Geothermics 31 (2002) 501–517

www.elsevier.com/locate/geothermics

Modelling and experimental validation of

H2S emissions in geothermal power plants
Aldo Baldaccia, Elisabetta Brunazzib,*,
Chiara Gallettib, Alessandro Pagliantib
a
Enel GreenPower, Via Andrea Pisano 120, I-56122 Pisa, Italy
b
Laboratory of Process Equipment, Department of Chemical Engineering, Industrial Chemistry
and Materials Science, University of Pisa, Via Diotisalvi 2, I-56126 Pisa, Italy

Received 23 October 2001; accepted 4 February 2002

Abstract
A commercial computer software, used to model and simulate geothermal power plants,
has been investigated by comparing simulation outputs with field data of existing plants.
Although most simulation results were in good agreement with the field data, the program
failed when predicting the H2S distribution between the plant streams. The computer program
has, therefore, been partly modified on the basis of pilot-scale experiments directed at inves-
tigating the H2S behaviour in the two main plant sections, i.e. the direct contact condenser
and the cooling tower. The modified version fits the field data well and is a useful tool for
assessing methods to reduce the environmental impact of releasing H2S into the atmosphere.
# 2002 CNR. Published by Elsevier Science Ltd. All rights reserved.
Keywords: Geothermal plant emissions; Hydrogen sulphide partitioning; Modelling

1. Introduction

One of the most important environmental impacts related to the use of geothermal
energy is the emission of hydrogen sulphide, H2S (Sanopoulos and Karabelas, 1997).
In the present work, hydrogen sulphide partitioning in the gas or vapour and liquid
streams of a geothermal plant has been investigated using data from Enel Green-
Power plants located in Tuscany (Italy). Enel GreenPower is the company of the

* Corresponding author. Tel.: +39-050-511-213; fax:+39-050-511-266.

E-mail address: e.brunazzi@ing.unipi.it (E. Brunazzi).

0375-6505/02/$22.00 # 2002 CNR. Published by Elsevier Science Ltd. All rights reserved.
PII: S0375-6505(02)00008-1
502 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Nomenclature

CG H2S concentration in the gaseous stream (mg/m3)

CL H2S concentration in the liquid stream (mg/l)
VG specific gas load [m3/(h.m2)]

Greek symbols

absorption efficiency

Subscripts
in incoming stream
out outgoing stream

Enel Group (the main Italian electric utility) responsible for electricity generation
from renewable sources (geothermal, hydro, wind, photovoltaic, etc.).
The power plants considered in this work are fitted with steam condensing tur-
bines. A typical scheme is shown in Fig. 1. The steam coming from the geothermal
well is fed to a separator, where the liquid content is removed from the steam frac-
tion and is drained to a basin. The outgoing vapour is expanded in a turbine down
to approximately 0.1 bar and then fed to the direct contact condenser. This con-
denser consists of a horizontal cross-flow section followed by a vertical counter-flow
section, in which water from the cooling tower is atomised by nozzles. The con-
densate is recirculated to the cooling tower, while the non-condensable gases exiting
the condenser are compressed up to about 0.3 bar in a first compression stage. After

Fig. 1. Sketch of a geothermal plant.

 A. Baldacci et al. / Geothermics 31 (2002) 501–517 503

Table 1
Composition (mg/kg) of the average steam content of the wells of the Larderello and Travale-Radicondoli
fields

H2O CO2 H2 H2S CH4 N2 NH3 H3BO3

Larderello 952,980 45,190 50 790 270 140 195 385

Travale-Radicondoli 971,320 27,920 5 180 250 235 40 50

having been cooled by cooling tower water in an intercooler, the gases are brought
to a pressure of 1.02 bar in the final compression stage before being discharged into
the atmosphere. This constitutes the ‘‘primary emission’’, while the ‘‘secondary
emission’’ is represented by the gaseous emission released from the cooling tower.
The liquid collected in the basin, which also comprises in part cooling tower water,
is reinjected into the geothermal field.
A computer program, designated ‘‘CNDSR’’ (Weres, 1983a), has been used to
simulate the behaviour of some geothermal plants. By comparing the obtained out-
puts with the field data from these plants, it was found that, although most simula-
tion results were in good agreement with field data, the program was unable to
predict the H2S concentration in the liquid and gaseous streams with sufficient
accuracy (Weres, 1983b, 1984a, 1984b).
In order to understand how the H2S is distributed between the liquid and the
gaseous streams of geothermal plants, pilot-scale experiments were carried out by
simulating conditions in the direct contact condenser and the cooling tower. In
particular, an estimate was made of the effect of some operating parameters (such as
the pH of the solutions) on the concentrations of the pollutant H2S in the gaseous
emissions.
The CNDSR program was slightly modified to account for the results of the pilot-
scale experiments, and the performance of the modified version of the computer
program was validated against field data from the plants.

