high-
enthalpy wells, a phenomenon that occurs between the bubble point and the well head. This code
calculates the bubble point and the partial gas pressures after degassing. The codes have been tested
and the results are satisfactory.
The prevention of scaling, which was considered as the fourth most important topic, was carried out
at the same time as the corrosion prevention studies. It appears that the good corrosion inibitors are
often poor scaling inhibitors and that a good CaC03 scaliig inhibitor is much less efficient in
inhibiting the deposition of mackinawite. The once again shows the necessity of adapting each
inhibitor to a specific fluid accordiig to the desired final result.
Study of corrosion and scaling in diphasic flow conditions or, more generally, the two-phase flow
studies comprised the fifth objective of the study. The velocity measurements were carried out in a
horizontal flow loop, where air-water two-phase flow developed in a 50.8 mm i.d. pipe. Regarding
the shear stress experiments, measurements were carried out at nearly atmospheric pressure, in a
newly constmcted horizontal flow loop. Liquid-to-wall shear stress, at various pipe circumferential
locations was measured using the electrodiffusion technique. At relatively small liquid flow rates,
and for gas velocity above IOmIs, the so-called "stratifiedlatomisation" flow (da) regime prevails.
The main features of this regime are the appearance of disturbance waves, the liquid droplets
entrained in the gas phase and the drastic change of the average gaslliquid interface profile from flat
to concave.
The study of corrosion and scaliig in diphasic flow conditions was undertaken on an artesian
production well, which was operating without treatment with additives. An auxiliary injection tube
was put down the well. Fitted with coupon-holders, corrosion coupons were placed at three depths:
150 m (monophase zone), 60 rn (bubbling point) and 4 m (biphase zone). Measurement of the rate
of corrosion shows a slight increase with the degassing of the fluid. The products of corrosion are
examined by using metallographic microscope. Concerning stearn washing in the well, direct
injection of an alkaline solution in the well allows protection of well casing in al1 the cases in which
a corrosive condensate may form in the well. The theoretical investigation conducted demonstrated
the feasibility of this process, in particular with regard to the phenomenon of well flooding and the
identification of the liquid flowrate which allows good protection of pipe wall at an acceptable
increase of pressure losses.
The last aims of this study was "corrosion and scaliig monitoring". In order to monitor the
corrosion rate of carbon steel and to maintain the effectiveness of a treatment by a corrosion
inhibitor in a given geothermal plant, several different methods must be used, each having its own
limitations, its advantages and disadvantages. The work done has contributed to the adaptation and
the use of three type of methods for geothermal applications. These methodes included chemical
analysis, weight loss and electrochemical methods. A methodology for the detection and assessment
of perforations in well casings was carried out: wells often penetrate fresh water aquifers which are
used as a drinking water resource in the Paris region. Following localized or prolonged corrosion of
the casing by the geothermal fluid, the casing may be pierced. Dependiig on the existence or
absence of dual completion in the area of the perforation, the geothermal fluid may enter into the
water from the adjacent aquifer, thus creating the risk of pollution of the water. M e r examination
of the various water-migration possibilities with one or two casing perforations in a production or
injection well, the different detection methods for perforations are discussed in terms of their
limitations and accuracy. In al1 cases, a logging tool is necessary to confirm the existence of a
perforation and to locate its depth.
Conceming scale monitoring, the scale removed from the well or deposited on steel coupons was
characterized by classical chemical analysis, metallographic microscopy of polished sections, X-ray

diffractometry, scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry
(EDS). The experjments show that carbon steel samples suffer fairly general corrosion. The
corrosion rate and scale thickness decrease as a function of the fluid flowrate. The inhibitor
considerably reduces both corrosion rate and scale thickness.
Electrochemical methods for the surveillance and investigation of corrosion modes and corrosion
rates in geothermal applications derive directly form the study reported above (2nd theme).
Two specific tools was developed in order to be used for experimental measurements or
interpretation of experimental data: TAFEL II is a program for computation of corrosion rate and
polarisation resistance by using the integral method. LEAC is a program for experimental data
acquisition, to assist the matrix electrode system via a multiplexing hardware system. It allows the
measurement of the current distribution andlor open circuit electrode potential.
It was studied the automatic dosing possibiity in optimal quantities of the inhibitors in geothennal
systems. So it was designed an automatic system controlled by computer through the electrical
signal given by a multifunctional sensor for corrosion, scale and temperature. This signal controls
the actuator (the assembly motor-pump) which inject the inhibitor inside the geothemal well.

