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FINAL REPORT
August 2021
Mannvit has designed and constructed a pilot plant and conducted two tests
to assess options for planned expansion developments at Dieng. GEOKEM
has been engaged to review the final report of the tests.
Two tests have been run on the pilot plant with fluid from well HCE-7C. The
tests investigated Options 1,4 and 6 from the Thermochem Indonesia (TCI)
report entitled “Silica Scale Mitigation Study for Dieng Units 2 and 3”.
The TCI report recommended acid dosing into the two-phase fluid. This was
found to cause unacceptable corrosion, and acid dosing was shifted to the
separated brine. Unfortunately, this meant that the acid was added at a
temperature below the silica saturation temperature (SST) and silica
polymerisation to form colloids had already begun. The bulky silica scaling
from geothermal brines is due to colloidal deposition and consequently it is
impossible to distinguish whether the silica scaling observed in both tests
would occur if no colloidal silica was present.
Silica scaling was observed on all coupons exposed in both of the tests.
Significant amorphous arsenic sulfide scaling was observed on coupons from
the brine after the heat exchangers in test 1. Antimony sulfide scaling was
observed in the coupon after the first heat exchanger in test 1. The sulfide
scaling would seem to tip the balance towards a steam flash plant, rather than
a binary plant. In test 2, only silica scaling was observed on the coupons.
The addition of condensate to the brine raised the pH to values where silica
polymerisation would again be expected, and negated the reason for acid
addition. Consequently, addition of condensate should not be considered if
acid dosing is utilised
Recommendations:
• That tests be conducted to determine the first stage separation
temperature above the silica saturation temperature to enable acid
addition to the brine before silica polymerisation commences. These tests
should run for a minimum of 1 week each in order to obtain conclusive
results.
• Possibly investigate the acidified brine reacting with drill cuttings from the
formation in a flow-through autoclave.
• At the end of each test, flush the plant with fresh water before shutting
down to prevent silica and sulfide deposition on the coupons as the plant
is closed down and the brine cools.
Mannvit was engaged to design and construct a pilot plant and to conduct two
initial tests to investigate the likelihood and severity of silica and other scaling
in different conditions. GEOKEM was engaged to review the results of these
pilot plant tests.
2.0 TEST1
2.1 EXPERIMENTAL
The first pilot plant test was for Options 1 and 4 from the original proposal.
As with setting up any pilot plant, there were some problems at the start of this
test:
• There was solid material being produced from the well causing pressure
variation
• The acid dosing into two-phase fluid was found to be causing severe
corrosion and so dosing was then shifted into the brine after the separator
• A pressure transducer was found to be wrongly calibrated and the
separator was therefore operated at well below target
pressure/temperature.
The pressure transducer error was corrected after three days and the test was
restarted with replacement coupons, but the formation rock chips in the holdup
vessels were not replaced.
Review of Pilot Plant Tests – Dieng Page | 6
The automatic pH measurement system rapidly became inoperable due to sulfide
scaling and was replaced by manual periodic pH measurement. Brine from
various sample points was collected during the test. The test ran for 13 days. At
the conclusion of the test, coupons were withdrawn and analysed and the rock
chips in the holdup vessels were also analysed.
2.2 RESULTS
General
Unfortunately, the data records could not be recovered from the datalogger.
However, pressures, temperatures and pH from the screenshot data were
reasonably constant throughout the test, although it appears that the acid dosing
was halted for ~ 12 hours between the dates of 1st and 2nd of May due to dosing
pump problems.
Shifting the acid dosing to the separated brine from the two-phase fluid meant
that the acid was then dosed at a pressure of ~ 21 bara (215°C). With a silica
concentration of 1130 - 1145 ppm, the separated brine is already oversaturated
with respect to amorphous silica and silica polymerisation to colloidal silica will
probably have commenced. As the voluminous silica scaling is due to colloidal
silica, and the acid is added to delay silica polymerisation, the acid needs to be
added to the brine before silica polymerisation commences. The silica saturation
temperature (SST) is the temperature at which the silica concentration in the
separated brine just reaches amorphous silica solubility. The SST for HCE-7C is
estimated to be 222°C from TFT and chemical data collected in September 2020.
The difference in concentration between the total silica (1145 ppm) and the
monomeric silica (1062 ppm) also indicates that the silica has already
polymerised. As well, the operational data shows that although the separated
brine was initially at 215°C, for much of the latter testing the temperature of the
separated brine was below 210°C, further increasing the silica saturation.
From the test data, assuming a dose rate of 2.5 vol% sulfuric acid of 7 litres/hour,
the calculated dose rate of 98% sulfuric acid required for a 25°C pH of 4.6 is
calculated to be 59 gms of 98% sulfuric acid per tonne of brine. This dose rate is
dependent on the chemistry of the brine and particularly on the bicarbonate
concentration in the separated brine.