2. The geothermal plants

The geothermal plants considered in this work have power ratings ranging from 8
to 60 MW. They are located in Tuscany, in the geothermal fields of Larderello/
Travale-Radicondoli and Mount Amiata.
Table 1 reports the typical chemical composition of the fluid extracted in the
Larderello/Travale-Radicondoli area. The fluid is a gas-steam mixture with tem-
perature in the range of 150–260
C. The gas content ranges from 1 to 20% (in
weight), with an average of 5%. The average flow rate from a well is about 5 kg/s
and the pressure at the wellhead can vary from 5 to 70 bar, which means that it is
quite difficult to generalise the steam composition data.
Table 2 reports typical data for geothermal plants of 8, 20 and 60 MW power,
respectively. The power plants are designated by capital letters.
504 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Table 2
Typical data for geothermal plants with 8, 20 and 60 MW capacity

Geothermal plant A B, C, D, E, F G

Power 8 MW 20 MW 60 MW

Turbine
Steam flow rate (t/h) 55–72 55–110 400
Gas in the steam (wt.%) 2.7–3.4 2–12 2–5
H2S in the gas (wt.%) 1.2–2.4 1–3 1–3
Pressure of the inlet steam (bar) 7–11 5–20 5–12
CO2 in the gas (wt.%) 96–98 96–98 96–98
T max in the inlet steam (
C) 200 280 260
Pressure of the discharged steam (bar) 0.08 0.08–1 0.08
Condenser
Flow rate of the inlet water (m3/h) 2400–3200 2400–4800 20,000
Temperature of the inlet water (
C) 25 25 25
Temperature of the outlet water (
C) 35 35 35
Compressor
Non-condensable gas flow rate (t/h) 1.8–2.5 1.5–13.5 4.9–20
Temperature of the inlet gas (
C) 26 26 26
Pressure of the inlet gas (bar) 0.07 0.07 0.07
Temperature of the discharged gas (
C) 176 175–225 175–225
Pressure of the discharged gas (bar) 1.1 1.1 1

T cooling water (
C) 7–10 7–10 7–10
Cooling tower
Cooling water flow rate (m3/h) 14002 3000–6000 10,000–20,000
Temperature of the inlet water (
C) 35 35 35
Temperature of the outlet water (
C) 25 25 25
Flow rate of the saturated air (m3/h) 106 106–2.5106 13106
Cells number 2 2–3 8
Max dimension of one cell (mm) 11.612.5 12.614.4 16.217
Max total height (m) 16.5 18 20

3. The pilot-scale experimental apparatus

Pilot-scale experiments of desorption and absorption operations were performed

to reproduce the desorption of H2S into the air from the liquid cooled in the cooling
tower (desorption experiments) and the absorption of H2S from steam into the
cooling liquid in the direct contact condenser (absorption experiments). Attention
was mainly focused on the effects of the operating parameters, such as the pH of the
solutions, on the distribution of H2S between liquid and gaseous phases.
The test rig was set up at the Department of Chemical Engineering, Industrial
Chemistry and Materials Science, University of Pisa, Italy. The experimental appa-
ratus consisted mainly of a packed column, which was used to contact the gaseous
and the liquid streams both in the desorption and the absorption experiments. The
column was 2 m high with an inner diameter of 100 mm and was equipped with
nozzles reproducing the working conditions either in the direct contact condenser or
in the cooling tower. The packing material reproduced the polypropylene grids
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 505