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to distinct cunent from ancient bacterial activity in the wells-reservoir system. In: Proceediigs of
the International Symposium, Geothennics 94 in Europe, from Research to Development, BRGM
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HARMANDAS N.G., IGNATIADIS I., KOUTSOUKOS P.G. (1996) - Comparative study of the
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geothemal environment. Seventh six-monthly report of the JOULE il programme (contract no
geothemal systems", July 18, 1996, Paris, France, pp.53-62.
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IGNATIADIS 1. (1993a) - Experimental concentration versus time curves for the iron (II) sulphide
precipiiation reaction in partly reconstituted geothermal fluids in the presence and absence of
surfactant additive and their interpretation. First six-monthly report of the JOULE II programme
(contract no JOU2-CT92-0108, BRGMICCE DG XII), "Control of corrosion and scaling
phenomena in geothermal systems", September 93, Patras, Greece, pp. 59-106.
IGNATIADIS 1. (1993b) - Estimation of the solubility product of the iron sulphide controlling the
solubility of iron and sulphides dissolved in geothermal fluids from production weliheads in the
Paris Basin. Fust six-monthly report of the JOULE II programme (contract no JOU2-CT92-0108,
September 93, Patras, Greece, pp. 107-124.
IGNATIADIS 1. (1994) - Origins of the increased dissolved sulphide concentrations noted in
geothemal fluids at production wellheads in the south and east of the Paris basin. In: Proceediigs of
the International Symposium, Geothemics 94 in Europe, from Research to Development, BRGM
(ed), Orlans, France, 8-9 Febmary 1994, pp. 241-248.
IGNATIADIS I., ABOU AKAR A., AMALHAY M., BRAY Ph., LESUEUR H., LONGIN G.
(1994a) - Recommandations relatives au suivi de l'efficacit des traitements pai inhibiteur de
corrosion en gothermie basse nergie. Convention Ademe-BRGM 3 07 0001. Rap. BRGM R
38123, 89 p, 9 fig., 13 tabl., 3 am.
IGNATIADIS I., ABOU AKAR A., AMALHAY M. (1994b) - Methods for monitoring corrosion
and the efficiency of treatment by corrosion inhibitor on the geothemal projects of the Paris basin.

Control of corrosion and scaling in geothermal sysrems
Second six-monthly report of the JOULE II programme (contract no JOU2-CT92-0108,

Febmary 1994, Paris, France, pp. 57-72.
IGNATIADIS I., ABOU AKAR A., AMALHAY M. (1994~)- Methods for monitoring corrosion
and the efficiency of treatment by corrosion inhibitor on the geothermal projects of the Paris basin.
In: Proceedings of the International Symposium, Geothermics 94 in Europe, from Research to
Development, BRGM (ed), Orlans, France, 8-9 Febmary 1994, pp. 257-266.
IGNATIADIS I., ABOU AKAR A., AMALHAY M. (1994d) - Monitoring of corrosion and the
efficiency of treatment by corrosion inhibitor on the geothermal projects of the Paris Bassin. In:
Proceediigs du 2me Colloque Europen "Corrosion dans les Usines Chimiques et Parachiiiques,
Grenoble 21-22 Septembre 1994, CEFRACOR (ed), Paris, France, Section C2 P15-1 - P15-8.
IGNATIADIS I., PEYROT N. (1994) - Estimation of the solubility product of the iron sulphide
controlliig Fez+ and S2- solubilities in geothermal waters. Poster presentation in the 8th European
Union of Geosciences, 9-13 April 1995, Strasbourg, France, 9-30 April 1995. In: Proceediigs of
EUG8, Terra abstracts, Abstract supplement Nol, to Terra nova, Vol. 7, 1995, p. 322.
IGNATIADIS I., AMALHAY M. (1995) - Comparative study of the effectiveness of various
organic surfactants in inhibiting carbon steel corrosion in a partial reconstituted geothermal
environment. Sixth six-monthly report of the JOULE II programme (contract no JOU2-CT92-0108,
December 15, 1995, Thessaloniki, Greece, pp. 47-86.
IGNATIADIS I., AMALHAY M., COTICHE C. (1995) - Comparative study (long-term) of the
carbon steel corrosion rate in untreated and treated geothermal fluids using coupons. Sixth six-
monthly report of the JOULE II programme (contract no JOU2-CT92-0108, BRGMICCE DG XII),
"Control of corrosion and scaliig phenomena in geothermal systems", December 15, 1995,
Thessaloniki, Greece, pp. 33-46.
IGNATIADIS I., ABOU AKAR A., COTICHE C. (1996) - Analysis and consequences of bacterial
proliferation in casings and resewoirs of geothermal doublets of the Paris basin. In: Proceedings of
EUROCORR'96, Nice (France), Septembre 1996, pp. V P l - I N Pl-4.
IGNATIADIS I., AMALHAY M. (1996a) - The effect of iron sulfide deposits on corrosion of
carbon steel in a natural and treated geothennal water using electrochemical techniques and X-ray
diffractometry. In: Proceediigs of EUROCORR'96, Nice (France), Septembre 1996, pp. II P21-
1/11 P21-4.
IGNATIADIS I., AMALHAY M. (19960) - Identification of the role of iron sulfide deposits on
corrosion of carbon steel in untreated and treated geothermal environment thought electrochemical
techniques and X-ray diffractometry. In: Proceediigs of the 47th Annual Meeting of the
International Society of Electrochemistry, September 1-6, 1996, Veszprm and Balatonfred
(Hungary), pp. P6a-10.
IGNATIADIS I., AMALHAY M., ABOU AKAR A., COTICHE C. (1997) - Analyse et
consquences de la prolifration bactrienne sur les tubages et dans le rservoir @roche ou lointain)
des doublets gothermiques du bassin de Paris. Ecole thmatique CNRS "Biodtrioration des
matriaux". Saint Avit devialard, 30 septembre - 6 octobre 1995. Editions de la Physique, Les Ulis.
Biodtriotation des matriaux. L'article de 26 pages sera publi en 1997 dans le livre de l'cole
thmatique.
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rapid electrochemical tests. Seventh six-monthly report of the JOULE II programme (contract no