Line 1 results
The acidified brine was passed through two heat exchangers, which Mannvit
called a Vaporizer and Preheater. After the two heat exchangers, condensate
was added to the brine. This setup is simulating a bottoming plant. The
temperature was reduced to ~ 100 °C in the ‘vaporiser’ and further to ~ 80°C in
the ‘preheater’. Condensate was added to the brine and then passed through the
holdup vessels. After exiting the holdup vessels, the temperature was ~ 70°C.
From the coupon data at C04 before the first heat exchanger, there is some silica
scaling just after acid dosing. The scaling rate is estimated as 0.5 – 1.4
mm/year. This may be due to the amount of polymerised silica present
throughout the test as mentioned above, or it could also be due to the increased
likelihood of silica polymerisation and scaling while the acid dosing pump was not
in service during the test. The SEM photomicrograph (Appendix D9 in test 1
report) is characteristic of spherical colloidal silica. The aluminium content in the
The scaling on the coupon (C05) exiting the first heat exchanger showed the
presence of silica (87wt%), antimony sulfide(10wt%) and arsenic sulfide (3wt%).
The reddish colour of the scale indicates that the antimony sulfide was present as
amorphous antimony sulfide, rather than crystalline stibnite. The exit
temperature of this heat exchanger was ~ 100°C. The antimony sulfide
concentration was ~ 3 times the arsenic sulfide concentration as expected due to
the lesser solubility of the antimony sulfide. From the photomicrograph Appendix
D11 Test 1 report), it appears that the bulk of the sample is large colloidal silica
spheres. Once again, it is difficult to tell whether the silica that is deposited is
due to the amount of polymerisation throughout the test, or to deposition during
the period of no acid addition. The small sulfide colloids on the surface of the
larger silica colloids would probably have been precipitated during plant
shutdown. This could be avoided by flushing the plant with fresh water before
shutting down. From the SEM analysis, there is no alumimium present in the
scale. This is expected from many previous experiments, where the initial silica
deposition quantitatively removes nearly all of the aluminium.
The scaling on the coupon (C06) exiting the second heat exchanger also showed
the presence of silica (51wt%), arsenic sulfide (46wt%) and antimony sulfide
(3wt%). The deposit had the typical yellow/orange colour of arsenic sulfide. The
exit temperature was 76 – 80 °C and the amount of scale was significant which
would severely impact regular electricity production from a bottoming plant with
these temperatures.
Scaling on the coupon (C07) after the holdup vessels showed only the presence
of silica (81wt%), and arsenic sulfide (19wt%). The amount of scaling was
significant. Slightly cooler condensate was added to the brine before entering the
holdup vessels. Although this dilutes the silica and reduces the SSI from ~4.6 to
~2.9 at 80°C, it has the effect of raising the pH and negating the purpose of
adding the acid to halt silica polymerisation. For a lot of the time, it also reduced
the temperature to ~70°C where the SSI is increased to ~3.3.
Line 2 results
Line 2 was testing Option 1 and this was simply separating at high
temperature/pressure and acidifying the brine. The coupon (C08) immediately
after acid dosing was composed of silica (79wt%), with some alumina (4 wt%)
and some corrosion products or background metal from the coupon. The amount
of scale deposited is similar to that observed in Line 1 before cooling.
The scale on the coupon (C09) after the holdup vessels was composed of silica
(66 wt%) and iron oxide (34%). Measured thickness was greater than that
observed before holdup. However, the degree of silica polymerisation (the
difference between total and monomeric silica) is the same within experimental
error between before and after holdup.
3.0 TEST 2
3.1 EXPERIMENTAL
This test was to investigate Option 6 and a variation of Option 6. The target
conditions were an initial separation at 215°C followed by a second flash and
separation at 127°C. In Line 1, cold condensate was added to the brine and it
was then passed through the holdup vessels. The two heat exchangers in Line 1
were not connected. In line 2, no condensate was added and the brine was just
passed through the holdup vessels.
After four days, suspected severe scaling at the inlet to the second separator
caused the test to be halted.
3.2 RESULTS
General
Flows through Line 1 and Line 2 were reasonably constant throughout the test.
The pH varied a small amount but was always below pH = 5.0. The target
second flash temperature of 127°C became 132 – 139 °C. There seemed to be
a significant temperature drop through the holdup vessels in Line 2.
The two-phase brine was again separated at 215°C, which is below the silica
saturation temperature. Consequently, a significant proportion of the silica had
polymerised before acid was added to the brine, as witnessed by the difference
between the total silica and monomeric silica analyses. This difference is greater
than that measured in Test 1.