inside Enel cooling towers and provided a specific surface area of 39.5 m2/m3. The
experimental loop is shown in Fig. 2.
In the desorption experiments, air at room conditions is compressed up to 6 bar
using the centrifugal compressor P1 (which permits flow rates up to 280 Nm3/h) and,
after being separated from the condensate in D1, is accumulated in D2. The air
leaving D2 passes through filter F1 and is expanded to 3 bar through valve V1
before feeding packed column C1. The flow rate is measured by a set of rotameters,
each of which is fitted with shut-off and control valves. The aqueous solution con-
taining sulphides to be stripped was charged in tank D4. If desorption experiments
were performed on high pH values, the solution could be directly fed to the top of
the column by volumetric pump G1. In the case of desorption experiments on low
pH values, an acid solution was charged in a second tank, D5, and mixed, just
upstream of the column inlet, with the aqueous solution containing sulphides com-
ing from D4. By adjusting the flow rates, the resulting stream pH could be varied
from a value of 6.7 to 8.5, which represents the typical range observed in real geo-
thermal plants. The second line from D5 was used to reduce the pH of the liquid
feeding the column, rather than obtaining low pH values directly in D4, in order to
avoid sulphide stripping through contact with air. The liquid stream exiting the
packed column was drained to trap D3, containing sodium hydroxide, in order to
avoid air infiltration and to prevent the sulphides from stripping into the environ-
ment. The air exiting from the top was released through the chimney, B1. The
experimental procedure consisted of preparing the sulphide solutions by dissolving
defined amounts of nonahydrate sodium sulphide in known volumes of water and
correcting the pH value, by adding NaOH where necessary. The liquid solution was
then fed to the column by pump G1 or, in the case of low pH values, by pumps G1
and G2. Once steady operating conditions were achieved, samples of both the gas-
eous and liquid streams were taken and their sulphide concentrations analysed.
The absorption experiments were performed using the same packed column as for
the desorption experiments. The experimental loop was modified by inserting a
device for adding H2S into the gaseous stream upstream of column C1. This device
consists of a stripping column with an inner diameter of 90 mm, slightly inclined
with respect to the horizontal. The column was fed with two liquid streams, one
containing sodium sulphide and the other hydrochloric acid. H2S was produced by
the reaction and was carried into the air stream, which was fed to the packed col-
umn. Two sample systems were inserted in the gaseous line, one upstream and the
other downstream of the column C1, consisting of traps containing 0.1 M NaOH. In
the liquid streams, the sample systems consisted of valves for collecting liquid in 100
cm3 beakers containing 25 cm3 of 0.1 M NaOH. In the NaOH trapping solution,
sulphides are totally dissociated as S2-. The experimental procedure consisted of
preparing the sulphide solutions by dissolving defined amounts of nonahydrate
sodium sulphide in known volumes of water. The absorbing liquid stream was pre-
pared by filling a tank and adjusting the pH by adding NaOH or HCl. The air
stream was then started up, the flow rate was adjusted using a rotameter, and the
diaphragm pump that feeds the sulphide solution was turned on. The 1 M HCl
solution was added to a ‘‘T’’ pipe downstream of the diaphragm pump. The pump
 506
A. Baldacci et al. / Geothermics 31 (2002) 501–517
Fig. 2. Experimental apparatus for desorption and absorption tests.
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 507

feeding the absorbing solution was started up, and the flow rate was regulated on the
basis of the rotameter indication. Once steady operating conditions were reached,
samples were taken of both the gaseous and liquid streams and their sulphide con-
centrations analysed.
The flow rates used in the pilot-scale experiments simulate the operating condi-
tions of a typical geothermal plant (plant ‘‘A’’) situated in the Larderello field, with
a power capacity of 8 MW. As regards the cooling tower, normal air flow rate was
1,000,000 m3/h and the water flow rate was 1400 m3/h for a tower cross-sectional
area of 145 m2. This means there was a specific air load of 6900 m3/(h.m2) and a
specific liquid load of 9.6 m3/(h.m2). By considering the cross-sectional area of the
pilot-scale desorption column, gas and liquid flow rates of 50 m3/h and 75 l/h, respec-
tively, were obtained. Regarding the direct contact condenser, the non-condensable
gas flow rate of 1968 kg/h and the cooling water flow rate of 1400 m3/h [specific
loads of 71.4 m3/(h.m2) and 590.6 m3/(h.m2), respectively], were scaled down to the
cross-sectional area of the absorption column to yield a non-condensable gas
flow rate of 4.6 m3/h and a liquid flow rate of 550 l/h. Only the vertical part of the
condenser was considered, which had a cross-sectional area of 19.6 m2.
The sulphide analysis was made by spectrometry, using a HACH test-kit. This is
based on the reaction between sulphides and N,N-dimethyl-p-phenylenediamine
sulphate to form methylene blue. The absorbance is measured at 665 nm wavelength
in a Perkin-Elmer UV/VIS Lambda 3B spectrophotometer. The method could only
be used for sulphide concentrations up to 0.6 mg/l, so the samples had to be diluted
by adding distilled water.

