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technical paper
TP1058EN.docx Feb-10
platformer and other various needs around the 4. High maintenance of boilers due to scaling.
refinery. The specification for this boiler feed water is
0.1 µS/cm and 20 ppb total silica. 5. High maintenance of turbines due to scaling
which leads to vibration of the turbine.
The bore hole water requires special attention if it is to
be treated to become boiler feed water; this is due to Many problems encountered by silica contamination
the fact that it is constantly high in both colloidal and could have been understood better if only colloidal
reactive silica (up to 120 ppm) and total hardness (up silica and reactive silica had been differentiated at
to 400 ppm). The ionic make up of this water is due to the offset.
the geological characteristics of the Philippines, which
are of volcanic origin. reactive and colloidal silica
Total silica is the term given to the sum of colloidal
demineralization plant configuration and ionic silica found in water. Silica exists in a wide
Previously the feed water for the production of steam range of structures, from a simple silicate to a
was pretreated with a Hot-lime Process Softener complicated polymeric material. The polymers
(HPS). This was then followed by a standard structure can persist when the material is dissolved
SAC/SBA/MB demineralization system. The HPS in surface waters. The size of the silica polymer can
system was used due to the high silica and hardness be substantial, ranging up to the colloidal state.
levels. The theory behind this process is that lime is Colloidal silica can be found in surface waters but
added to the feed water at high temperature, this not usually at significant concentrations, high
precipitates out the hardness and silica in the feed concentrations are found in well waters that derive
water, this is then fed to the demineralization plant for from areas of volcanic activity.
polishing to the required specification. detection of colloidal and reactive silica
The problems that are encountered with the operation The polymeric form of Silica does not complex in the
of this unit are high in number, these include, high standard molybate based colorimetric test for silica
maintenance of HPS unit due to discharge of sludge - this form is termed non-reactive. The polymeric
waste, intensive manpower to operate due to the form of silica is not thermally stable, and when
possibility of lime carryover to the demineralization heated in a boiler reverts back to the basic silica
system, increasing difficulty in disposing of the sludge monomer, this is reactive with moly bate. Analysis of
waste produced by the system, and the loss of energy a boiler feed water may reveal little or no silica,
caused by the need to cool the water to below 95°F while the boiler blows down measurements may
(35°C) before it enters the demineralization plant. The show high levels. High boiler water silica and low
final point is essential when HPS is pre-treating a feed water silica values are often a sign that
standard SAC/SBA/MB demineralization plant due to colloidal silica is present in the make-up feed water.
the temperature specifications of the resin in the
plant, which leads to the feed water having to be Colloidal silica is difficult to measure directly, and is
heated twice before entering the boiler! usually done by measuring the total silica in the feed
water, and then subtracting the amount of ionic
silica. The balance is the total amount of colloidal
problems encountered with silica contamination silica.
If silica is not removed before entering a plants steam removing silica from feed water
system, the consequences to the life cycle of the plant
can be quite considerable. Common problems The varied forms of silica in water different
associated with silica contamination are as follows: technologies need to be applied to remove them.
Reactive silica dissolved in water dissociates to form
1. Contamination of product. a weak acid, the slight negative charge results in an
2. Reduced efficiency of steam turbines due to silica affinity to Strong Base Anion resin and is therefore
depositing on turbine blades. removed effectively using demineralization units.
However, the colloidal form is a little more difficult
3. Reduced efficiency of boiler due to scaling. to remove from feed water due to its neutral charge,
and has in some cases had a negative impact on the
Page 2 TP1058EN.docx
demineralization unit itself. There are some Other options include the use of Antiscalents, which
microporous resins on the market that are capable of promote super-saturation of silica, and hence
removing colloidal silica however the resin choice increases its solubility, or limiting the % recovery of
must be tailored to the water source as the colloid will the unit and hence the concentration factor. The
only be absorbed into a narrow range of pore sizes. latter is rarely used due to environmental
One of the biggest problems with this is that if the feed constraints and raw water cost.
water composition changes the plant can become
It is important to note at this stage that Silica fouling
inefficient and unreliable.
of membranes is practically irreversible as there is
Colloidal silica can also contaminate cation resin no known method to clean RO membranes once they
within a mixed bed as a result of poor separation this are scaled with silica. Hence, as this occurrence is
can lead to an increase in silica content to the boiler only rectified with membrane replacement, the
feed water. choice of pretreatment when running an RO on high
silica water is one that should not be taken lightly!