The pH is measured in the HP brine before the second flash. When the HP brine
is flashed to 132 °C, some CO2 is lost from the brine fraction and the pH
increases slightly. From the information in Table 4 in the Test 2 report, the pH
rises from 4.5 to 5.0. Consequently, the target pH in the brine to be tested is
greater than the target pH.
From the data given, the required dose rate of 98% sulfuric acid is calculated to
be 55 gms of 98% sulfuric acid per tonne of brine, which is similar to that
calculated for Test 1.
Line 1 results
Unfortunately, no chemical samples were taken of the undiluted brine at 137°C in
either line 1 or line 2. The calculated total silica concentration is 1354 ppm in
the brine from the LP separator. The brine at 137°C was then diluted by ~ 45%
with condensate at 47°C. This reduced the Silica Saturation Index (SSI) from
2.47 at 137°C to 2.36 at 95°C. However, once again, in the process of dilution,
the pH was raised from ~ 5.0 to ~6.3. This rise in pH allows the silica to start
polymerising and silica to deposit in the holdup vessels. Consequently, the
addition of the condensate is having a detrimental effect on silica scaling.
Analyses of the brine before and after the packed bed in Line 1 (Table 9 in test 2
report) show that there has been a significant deposition of silica onto the
formation material in the bed.
Line 2 results
The analysis of the separator sample from S01 shows a large difference between
the total silica and monomeric silica analyses, which indicates significant silica
polymerisation. There is even greater silica polymerisation shown in the sample
from the outlet (S24). The difference probably occurs due to growth of the silica
particles in the holdup vessels. The energy required for a silica monomer to
attach to a colloid is much less than that required to form a nucleus of a new
colloid. On both the inlet (C08) and outlet (C09) coupons, the scale consists of
essentially pure silica. The amount of scale on each coupon would probably be
prohibitive in a production scenario. The morphology of the surface in the C08
coupons is very typical of colloidal silica deposition. The SEM photomicrographs
confirm the colloidal nature of the scale on both the input and output coupons.
There were no brine analyses for the inlet and outlet of the packed bed in Line 2.
From the photos of the packed bed, it appears that most of the silica was
deposited on the bottom of the packed bed.
4.0 DISCUSSION
In a dual flash arrangement when the brine is flashed from HP to LP, acid gases
are lost to the vapour phase and the pH of the resultant LP brine is raised.
Consequently, in order to maintain a pH of 4.6 in the LP brine, the pH of the HP
brine after acid addition will need to be lower than 4.6. Alternatively, two-stage
acid dosing in both HP and LP brine may be utilised. A calculation shows that in
order for a pH25 of 4.6 in the LP brine at 150°C, a pH25 of ~ 4.4 is required in the
HP brine before flashing.
Because arsenic and antimony sulfides are precipitated from cooled acidified
brine, sampling of acidified brine for arsenic and antimony can be difficult. As
suggested previously, the samples for As and Sb analysis should have been
preserved in caustic solution. As well, the samples should be collected at as high
a temperature as possible while still preventing flashing, and at a high flow rate.
Samples collected during tests 1 and 2 will return arsenic and antimony analyses
that are incorrect due to incorrect sampling and preservation.
Unfortunately, coupons were not installed in the turnarounds in the first heat
exchanger as recommended. Consequently, it is not defined at what
temperature the arsenic and antimony sulfides started to deposit. The
geochemical thermodynamic data for the amorphous antimony and arsenic
sulfides are not well defined, and consequently, the temperature at which they
might start to deposit cannot be reliably calculated. This becomes important if
subsequent flashes of acidified brine are contemplated.
The testing proved that acid injection into the two-phase line is not feasible due to
severe corrosion.
5.0 RECOMMENDATIONS
The severity of the arsenic sulfide scaling would appear to make a conventional
ORC binary plant less desirable than a conventional flash plant. Consequently,
future pilot plant testing should initially concentrate on defining possible flash
plant operation parameters.
After sufficient tests have confirmed parameters for a flash development, repeat
the heat exchanger tests to find the temperature at which the arsenic sulfide
starts precipitating. Possibly with coupons in the turnarounds in the first heat
exchanger.
Measure the silica concentration in the steam condensate at the initial separation
There is a technique available where the acidified brine is reacted with drill
cuttings from the formation in a flow-through autoclave. This technique can
possibly clarify interaction with the formation, but will not categorically define the
life of a reinjection well. This may be worth investigating in place of the packed
bed experiments.
It is recommended that at the end of each test, the plant is flushed with water to
prevent silica and sulfide deposition on the coupons as the plant is closed down.