JOU2-CT92-0108, BRGMICCE DG XII), "Control of corrosion and scaliig phenomena in

geothermal systems", July 18, 1996, Paris, France, pp.33-51.
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prinpimo down-hole fluid sampler. Seventh six-monthly report of the JOULE II programme
(contract no JOU2-CT92-0108, BRGMICCE DG XII), "Control of corrosion and scaling
phenomena in geothermal systems", July 18, 1996, Paris, France, pp.63-70.
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concentration versus t h e curves for the iron (ii) sulphide precipitation reaction in partly
reconstituted geothermal waters and their interpretation. Poster presentation in the 8th European
Union of Geosciences, 9-13 April 1995, Strasbourg, France, 9-30 April 1995. In: Proceediigs of
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6. List of publications related to the project (1993-1996)
BRGM
ABOU AKAR A., BOENS P. (1996) - Modelling of corrosion and scaling phenomena in low
enthalpy geothermal wells. In: Proceedings of EUROCORR'96, Nice (France), septembre 1996, pp.
XV P2-11 XV P2-4.
ABOU AKAR A., BOENS P. (1995) - Modlisation des phnomnes de corrosion-dpts sur les
parois des tubages en acier des exploitations gothermales. 1. Proposition d'un modle de simulation
des phnomnes de corrosion-dpts. Rap. BRGM R 38612 GGP DR 95, 5@.
ABOU AKAR A., IGNATIADIS I., LESUEUR H. (1995). Methods for detecting perforations in
casings of wells exploiting geothermal fluids. In: Proceediigs of the World Geothermal Congress,
1995, Florence, Italy, 18-31 May 1995 (International Geothermal Association, Inc., Auckland, New
Zeland, 1995, Volumes 1 to 5), 4, pp. 2397-2402.
ABOU AKAR A., IGNATIADIS 1. (1995) - Modelling of the deposition phenomena in geothermal
wells in the Paris basin. In: Proceediigs of the World Geothermal Congress, 1995, Florence, Italy,
18-31 May 1995 (International Geothermal Association, Inc., Auckland, New Zeland, 1995,
Volumes 1 to 5), 4, pp. 2491-2496.
ABOU AKAR A., IGNATIADIS I., LESUEUR H., LONGIN G. (1994) - Risque de pollution des
nappes d'eau douce du fait des exploitations gothermales de l'aquifre du Dogger du Bassin
parisien. 4. Mthodologie de dtection des percements intervenus sur le tubage d'un puits
gothermique. Convention Ademe-BRGM 2 07 0028. Rap. BRGM R 38035,47 p., 10 tabl., 2 ann.
ABOU AKAR A., IGNATIADIS 1. (1994)- A new mode1 for iron sulfide deposition in geothermal
wells. In: Proceedings of the International Symposium, Geothermics 94 in Europe, from Research
to Development, BRGM (ed), Orlans, France, 8-9 February 1994, pp. 215- 222
ABOU AKAR A., LAFFORGUE M. (1994). Etude de la corrosion par coupons en acier au carbone
placs en zones monophasique et diphasique sur la centrale gothermique de Chelles (Seine-et-
Marne). Rap. BRGM R 37832 GGP-DR-94,91p.
AMALHAY M., IGNATIADIS 1. (1996) - Application de la difractomtrie des rayons X l'tude
lectrochimique de la corrosion de l'acier au carbone en milieu gothermal rel et trait. Journal de
physique IV,colloque C4, vol. 6, pp. 913-920.
AMALHAY M., IGNATIADIS 1. (1996) - Study of the behaviour of a carbon steel in a natural or
modified and treated geothermal environment. In: Proceedings of EUROCORR196,Nice (France),
septembre 1996, pp. II P15-ILI P15-4.
AMALHAY M., IGNATIADIS 1. (1995) - Comparative study of the effectiveness of various
organic surfactants in inhibiting carbon steel corrosion in a natural geothermal environment. In:
Ann. Univ. Ferrara, Proceediigs of the 8th European Symposium on Corrosion Inhibitors (8 SEIC)
18th-22nd September, 1995, Ferrara, Italy, no special, Sez. V, suppl. nOIO,pp. 1355-1366.
AMALHAY M., COTICHE C., IGNATIADIS 1.(1995) - Study of the electrochemical behaviour of
a carbon steel in a real and treated geothermal environment. In: Proceedings of the World
Geothermal Congress, 1995, Florence, Italy, 18-31 May 1995 (International Geothermal
Association, Inc., Auckland, New Zeland, 1995, Volumes 1 to 5), 4, pp. 2369-2374.
AMALHAY M., ABOU AKAR A., IGNATIADIS 1. (1995) - Overview of the deposition
phenomena in geothermal wells in the Paris Basin. In: Proceediigs of the World Geothermal
Congress, 1995, Florence, Italy, 18-31 May 1995 (International Geothermal Association, Inc.,
Auckland, New Zeland, 1995, Volumes 1 to 5), 4, pp. 2497-2502.
AMALHAY M. (1994) - Contribution l'tude des phnomnes de corrosion-dpt et de leur
inhibition dans les tubages en acier au carbone des puits gothermiques. Thse d'universit.
Universit de Provence Aix Marseille 1, BRGMIDRIGGP. Dcembre 1994, 216 p.