4. The CNDSR simulation program

The CNDSR simulation code, written in FORTRAN by Weres (1983a), permits

the simulation of a geothermal plant. The software can either be applied to a single
plant section or to the entire power plant. These two investigation methods are
called ‘‘ONEBOX’’ and ‘‘MULTIBOX’’ procedures. In the ONEBOX procedure,
the single plant unit is modelled as a Continuous Stirred Tank Reactor (CSTR),
assuming that the outgoing streams are in thermal and chemical equilibrium. In the
MULTIBOX procedure, the whole power plant is modelled as interconnected sec-
tions (‘‘boxes’’), and the distribution of the components between the gaseous and the
liquid streams is computed for each ‘‘box’’.
The CNDSR considers 13 variables: water, heat, hydrogen sulphide, ammonia,
combined carbon dioxide (as carbonic acid, bicarbonate and carbonate), free carbon
dioxide, sulphur dioxide, boric acid, oxygen, nitrogen, thiosulphuric acid, sulphuric
acid and sodium hydroxide. For each box, the program calculates the water dis-
tribution between the gaseous and the liquid phases, the partial pressures of water
and gases, the pH and the concentration of the components. All of the chemical
reactions and the phase distribution relationships are modelled assuming total equi-
librium: the only exception is the CO2 hydration reaction, which could be computed
either at steady state or considering the kinetics of the reaction. If the latter option is
508 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Fig. 3. Box model of a typical geothermal plant.

chosen, the value of the contact time between the liquid and the gaseous phases in
the plant must be given in the input section.
The program is structured in two sections, each built up from subroutines. The
‘‘KINBOX’’ section calculates the chemical steady state, while the ‘‘FLOWS’’ sec-
tion estimates the transfer of the chemical compounds between the model boxes.
The CNDSR was applied, using the MULTIBOX procedure, to typical geother-
mal plants, modelling them by ‘‘boxes’’ as shown in Fig. 3 (Mariani, 1996). The
TURB box collects the steam coming from the turbine. This box works as an input
box, because it contains the properties of the fluid feeding the plant, and does not
represent a real unit. The steam is then fed to the MC1 box (the direct contact con-
denser). The liquid phase leaving MC1 is drained to the HWEL box, while the
vapour phase is fed to the IC1 box, which represents the intercooler. The outgoing
liquid phase from IC1 is drained to HWEL, which collects the condensate before
feeding the cooling tower. Non-condensable gases from IC1 are discharged into the
output VENT box. The cooling water used in MC1 and IC1 comes from the BASI
box, which represents the cooling tower basin, and it is shared appropriately
between the two boxes (92% of the water is fed to MC1, while 8% goes to IC1). The
air feeding the cooling tower comes from AIRI and, after being mixed with air
coming from the SEPA box, is finally fed to the TOR box. In order to simulate a
real cooling tower, it was assumed that a volume equal to 10% of all the saturated
air leaving the tower will be recirculated back to the tower inlet.

5. Experimental results

Table 3 reports the experimental results obtained by the desorption operations.

The specific gas load that simulates the operational cooling tower is 6900 m3/(h.m2),
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 509

Table 3
Desorption experiments: specific liquid load of 9.6 m3/(h.m2)

Specific gas flow rate Liquid CL,in CL,out CG,out CL,out/CL,in

[m3/(h.m2)] pH (mg/l) (mg/l) (mg/m3) (%)

6900 6.4 44.5 21.98 10.5 49.3

6900 7.3 47.98 27.78 7.1 58
6900 8.7 76.2 53.2 13.1 69.8
6900 9.5 69.65 54.93 11.4 78.8
6900 10.3 81.23 73.8 4.8 90.8
6900 10.8 88.4 85.7 3.25 96.9
2885 6.8 9.93 3.89 7.8 39
2885 7.3 39.5 18.7 23 47
2885 7.7 24.2 13 9.3 53
2885 7.9 24.5 14.4 10 58
2885 8 26.26 15.32 3.3 60
2885 8.2 35.1 24.2 7.2 69
2885 9.6 59.9 52.6 3.1 87

Fig. 4. Desorption experiments: comparison between experimental data [specific liquid load of 9.6 m3/
(h.m2) and two different specific gas loads] and computed data using the CNDSR program. (CL=[H2S] in
liquid).