Reverse Osmosis is a technology that is effective at
removing silica in both its reactive and non-reactive
state. The following are examples of the typical % design choices
rejection values of Reverse Osmosis, utilizing Poly Due to the composition of the feed water available at
Amide thin film composite membranes (PA). the refinery, there were limitations on the
1. Reactive Silica > 80% configuration of the equipment SUEZ could use:
The softener unit comprises of six five-foot diameter Reverse Osmosis % Rejection = 94% to 97%
vessels loaded with cation resin in the sodium form.
Feed water pH after NaOH addition = 9.5 to 10.5**
These units are set up in parallel and run as two
streams of three vessels, which allowed us to operate **Dependent on silica content of feed water
one stream in service with the other in regeneration / Tables 1, 2 and 3 represent the feed, product and
standby mode. The unit was designed to run at a flow concentrate concentrations from the system. Also, a
rate of 110 m3/h constantly with a feed total hardness graph of differential pressure is presented and in-
of up to 400 ppm. The unit is regenerated out recovery. (figure 3)
Page 4 TP1058EN.docx
table 3: concentrate concentrations
conclusion
Since installing the unit at the refinery, Pilipinas
Shell has benefited both technically and
economically. They have eliminated the troublesome
HPS softener as a pretreatment to the
Demineralization plant and hence the waste
associated with the unit. All waste from the softener
/ RO system are routed to drain, although the high
pH waste stream (pH~10) is blended with another
wastewater stream at the plant to reduce the pH and
silica concentration. This method of lowering the pH
table 2: product concentrations was decided due to the fact that if acid is added to
lower the pH there would also have been the
possibility of silica precipitation due to the
concentration being 220 ppm - 335 ppm1 at 77°F
(25°C).
TP1058EN.docx Page 5
Another benefit to the refinery was the fact that the to be heated once before the boiler, instead of the
water produced by the RO system was of a much previous set up which involved heating the water for
higher quality than that produced by the HPS plant. As the HPS process (which utilized steam), cooling the
the TDS of this water was much lower than the HPS water down to meet the demineralizer temperature
water the run lengths of the Demineralizer were specification 100°F (38°C), and finally reheating
increased dramatically which led to major cost savings before the deaerator.
on commodity chemicals. This was due to a reduction Last but by no means least, one of the major
of chemicals such as H2SO4 and NaOH, which are benefits that has been recognized by the refinery is
used for demineralizer regenerations. There was also the increased reliability of the new technology. After
a reduction in maintenance costs of the demineralizer eliminating a particularly troublesome piece of
unit due to reduction in its workload, and the fact that equipment, which at times caused reduction in the
there was no more carry over from the HPS, which production capability of the plant, the refinery now
sometimes blocked the beds and damaged the resin. enjoys the benefit of increased inventories of treated
Other cost savings, as said earlier were through water. Pilipinas Shell Petroleum Corporation have
energy savings, these were substantial and were the entered the new millennium knowing that this
major factor in influencing the refinery to install the precious resource is in the hands of a first-class
reverse osmosis system. Now, the feed water had only water treatment company.
Page 6 TP1058EN.docx
references
1. Dyson, Mark G. How can colloidal silica and TOC
reduction increase the life cycle of power stations,
1999.
2. Threlfall, David P. The use of membrane
technology for the production of DI water in
environmentally sensitive areas, 1999.
3. Miller, William S. Reverse Osmosis membrane
technology for make-up systems.
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