AMALHAY M., GAUTHIER B., IGNATIADIS 1. (1994a) - The influence of some physico-
chemical parameters and exploitation conditions on corrosion and scaliig in geothermal wells in the
Paris Basin. In: Proceedings of the International Symposium, Geothermics 94 in Europe, from
Research to Development, BRGM (ed), Orlans, France, 8-9 Febmary 1994, pp. 233-240.
AMALHAY M., ABOU AKAR A., IGNATIADIS 1. (1994b) - Study of the deposition phenomena
in geothermal wells in the Paris Basin. In: Proceediigs of the International Symposium,
Geothermics 94 in Europe, from Research to Development, BRGM (ed), Orlans, France, 8-9
Febmary 1994, pp.223-232.
AMALHAY M., IGNATIADIS 1. (1993) - Etude du comportement de l'acier au carbone API K55
dans le fluide gothennal dgaz. Rapport BRGM n0R37868 IRG SGN 93, 39 p.
AMALHAY M., IGNATIADIS 1. (1993) - The effects of some physico-chernical characteristics and
exploitation conditions on corrosion and scaling in geothermal wells in the Paris bassin. PEH 93,
(Physique en Herbe), Paris, France, 6-12 Juin 1993. Proceediigs, pp. 45-47.
ARFAOUI S. (1995) - Etude comparative de l'action de diffrents inhibiteurs de corrosion sur le
comportement lectrochiiique d'un acier au carbone dans un fluide gothermal reconstitu, Rapport
de stage d'ingniorat ENSEEG, 57p.
BATTAGLIA D. (1995) - Modlisation des phnomnes de corrosion-dpts dans les tubages des
puits gothermaux. Rapport de stage d'ingnieur EEIRE, 58p.
BOENS P. (1995) - Modlisation des phnomnes de corrosion-dpts sur les parois des tubages des
puits gothermiques, Rapport de stage d'ingniorat ENSEEG, 44p.
BRAY P., LESUEUR H., IGNATIADIS I., BOISDET A. (1993) - Instrumentation et tlgestion du
rservoir gothermique du Dogger du bassin de Paris. Rapport BRGM n0R37868 IRG SCiN 93, 66
p, 4 Volumes.
CORTON S. (1994) - Comportement des matriaux non-mtalliques dans une eau gothemale
contenant des additifs de limitation de son pouvoir corrosif. Rapport de stage d'ingniorat (2me
anne) de 1'Ecole Suprieure dlEnergie et des Matriaux (ESEM), soutenu le 15 dcembre 1994.
BRGMIDRIGGP. Septembre 1994, 52 p.
COTICHE C. (1994) - Etude du comportement lectrochimique d'un acier au carbone dans un
fluide gothermal rel et trait. Rapport de stage d'ingniorat (3me anne) de 1'Ecole Nationale
Suprieure de Chimie de Toulouse (ENSCT), soutenu le 22 juin 1994. BRGMIDRIGGP. Juin 1994,
50 p.
DETOC-KARIMI S., IGNATIADIS 1. (1994) - Slection et optimisation des mthodes d'analyse des
espces du soufre produites lors de l'oxydation du sulfure d'hydrogne des fluides gothermaux. In:
Proceediigs of the First International Research Symposium on "Water treatment by-products".
Communication orale N028-1, Poitiers, France, 29-30 Septembre 1994.
DETOC-KARIMI S., IGNATIADIS 1. (1994) - Kinetics of oxidation of hydrogen sulfide by
hydrogen peroxide in actual geothermal fluids. In: Proceedings of the First International Research
Symposium on "Water treatment by-products". Communication orale No28-2, Poitiers, France, 29-
30 Septembre 1994.
DEZAIACOMO 0. (1994) - Produits de corrosion en milieu gothermal rel : nature, formation,
croissance et influence sur la corrosion de l'acier au carbone. Rapport de stage de fin de Matrise de
C h i e (Universit d'Orlans) soutenu le 29 juin 1994. BRGMIDRIGGP. Juin 1994, 52 p.
DRIEUX J.J., ROQUE C., IGNATIADIS I., JULIEN E., GIROU A. (1996) - Proposition d'une
sonde de contrle des phnomnes de dpt-corrosion. Pilotage de l'injection d'un inhibiteur dans
un puits gothermique. In: Proceedings du colloque "Journes Information Eaux (JIE-96), Poitiers,
Septembre 1996 (France) pp. P18-11P18-4.
DRIEUX J.J., JULIEN E., GIROU A., IGNATIADIS I., ROQUE C. (1996) - Electrochemical
device for the prevention of corrosion-scaliig phenomena in geothermal installations. In:
Proceedings of EUROCORR196,Nice (France), septembre 1996, pp. II OR15-ID1 OR15-4.