but another set of tests was also performed using a different specific gas load, 2885
m3/(h.m2), in order to evaluate the influence of gas velocity on desorption efficiency.
The experimental results were compared with the outputs from the CNDSR pro-
gram simulation of pilot-scale operations using the ONEBOX procedure, in order to
estimate the deviation from equilibrium conditions. Fig. 4 shows the desorption data
as ratios of H2S in the outgoing liquid to the H2S in the incoming liquid vs. the pH
values. Logically, a pH increase produces a reduction of the stripped H2S. The cir-
cles represent experimental data that were obtained using the same specific load as
510 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Table 4
Absorption experiments: specific liquid load of 71.4 m3/(h.m2); specific gas load of 590.6 m3/(h.m2)

Liquid CG,out CG,in CL,out
=(CG,in-CG,out)/CG,in

pH (mg/m3) (mg/m3) (mg/l) (%)

5.3 85 83 0.37 2
6.3 120 108 0.52 10
7.4 93 70 0.81 25
8.4 95 35 2.39 63
8.9 91 20 3.3 78
9.1 94 14 3.65 85

Fig. 5. Absorption experiments: comparison between experimental data and computed data using the
CNDSR program [specific liquid load of 71.4 m3/(h.m2); specific gas load of 590.6 m3/(h.m2)]. (CG=[H2S]
in gas).

the real cooling tower. The solid line refers to the perfect equilibrium hypothesis,
calculated by the CNDSR program. A divergence was noted between experimental
data and computed data. The pilot-scale experiments were performed on an overall
packing height of 2 m, while the overall packing height of the actual cooling tower is
5 m, so that a higher efficiency is to be expected in the real tower compared to that
obtained in the pilot-scale experiments. The experimental data suggest, however,
that the real conditions are quite far from ideal behaviour.
A comparison of experimental data referred to different specific gas loads revealed
that the desorption efficiency is slightly higher for lower gas velocity. Interfacial
surfaces being equal, this is related to the longer contact time. Despite the small
difference between the two sets of results, it can however be concluded that the des-
orption efficiency is not affected substantially by gas velocity.
The absorption tests are summarised in Table 4. These experiments reproduce the
operation of the direct contact condenser. Fig. 5 compares the experimental data
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 511

with the equilibrium conditions computed by the CNDSR program using the
ONEBOX procedure with absorption data. The vertical axis represents the absorp-
tion efficiency, which is defined as

CG;in  CG;out

¼ ð1Þ
CG;in

where CG,in and CG,out are the H2S concentrations of incoming and outgoing gas-
eous streams, respectively.
Logically, an increase in pH improves the absorption efficiency, which increases to
about 100% for pH values higher than 9. In particular, in the range of pH=7–8,
typical of geothermal plant operations, the difference between computed and field
data is about 50%.
It should be noted that there is a deviation from the equilibrium conditions both
for the desorption and the absorption experiments.

6. Analysis of the CNDSR performance and modified version

The geothermal plant ‘‘A’’ was simulated by the CNDSR program; the software
inputs were the fluid composition data of the plant, collected by Enel in the period
November–December 1995. The input data are listed in Table 5.
The simulation results were compared with field data to estimate program per-
formance. The comparison included the following parameters: H2S partitioning
between primary and secondary emissions, H2S concentration, and pH of the liquid
streams feeding and leaving the cooling tower. The results for H2S partitioning and
concentrations were quite different from actual data, which could be related to the
fact that perfect thermal and chemical equilibrium is incoherent with real behaviour,
as was proved in the pilot-scale experiment.
The CNDSR was then adjusted to correct the equilibrium hypothesis and to
account for the difference (evaluated by the pilot-scale experiments) between actual
and perfect equilibrium conditions. This was achieved by modifying the KINBOX
section, by inserting two corrective factors in the equations that calculate the H2S
partitioning between the liquid and gaseous phases in the direct contact condenser
and the cooling tower boxes. The corrective factor was CC1=0.7 for the boxes
referring to the condenser (KBX=2), and CC2=15 for the boxes representing the
cooling tower (KBX=5). The subroutine lines added were:

CC1 ¼ 0:7
CC2 ¼ 15
ð2Þ
IFððKBX:EQ:2Þ:AND:ðKC:EQ:3ÞÞ FVðKCÞ ¼ FVðKCÞ  CC1
IFððKBX:EQ:5Þ:AND:ðKC:EQ:3ÞÞ FVðKCÞ ¼ FVðKCÞ  CC2

