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Water Technologies & Solutions

technical paper

reverse osmosis pretreatment of high silica waters


Authors: Matthew J. White, Account Engineer, Ionics, was chosen as the best suited technology to treat
Jorge L. Masbate Jr., Technologist, Pilipinas Shell the water source at the refinery. It will also highlight
Petroleum Corporation and Simon G. Gare, Senior the problems that can be encountered running
Applications Chemist, Ionics Reverse Osmosis units on high silica and high
hardness water. We will then go on to discuss the
Note: Ionics was purchased by SUEZ in 2005.
performance of the installed system at the refinery,
and the benefits that the refinery is currently
introduction enjoying as a result of installing the unit.
A Shell petroleum refinery in the Philippines
experiences high silica in its feedwater, the silica has refinery location and water supply
been determined to be a combination of Reactive and
The oil refinery was first commissioned in 1968 and
Colloidal. They had previously been treating their
has a capacity of 165,000 barrels per day. It is
demineralization plant with a Hot Lime Softener (HPS).
located in Tabangao, Batangas City, which is about
The decision to evaluate other forms of pretreatment
62 miles (100 km) south of the capital city of the
to the demineralization plant at the refinery was taken
Philippines, Manila. The refinery lies in the southern
by the process team after evaluating costs of both
part of Batangas, which is generally characterized
operation and maintenance of the HPS unit, costs to
by moderately sloping to rolling terrain with slopes
the refinery through lost production caused by HPS
between 8 and 18%. It lies within the floodplains of 2
outages, the general unreliability of the unit, and
rivers, Malitam and Tabangao, and on a sloping
finally the increased environmental difficulties that
terrain underlain by quaternary pyroclastic.
were being encountered with regards to discharging
the lime waste of the plant. The location has two pronounced seasons, wet and
dry. The wet season generally extends from June to
The refinery therefore embarked on a study to explore
December while the dry season from Jan to May.
other alternatives to the current system to produce
Annual rainfall is about 70 inches (178 cm), the
demineralized water. Other technologies along with
mean monthly rainfall during wet season is 9.8
Reverse Osmosis were taken into consideration, but
inches (25 cm), and over dry season 1.97 inches (5
after taking all into account they decided that the most
cm). The mean annual temperature in the
effective, reliable, and economic way of producing
Philippines is 81.5°F (27.5°C), with a peak
water at the plant was to replace their troublesome
temperature of 94.6°F (34.8°C) in April and
HPS unit with Reverse Osmosis as a pretreatment to
minimum temperature of 70.5°F (21.4°C) in
their demineralization plant.
February. The mean annual humidity is 78%.
After evaluating both capital purchase and
The refinery has three deep wells within its
outsourcing, they decided that the outsourcing option
boundary, each of these have been sunk 55 yards (50
would be of more economic benefit to the company
meters) in depth. It is from these wells that the
rather than installing a capital system. In addition, it
refinery draws its water for various needs; these
would give them the benefit of a leading water
include jacket cooling water for the cooling towers
treatment company such as Ionics (now SUEZ) taking
and sanitary needs. They also use the above source
care of such a precious commodity.
in the production of high-pressure (50 Bar) steam,
This paper will discuss why Reverse Osmosis and the which is used for generating power in the steam
selected pretreatment to the Reverse Osmosis unit turbine, compressing gas in the refineries
Find a contact near you by visiting www.suezwatertechnologies.com and clicking on “Contact Us.”
*Trademark of SUEZ; may be registered in one or more countries.
©2017 SUEZ. All rights reserved.

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:

2. Colloidal Silica > 99.8% antiscalent / RO


Although there was adequate performance data for
pretreatment of reverse osmosis on high silica the Antiscalent system we did not pursue this
waters option due to the inability to actually monitor the
concentration of antiscalent present in the system
Silica is a sparingly soluble compound, pretreatment
on-line. The only way to control the concentration of
of the RO feed must therefore be considered when
antiscalent in the system is by proportional dosing.
designing a system to run on high silica waters. Two
The problems identified here were the possibility of
ways to affect the concentration of silica sustainable in
the dosing pump losing prime and it not being
the feed are to increase the temperature or the pH.
detected, or changes in feed water composition to
Increasing the temperature of the feed may be
which proportional dosing would not be able to
impractical when considering the energy cost and also
polyamide RO membranes have upper temperature react to. The result of either of the above situation
limits of ~100°F (38°C). would be catastrophic; there would be no way the
unit could be stopped except manually.
Increasing the pH however is a viable as polyamide
membranes have a wide tolerance for pH. In theory, it softener > NaOH addition > reverse osmosis
is predicted that at a pH of 10 the level of silica that
After evaluating all options, it was decided that the
can be maintained in the concentrate stream of an RO
most reliable way of pretreating the RO and
unit is around 400 ppm. (figure 1)
eliminate the potential of silica scaling the
membranes was to increase the pH of the RO feed
water to approximately 9.5 by dosing 50% NaOH. We
would then be able to sustain a silica concentration
in the RO concentrate of around 400 ppm and hence
be able to run the system at a recovery of around
65% based on a silica concentration in the feed of
~120 ppm. The benefit of using this method was that
it would give us the opportunity to monitor the pH of
the feed water and RO concentrate in-line and hence
set alarm points in the RO control panel to shut
down the unit if the NaOH dosing failed for whatever
figure 1: graph of pH against dissolved silica concentration
reason.
TP1058EN.docx Page 3
To utilize the system above, it was necessary to automatically on a counter and can be regenerated
eliminate any hardness in the feed water with softener manually in emergencies.
pretreatment. If pH is increased to above 9.5 without
polishing softener
softener pretreatment, the system would not work due
to the inevitable fouling of membranes due to large The polishing unit comprises of two five-foot
concentrations of hard ions which would form scaling diameter vessels loaded with cation resin in the
compounds such as CaCO3 etc. Although this can be sodium form. These units are set up in parallel and
cleaned off the membranes, the presence of such high are designed to run at a flow rate of up to 24,000
levels of hardness in the feed water would have led to gpm (90 m3/h), it is regenerated manually and has a
cleaning on an all too frequent basis, which was both run length of ~52 million gallons (~195,000 m3)
inefficient and uneconomic. The RO would also be based on an inlet feed hardness of 1ppm. The unit is
unable to tolerate even the smallest amount of reduced to 50% production for the regeneration of
hardness over a long duration due to possibility of the polishing softeners, which takes 1 hour per
irreversible silica scale forming on the bed of vessel and takes place every three months.
reversible hardness scale. To combat this, we
NaOH addition
installed a polishing softener unit downstream of the
softener unit to reduce the total hardness in the feed NaOH is added to the system using a controlled feed
water of the RO to below 0.1 ppm. Again, this could be system linked to incoming pH of the feed water to
monitored with an in-line hardness monitor linked to maintain a pH of 9.5 in the RO concentrate. The pH
the control panel of the RO, making the system full monitor is linked to a shutdown system should the
proof in the event of hardness leakage from the pumps or lines fail in any way.
softeners. reverse osmosis
The Reverse Osmosis unit on site contains Poly
system configuration
Amide thin film membranes in a 4 x 2 array. The unit
The unit at the refinery is designed to produce a flow is designed to run at a minimum recovery of 63%,
of up to 14,500 gpm (55 m3/h) on a continuous basis, although as we gain experience treating the water at
with a 95% service factor. The quality of water that the the refinery we hope to increase this to the
unit is designed to produce is a >95% rejection of the maximum 70% recovery.
Average Feed TDS, which can be calculated as follows.
Average feed TDS = (RO incoming feed TDS + RO operational data
Concentrate feed TDS) / 2 The system has now been supplying the refinery for
The system is made up of the following components: the past 8 months. In that time, we have seen a
slight increase in the pressures in the system over
activated carbon filtration
the baseline data. This increase is approximately
Two five-foot diameter activated carbon vessels were 6%, not enough to require cleaning, there has been
placed in parallel upstream of the unit to eliminate any no reduction in permeate flow or recovery of the
oxidants in the water, along with any hydrocarbon unit. Currently we are recording around a 64%
contamination occasionally found in the ground water recovery for the reverse osmosis unit at site. Below
supply. are the ranges of operational performance.

primary softener unit Reverse Osmosis % Recovery = 60% to 65%

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

figure 2: recovery and rejection (March to June)

table 1: feed 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.

TP1058EN.docx Page 7

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