GAUTHIER B., IGNATIADIS 1. (1994) - Relation between MglCa ratio and sulfide concentration
in geothermal fluids at wellheads in the Paris basin. Use of their variation versus time and flowrate
to distinct current from ancient bacterial activity in the wells-resewoir system. In: Proceedings of
the International Symposium, Geothermics 94 in Europe, from Research to Development, BRGM
IGNATIADIS I., AMALHAY M., ABOU AKAR A., COTICHE C. (1997) - Analyse et
consquences de la prolifration bactrienne sur les tubages et dans le rservoir (proche ou lointain)
des doublets gothermiques du bassin de Paris. Ecole thmatique CNRS "Biodtrioration des
matriaux". Saint Avit devialard, 30 septembre - 6 octobre 1995. Editions de la Physique, Les Ulis.
Biodtriotation des matriaux. L'article de 26 pages sera publi en 1997 dans le livre de l'cole
thmatique.
IGNATIADIS I., AMALHAY M. (1996) - Identification of the role of iron sulfide deposits on
corrosion of carbon steel in untreated and treated geothermal environment thought electrochemical
techniques and X-ray diffractometry. In: Proceediigs of the 47th Annual Meeting of the
International Society of Electrochemistry, September 1-6, 1996, Veszprm and Balatonfred
(Hungary), pp. P6a-10.
IGNATIADIS I., ABOU AKAR A., COTICHE C. (1996) - Analysis and consequences of bacterial
proliferation in casings and reservoirs of geothermal doublets of the Paris basin. In: Proceedings of
EUROCORR'96, Nice (France), Septembre 1996, pp. V P l - I N Pl-4.
IGNATIADIS I., AMALHAY M. (1996) - The effect of iron sulfide deposits on corrosion of
carbon steel in a natural and treated geothermal water using electrochemical techniques and X-ray
diffractometry. In: Proceedings of EUROCORR'96, Nice (France), Septembre 1996, pp. II P21-
1/11P21-4.
IGNATIADIS I., CHERADAME J.M., DAUMAS S. (1996) - Comparative tests to determine the
effectiveness of various bactericides on sulfate reducing bacteria in geothermal fluids. In:
Proceedings of EUROCORR'96, Nice (France), Septembre 1996, pp. V OR8-1N ORS-4.
IGNATIADIS 1. (1994) - Origins of the increased dissolved sulfide concentrations noted in
geothermal fluids at production wellheads in the south and east of the Paris basin. In: Proceediigs of
the International Symposium, Geothermics 94 in Europe, from Research to Development, BRGM
IGNATIADIS 1. (1994) - Problmes de matriaux dans l'exploitation de la ressource gothermique
du bassin parisien : historique, tudes et perspectives. In: Proceedings of the European Technology
Forum (Les entretiens de la Technologie). Communication orale, Atelier Matriaux-Energie. Palais
de Congrs, Paris, France, 15-16 Mars 1994.
IGNATIADIS I., LE DINH BA0 B. (1994) - Laboratory studies and field tests in a geothermal
environment for the determination of anti-corrosion properties of silica fms deposited on carbon
steel. In: Proceedimgs of the International Symposium, Geothermics 94 in Europe, from Research to
IGNATIADIS I., ABOU AKAR A., AMALHAY M., BRAY Ph., LESUEUR H., LONGIN G.
(1994a) - Recommandations relatives au suivi de l'efficacit des traitements par inhibiteur de
corrosion en gothermie basse nergie. Convention Ademe-BRGM 3 07 0001. Rap. BRGM R
38123, 89 p, 9 fig., 13 tabl., 3 ann.
IGNATIADIS I., ABOU AKAR A., AMALHAY M. (1994b) - Methods for monitoring corrosion
and the eficiency of treatment by corrosion inhibitor on the geothermal projects of the Paris basin.
In: Proceedimgs of the International Symposium, Geothedcs 94 in Europe, from Research to
IGNATIADIS I., ABOU AKAR A., AMALHAY M. (1994~)- Monitoring of corrosion and the
efficiency of treatment by corrosion inhibitor on the geothermal projects of the Paris Bassin. In:
EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-03 74 - final report 57