A KC value of 3 means that the considered component is H2S and FV(KC) is the
equation that computes the percentage of this component in the liquid phase.
512 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Table 5
Input data for simulation of geothermal plant ‘‘A’’

Inlet fluid Discharge from the compressor

Steam (t/h) 61 Gas (m3/h) 1212
Gas/steam (wt.%) 3.65 CO2 (wt.%) 81.3
P (bar) 6.7 H2S (wt.%) 0.78
T (
C) 185.1 CO2 (vol.%) 79.8
H2S (vol.%) 0.99
Condensate from the steam collector H2 (vol.%) 1.46
H2S (mg/l) 201 O2 (vol.%) 3.97
NH+4 (mg/l) 345 N2 (vol.%) 13.22
H3BO3 (mg/l) 50 CH4 (wt.%) 0.57
pH 5.89 Average molecular weight 37.64
H2S (kg/h) 21.3
Non-condensable gas from the steam H2S (% of the inlet value) 59.9
collector
CO2 (wt.%) 98.4 Liquid to the cooling tower
H2S (wt.%) 1.04 H2S (mg/l) 10.8
CO2 (vol.%) 95.77 NH+4 (mg/l) 280
H2S (vol.%) 1.3 pH 7.77
H2 (vol.%) 1.91
O2 (vol.%) 0.02 Liquid from the cooling tower
N2 (vol.%) 0.3 H2S (mg/l) 2.6
CH4 (wt.%) 0.7 NH+4 (mg/l) 278
Average molecular weight 42.83 pH 8

7. Analysis of the plant using the modified version of the CNDSR program

The modified CNDSR program was able to describe and fit the real fluid compo-
sition data satisfactorily. Fig. 6 graphically compares the H2S concentration in the
liquid fed to reinjection from the Enel field data vs. the simulation outputs from the
original and the modified versions. The changes introduced in the program did not
alter the program performance in predicting other parameters, such as the pH of the
stream to reinjection or the concentration of the boric acid in the same stream. Fig. 7
compares the concentrations of boric acid obtained with the original and the mod-
ified versions of the CNDSR program.

8. Analysis of other geothermal plants using the modified CNDSR program

The CNDSR program, both in its original and modified versions, was applied to
seven geothermal plants. The simulation outputs were compared with the field data
provided by Enel. The comparison was made on the basis of the gas discharged by
the compressor and the liquid fed to reinjection.
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 513

Fig. 6. H2S concentration in the liquid fed to reinjection: comparison between Enel field data and
CNDSR outputs for geothermal plant ‘‘A’’.

Fig. 7. H3BO3 concentration in the liquid fed to reinjection: comparison between Enel field data and
CNDSR outputs for geothermal plant ‘‘A’’.

In the case of the gas discharged by the compressor, the parameters considered
were the gas flow rate and the percentage of CO2 and H2S in the gas. Fig. 8 com-
pares the flow rates of the gas exiting the compressor measured by Enel in seven
geothermal plants with the values obtained by simulating the plants with the
CNDSR program in both its original and modified versions. The gas flow rates cal-
culated by both versions are in agreement; similarly, there were no significant dif-
ferences between the CO2 concentrations predicted by the original and the modified
CNDSR program.
Fig. 9 compares the percentage of H2S in the gas exiting the compressor measured
by Enel in seven geothermal plants with the values calculated by the original
CNDSR program, while Fig. 10 compares the available data with the values
obtained by the modified version of the program. It appears that the simulations
performed with the modified CNDSR program fit the field data better, while the
original version underestimates the percentage of H2S in the gas. The relative
root mean square errors are 0.12 and 0.22, respectively. Thus, regarding the gas
stream exiting the compressor, the lines inserted in the computer program did not
514 A. Baldacci et al. / Geothermics 31 (2002) 501–517

Fig. 8. Flow rates of the gas discharged by the compressor: comparison between Enel field data and
computed data using the original and modified CNDSR program for the geothermal plants investigated
(‘‘A’’, ‘‘B’’, ‘‘C’’, etc.).