Control of corrosion and scalingin geothermal systems
Proceedings du 2me Colloque Europen "Corrosion dans les Usines Chimiques et Parachiimiques,
Grenoble 21-22 Septembre 1994, CEFRACOR (ed), Paris, France, Section C2 P15-1 - P15-8.
IGNATIADIS I., PEYROT N. (1994) - Estimation of the solubility product of the iron sulfide
controlling Fe2+ and ~ 2 solubilities
- in geothermal waters. Poster presentation in the 8th European
Union of Geosciences, 9-13 April 1995, Strasbourg, France, 9-30 April 1995. In: Proceedigs of
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Geosciences, 9-13 April 1995, Strasbourg, France, 9-30 April 1995. In: Proceedigs of EUG8,
Terra abstracts, Abstract supplement Nol, to Terra nova, Vol. 7, 1995, p.72.
PEYROT N. (1993) - Contribution i'tude de la cintique de formation des sulfures de fer en
solutions gothermales reconstitues. Rapport de stage de DEA de Cintique Chimique Applique,
Universit d'Orlans-BRGM, 28 juin 1993, 48 p.
CEBELCOR
SINGH A.K., POURBAIX A. (1996a) - E-pH diagrams for the Fe-S-Hz0 system", to be published.
SINGH A.K., POURBAIX A. (1996b) - Corrosion of carbon steel in the presence of sulfides and
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Interna1 Cebelcor report (1996).
AMALHAY M., POURBAIX A. (1997) - Contribution l'tude de la corrosion localise du fer et
de l'acier 13% Cr en milieu H2S. Rapports Techniques de Cebelcor.
AMALHAY M., POURBAE A. (1997) - Contribution to the study of localized corrosion of iron
and 13%Crstainless steel in H2S environment. To be submitted to Corrosion Science.
CPERI
ANDRITSOS N., KARABELAS A.J. (1995) - An experimental study of sulfide scale formation in
pipes. In: Proceedings of the WORLD GEOTHERMAL CONGRESS 1995, ed. E. Barbier et. al.,
Florence, Italy, 18-31 May, 1995. pp. 2469-2474.
KOSTOGLOU M., KARABELAS A.J. (1994) - Evaluation of zero order methods for simulating
particle coagulation. J. Colloid Inte@ace Sei. 163, pp. 420-431.
KOSTOGLOU M., ANDRITSOS N., KARABELAS A.J. (1995) - Flow of supersaturated solutions
in pipes. Modelig bulk precipitation and scale formation. Chem. Engng Comm. 133, 107-131.
PARAS S.V., KARABELAS A.J. (1992) - Measurements of local velocities inside thin liquid films
in horizontal two-phase flow. Experiments in Fluidr 13, 190-198.
PARAS S.V., VLACHOS N.A., KARABELAS A.J. (1994) - Liquid layer characteristics in
stratified-atomization flow. Int. J. Multiphase Flow 20, 5, 939-956.
PARAS S.V., VLACHOS N.A., KARABELAS A.J. (1996) - LDA measurements of local
velocities in horizontal Stratifiedlatomization Two-phase Flow. In: Proceedigs of the International
Congress of Chemical & Process Engineering, Praha, Chech Republic, August 25-39, 1996.
VLACHOS N.A., PARAS S.V., KARABELAS A.J. (1994) - Liquid-to-Wall Shear Stress
Distribution in Stratifiedlatomization Flow. Accepted for publication Int. J. Multiphme Flow, 1996.
58 EEC-DG Xll-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

Control o f corrosion and scaling in geotherrnal systems
CPR
ANDREUSSI P., MINERVINI A., PAGLIANTI A., SABATELLI F. (1994) - Two-Phase Flow of
Brine in Long Pipelines: Analysis of Field Experiments. Geothermics, 23, p. 33-41, JOUG-0005-C.
ANDREUSSI P., PAGLIANTI A., PASQUALETTI A.(1995) - Design of an Absorption Column
for Steam Washing, Proc. World Geothermal Congress, Firenze.
MARINI L., GUIDI M., ANDREUSSI P., CORSI R. (1994) - The Computation of Dew Point and
Liquid Composition of Geothermal Steam", Geothermics, 23, p. 233-255, JOUG-0005-C.
NARDINI G., PAGLIANTI A., VIVIANI E. (1993) - Abatement of Hydrogen Chloride in
Structured Packiigs. In Proc. Geothermal Resources Council, S. Francisco, p. 387-393, JOUG-
0005-C.
NARDINI G., PAGLIANTI A., TRAVERSARI F., MONDELLO B. (1994) - An Analysis on the
Efficiency of Vane Type Demisters. In Geothermal Resources Council, Salt Lake, p. 543-548,
JOUG-0005-C.
PAGLIANTI A., VIVIANI E., BRUNAZZI E., SABATELLI F. (1996) - A Simple Method to
Compute Hydrogen Chloride Abatement in Geothermal Power Plants", Geothermics, 25, p. 37-62.
SOLDATI A., ANDREUSSI P. (1995) - On the Development of a Mechanistic Mode1 for Vertical
Amular Two Phase Flow, Proc. Second Italian Conference on Chernical and process Engineering,
Florence, May 15-17.
SOLDATI A., ANDREUSSI P. (1996) - The Influence of Coalescence on Droplet Transfer in
Vertical Annular Flow, Chem. Engng. Sci., 51, p. 353-363.
VIVIANI E., PAGLIANTI A., SABATELLI F., TARQUIN1 B. (1995) - Abatement of Hydrogen
Chloride in Geothermal Power Plants", In Proc. World Geothermal Congress Firenze, p. 2421-
2426.
ICEIHTCP
Andritsos N., Kontopoulou M., Karabelas A.J., Koutsoukos P.G. (1997) - Calcium carbonate
deposit formation under isothermal conditions. Can J. Chem. Eng. In Press.
Harmandas N., Koutsoukos P.G. (1997) - The formation of iron (ii) sulfides in aqueous solutions.
J.Crysta1 Growth, In Press.
Klepetsanis P.G., Lampeas N., Kioupis N., Koutsoukos P.G. (1995) - The effect of mineral
deposits on stainless steel. In: Minera1 Scale Formation and Inhibition, Ed. Z. Amjad, Plenum
Press, New York, 1995, pp. 131-144.
Klepetsanis P.G., Drakia P., Koutsoukos P.G. (1995) - The calcite-hydroxyapatite system. Crystal
growth studies in aqueous solutions. In: Minera1 Scale Formation and Inhibition, Ed. Z. Amjad,
Plenum Press, New York, 1995, pp. 251-260.
Kobotiatis L., Tsikrikas Ch., Koutsoukos P.G. (1995) - Investigation of the corrosion of Al-7075 in
NaCl. Effect of the oxalate anions. Corrosion, vol. 51, pp. 19-29.
Kobotiatis L., Kioupis N., Koutsoukos P.G. (1997) - The electronic properties of the passive films
grown on AA7075 in solutions containing oxalate and chromate. Corrosion, In Press.
Lampeas N., Koutsoukos P.G. (1994) - The importance of the solution pH in the corrosion of
aluminium in aqueous chloride media. Corrosion Science, vol. 36, pp. 1011-1025.
Malollari 1. Xh., Klepetsanis P.G., Koutsoukos P.G. (1995) - Precipitation of strontium sulfate in
aqueous solutions at 25C. J. Cystal growth, vol. 155, pp. 240-246.
Sabbides Th.G., Koutsoukos P.G. (1993) - The crystallization of calcium carbonate in artificial
seawater; role of the substrate, Journal of Crystal Growth, vol. 133, pp. 13-22.
Sabbides Th.G., Koutsoukos P.G. (1995) - The dissolution of calcium carbonate in the presence of
magnesium and inorganic orthophosphate. In: Minera1 Scale Formation and Inhibition, Ed.
Z. Amjad, Plenum press, New York, 1995, pp. 73-86.

Control o f corrosion and scaling in geothermal systerns
Sabbides Th.G., Koutsoukos P.G. (1996) - The effect of surface pretreatrnent with inorganic
orthophosphate in the dissolution of calcium carbonate. J. Cqstal Growth, vol. 165, pp. 268-272.
Symeopoulos B.D., Koutsoukos P.G. (1993) - Radioanalytical monitoring of the formation of
barium sulfate in aqueous solution. J.Radioanalytical and Nuclear Chemistry, vol. 173, pp. 23-26.
Symeopoulos B.D., Koutsoukos P.G. (1993) - The use of radioanalytical methods in nucleation and
crystal growth studies: the barium sulfate system. Appl. Radiat. Isot., vol. 44, pp. 894-896.
BBPDICM
Chitanu G.C., Anghelescu-Dogam A.G, Carpov A. (1994) - Chemical reactions on maleic
Anhydride Copolymers. Semiamidation. IXfi Session of Scientific Communications "Progress in the
Polymer Science" at the Days of the Romanian Academy in Iasi, October 6-9, 1994, Iasi
(Romania).
Chitanu G.C., Lingvay I., Zaharia I.L., Anghelescu-Dogam A.G., Carpov A. (1995) - Some Data
Concerning the Anticorrosion Activity of Maleic Polyelectrolytes. First International Symposium on
Polyelectrolytes, Polyelectrolytes, Potsdam '95, September 18-22, 1995, Potsdam (Gemany).
Chitanu G.C., Ligvay I., Anghelescu-Dogam A.G., Zaharia I.L. (1995) - Maleic derivatives for
antocorrosion treatment in geothermal systems. Xfi Session of Scientific Communications "Progress
in the Polymer Science" at the Days of the Romanian Academy in Iasi , October 5-7, 1995, Iasi
(Romania).
Lingvay I., Chitanu G.C., Pacala C., Carpov A. (1994) - Contributions to prevent the corrosion and
the depositions in freezers with sea water. Proceedings of International Conference on UK
Corrosion and EUROCORR '94, Bournemouth, UK.
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corrosion and scale in heat exchangers with untreated water. 7th Conference on Physical Chemistry,
September 21-23, 1994, Bucharest (Rornania).
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Derivatives of Maleic Anhydride Copolymers. IXh Session of Scientific Communications "Progress
in thePolymer Science" at the Days of the Romanian Academy in Iasi, October 6-9, 1994, Iasi
(Romania).
Patent Applications:
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anhydride copolymers - Appl. no. C 1366/12.08. 1994.
Chitanu G.C., Zaharia I.L., Anghelescu-Dogam A., Carpov A. (1994) - Process of obtaining some
maleic anhydride-methylmethacrylate copolymers or terpolymers - Appl. no. C 1709/25.10.1994.
Chitanu G.C., Zaharia I.L., Anghelescu-Dogam A.G., Carpov A. (1995) - Process of synthesis of
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anhydride-N-vinyl-pyrrolidone copolymers and terpolymers - Appl. no. C/01004/06.05.1996.
Chitanu G.C., Zaharia I.L., Anghelescu-Dogam A.G., Carpov A. (1996) - Process of synyhesis of
some organic salts of some copolymers with carboxylic groups - Appl. no. C/01060/23.05.1996.
CAEL
Caire J.P., Juncu Gh., Cotarta V., (1996) - A cylindrical tanks inner cathodicaly protected with
extemal current source. Oral commu~cationto "Electrochemistry a Frontier Field of Theoretical
and Practical Interest" - 31 October - 3 November 1996, Cluj Napoca - Romania.
Cotaaa V., Juncu Gh. (1997) - A kinetic corrosion parameters in geotermal water solving with
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protected, submitted to J. Appl. Electochemistty.