Fig. 9. Content of H2S in the gas discharged by the compressor: comparison between Enel field data and
the simulation outputs of the original CNDSR program for the geothermal plants investigated (‘‘A’’, ‘‘B’’,
‘‘C’’, etc.).

significantly influence the calculation of any parameter other than the H2S con-
centration.
Regarding the liquid stream fed to reinjection, comparisons were made on the
basis of the pH and the concentrations of H3BO3, NH+ 4 and H2S. Both the original
and the modified versions satisfactorily predicted the pH, and the concentrations of
H3BO3 and NH+ 4 (there were no significant differences between the two versions).
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 515

Fig. 10. Content of H2S in the gas discharged by the compressor: comparison between Enel field data and
the simulation outputs of the modified CNDSR program for the geothermal plants investigated (‘‘A’’,
‘‘B’’, ‘‘C’’, etc.).

Fig. 11. NH+ 4 concentration in the liquid fed to reinjection: comparison between Enel field data and
simulation outputs of the original and the modified CNDSR programs for the geothermal plants investi-
gated (‘‘A’’, ‘‘B’’, ‘‘C’’, etc.).

Thus, the changes introduced in the program did not affect the calculation of these
parameters. As an example, Fig. 11 compares the ammonia concentration in the
liquid fed to reinjection against the values measured by Enel and those obtained by
simulating the plants with the original and the modified CNDSR program. It is clear
that the two versions of the program predicted the ammonia concentration in a
similar manner.
516 A. Baldacci et al. / Geothermics 31 (2002) 501–517

However, the advantage of using the modified version was evident from the value
obtained for the concentration of H2S in the liquid fed to reinjection. This was an
obvious result since the corrective lines were introduced in the CNDSR program
with the aim of rendering it adequate to estimate the H2S partitioning between the
plant streams.
As was shown for plant ‘‘A’’, the CNDSR program has to be adjusted for each
geothermal plant to improve its predictive performance. This means that appro-
priate corrective factors have to be estimated for each plant by performing pilot-
scale experiments that reproduce the specific plant operating conditions.
The high degree of accuracy in the prediction achieved with the modified version
of the CNDSR program makes it a useful tool when developing methods to reduce
the environmental impact of a geothermal plant. In the Introduction to this paper,
the gaseous emissions were classified as primary and secondary emissions. Since
primary emissions (compressor discharge) are easier to treat (Baldacci et al., 1997),
it could be appealing to shift the release of H2S from the secondary emission to the
primary emission, by, for example, acidification of the line between the condenser
and the cooling tower. Enel has carried out acidification experiments on power plant
‘‘A’’ to estimate the H2S partitioning between the two types of emissions (Baldacci
et al., 1996). Alternatively, the acidification solution could be simulated using the
modified version of the CNDSR program, by inserting the right amount of H2SO4
to obtain the required pH for the MC1 box. Fig. 12 shows the percentage of H2S
discharged by the compressor as primary emission vs. the pH of the liquid feeding
the cooling tower. Data from Enel experiments were compared with simulation
outputs from both the original and modified CNDSR. It can be seen that a good
prediction was achieved using the corrected version of the simulation program.

Fig. 12. H2S partitioning between primary emission (from the H.P. compressor) and secondary emission
(from the cooling tower): comparison between Enel field data and data computed using the CNDSR
program for geothermal plant ‘‘A’’.
 A. Baldacci et al. / Geothermics 31 (2002) 501–517 517

9. Conclusion

This work investigated the possibility of simulating an operational geothermal

plant by a simple computer program such as CNDSR. The original version of the
program provided acceptable predictions for the pH, the boric acid and ammonia
concentrations of the liquid fed to reinjection, some flow rates, and the composition
of the gases discharged from the compressor. In contrast, the calculated hydrogen
sulphide concentrations were unacceptable when compared with existing analyses of
geothermal field data. This discrepancy could be related to the hypotheses on ther-
mal and chemical equilibrium that form the basis of the program. The CNDSR
program was thus modified on the basis of pilot-scale experiments that provided
estimates of the H2S partitioning between liquid and gaseous phases in the direct
contact condenser and the cooling tower. The modified version matched the actual
data correctly, even for values of the liquid fed to reinjection. In other words, the
new program also considered the possibility that chemical equilibrium was not
reached. The modified computer program can be used, for example, to predict the
effects of plant operating parameters on the H2S distribution and, in this way,
investigate methods to reduce the environmental impact of a geothermal plant.

Acknowledgements

This work was financially supported by the ‘‘Ministezo dell ‘Universita’ e della
Ricecca Scierntifica’’ (ex-40% Funds). Dedicated to Professor Gianfranco Nencetti
on the occasion of his 70th Birthday

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