Juncu Gh., Cotarta V., Caire J.P. (1997) - Modlisation numrique de la protection cathodique de
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Montral, Canada, 2-5 juillet 1997.
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ICPE-CO0
see BBPDICM
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corrosion in geothermal fluid from west-Lituanian aquifers. In: Lietuvos mokslas ir pramone.
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Juzeliunas E., Leinartas K., Samueleviciene M., Miecinskas P. (1997) - EQCM study of iron
corrosion in geothermal fluid from west-Lituanian aquifers. Chemijia (ISSN 0235-7216) (accepted).

7. ANNEXES (Figures)
test 6
do tirne h
Figure 1: Redox potential (on Au) versus time. under N2, H2S and air.
(in 0.35 M NaCI)
-0.2 1 test 7
110 $0 30 do
time, h
PH
air
6 - air
5-
4 - , H2S I
r
3
O 110 $0
,
30 40
time. h
Figure 2: Redox potential (on Pt) and pH versus time. under

air and H2S (in 0.35M NaCI)
a42028.d~

Control of Corrosion and Scaling

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Control of Corrosion and Scaling

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DRAFT

CONTROL OF CORROSION AND SCALING

Project coordinated by BRGM (1. Ignatiadis)

Research funded in part by

Date: November 20th. 1996

PRESENTATION OF THE FINAL REPORT OF THE CONTRACTORS

JOULE II Project, contract Nos. JOU2-CT92-0108 and CIPD-CT93-0314

The 10 partners of the programme are:

1. BRGM, Research Division, Department of Geotechnical Engineering and Minera1 Technology

2. CEBELCOR, Centre Belge de 1'Etude de la Corrosion, Bmssels, Belgium

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 1

3. Chemical Process Engineering Research Institute (CPERI), Thessaloniki, Greece

4. Consorzio Pisa Ricerche, Centro TEA (CPR), Pisa, Italy

6. Bioactive and Biocompatible Polymers Department of the Petm-Poni Institute of

7. Computer Aided Electrochemistry Laboratory (CAEL) of the "Politechnica" University of

8. Central Research Institute for Chemistry (CRIC), Budapest, Hungary

9. Electrochemical Technologies and Active Anticorrosive Protection Laboratory of the Research

10. Institute of Chemistry (ICVL), Vilnius, Lithuania.

2 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0374 - final report 3

4 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 5

6 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final report 7

1. Introduction .Aim of the research .....................................................

2 . Work performed. results and discussion ..............................................

3. Preliminary conclusions ..................................................................

4 . General conclusion and future objectives .............................................

6 . List of publications related to the project (1993-1996) .............................

7 . Annexes: (figures) .........................................................................

8 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 .final report

1. INTRODUCTION - AIM OF THE RESEARCH

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 9

10 EEC-DG Xll-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 11

12 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 13

2. WORK PERFORMED, RESULTS AND DISCUSSION

2.1. Corrosion prevention

14 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 15

16 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 19

2.2. Corrosion studies

20 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 21

22 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final report 23

24 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final repori

2.3. Scale formation and modelling

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374 - final repori 25

- the establishment of different kinetic regimes as a function of diffusion length;

26 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report 27

28 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0374- final report

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0374 - final report 29

. the carbon dioxide hydrolysis

. the electroneutrality balance

30 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

2.4. Scale prevention

EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0708 and CIPD-CT93-0314 - final report 31

2.5. Corrosion and scaling in diphasic flow conditions

34 EEC-DG XII-Joule Programme-contract Nos JOU2-CT92-0108 and CIPD-CT93-0314 - final report

2.6. Corrosion and scaling monitoring