Technical

Paper

Reverse Osmosis Pre Treatment of High

Silica Waters
Authors: Matthew J. White, Account Engineer, Ionics, Jorge L. Masbate Jr., Technologist, Pilipinas Shell
Petroleum Corporation and Simon G. Gare, Senior
Applications Chemist, Ionics
Note: Ionics was purchased by GE Water & Process
Technologies in 2005.

Introduction
A Shell petroleum refinery in the Philippines experiences high silica in its feedwater, the silica has been
determined to be a combination of Reactive and
Colloidal. They had previously been treating their
demineralization plant with a Hot Lime Softener
(HPS). The decision to evaluate other forms of pre
treatment to the demineralization plant at the refinery was taken by the process team after evaluating
costs of both operation and maintenance of the
HPS unit, costs to the refinery through lost production caused by HPS outages, the general unreliability of the unit, and finally the increased
environmental difficulties that were being encountered with regards to discharging the lime waste
of the plant.
The refinery therefore embarked on a study to
explore other alternatives to the current system to
produce demineralized water. Other technologies
along with Reverse Osmosis were taken into consideration, but after taking all into account they
decided that the most effective, reliable and economic way of producing water at the plant was
to replace their troublesome HPS unit with
Reverse Osmosis as a pre treatment to their demineralization plant.
After evaluating both capital purchase and outsourcing, they decided that the outsourcing
option would be of more economic benefit to the
company rather than installing a capital system. In

addition, it would give them the benefit of a leading

water treatment company such as Ionics (now GE)
taking care of such a precious commodity.
This paper will discuss why Reverse Osmosis and
the selected pre treatment to the Reverse Osmosis
unit was chosen as the best suited technology to
treat the water source at the refinery. It will also
highlight the problems that can be encountered
running Reverse Osmosis units on high silica and
high hardness water. We will then go on to discuss
the performance of the installed system at the
refinery, and the benefits that the refinery is currently enjoying as a result of installing the unit.

Refinery Location and Water Supply

The oil refinery was first commissioned in 1968 and
has a capacity of 165,000 barrels per day. It is
located in Tabangao, Batangas City, which is about
62 miles (100 km) south of the capital city of the
Philippines, Manila. The refinery lies in the southern
part of Batangas, which is generally characterized
by moderately sloping to rolling terrain with slopes
between 8 and 18%. It lies within the floodplains of
2 rivers, Malitam and Tabangao, and on a sloping
terrain underlain by quaternary pyroclastics.
The location has two pronounced seasons, wet and
dry. The wet season generally extends from June to
December while the dry season from Jan to May.
Annual rainfall is about 70 inches (178 cm), the
mean monthly rainfall during wet season is
9.8 inches (25 cm), and over dry season 1.97 inches
(5 cm). The mean annual temperature in the Philippines is 81.5F (27.5C), with a peak temperature of
94.6F (34.8C) in April and minimum temperature of
70.5F (21.4C) in February. The mean annual
humidity is 78%.

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TP1058EN.doc Feb-10

The refinery has three deep wells within its boundary, each of these have been sunk 55 yards
(50 meters) in depth. It is from these wells that the
refinery draws its water for various needs; these
include jacket cooling water for the cooling towers
and sanitary needs. They also use the above source
in the production of high-pressure (50 Bar) steam,
which is used for generating power in the steam
turbine, compressing gas in the refineries platformer and other various needs around the refinery.
The specification for this boiler feed water is
0.1 S/cm and 20 ppb total silica.
The bore hole water requires special attention if it is
to be treated to become boiler feed water; this is
due to the fact that it is constantly high in both colloidal and reactive silica (up to 120 ppm) and total
hardness (up to 400 ppm). The ionic make up of this
water is due to the geological characteristics of the
Philippines, which are of volcanic origin.

Demineralization Plant Configuration

Previously the feed water for the production of
steam was pretreated with a Hot-lime Process Softener (HPS). This was then followed by a standard
SAC/SBA/MB demineralization system. The HPS system was used due to the high silica and hardness
levels. The theory behind this process is that lime is
added to the feed water at high temperature, this
precipitates out the hardness and silica in the feed
water, this is then fed to the demineralization plant
for polishing to the required specification.
The problems that are encountered with the operation of this unit are high in number, these include,
high maintenance of HPS unit due to discharge of
sludge waste, intensive manpower to operate due
to the possibility of lime carryover to the demineralization system, increasing difficulty in disposing of
the sludge waste produced by the system, and the
loss of energy caused by the need to cool the water
to below 95F (35C) before it enters the demineralization plant. The final point is essential when HPS is
pre treating a standard SAC/SBA/MB demineralization plant due to the temperature specifications of
the resin in the plant, which leads to the feed
water having to be heated twice before entering
the boiler!

Problems Encountered with Silica

Contamination
If silica is not removed before entering a plants
steam system, the consequences to the life cycle of
the plant can be quite considerable. Common problems associated with silica contamination are
as follows:
1. Contamination of product.
2. Reduced efficiency of steam turbines due to
silica depositing on turbine blades.
3. Reduced efficiency of boiler due to scaling.
4. High maintenance of boilers due to scaling.
5. High maintenance of turbines due to scaling
which leads to vibration of the turbine.
Many problems encountered by silica contamination could have been understood better if only colloidal silica and reactive silica had been
differentiated at the offset.

Reactive and Colloidal silica

Total silica is the term given to the sum of colloidal
and ionic silica found in water. Silica exists in a wide
range of structures, from a simple silicate to a complicated polymeric material. The polymers structure
can persist when the material is dissolved in surface
waters. The size of the silica polymer can be substantial, ranging up to the colloidal state. Colloidal
silica can be found in surface waters but not usually
at significant concentrations, high concentrations
are found in well waters that derive from areas of
volcanic activity.
Detection of Colloidal and Reactive Silica
The polymeric form of Silica does not complex in the
standard molybate based colorimetric test for silica
- this form is termed non reactive. The polymeric
form of silica is not thermally stable and when
heated in a boiler reverts back to the basic silica
monomer, this is reactive with molybate. Analysis of
a boiler feed water may reveal little or no silica,
while the boiler blow down measurements may
show high levels. High boiler water silica and low
feed water silica values are often a sign that colloidal silica is present in the make-up feed water.
Colloidal silica is difficult to measure directly and is
usually done by measuring the total silica in the
feed water and then subtracting the amount of

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ionic silica. The balance is the total amount of colloidal silica.

that can be maintained in the concentrate stream

of an RO unit is around 400 ppm. (Figure 1)

Removing Silica from Feed Water

The varied forms of silica in water different technologies need to be applied to remove them. Reactive silica dissolved in water dissociates to form a
weak acid, the slight negative charge results in an
affinity to Strong Base Anion resin and is therefore
removed effectively using demineralization units.
However, the colloidal form is a little more difficult
to remove from feed water due to its neutral
charge, and has in some cases had a negative
impact on the demineralization unit itself. There are
some macroporus resins on the market that are
capable of removing colloidal silica however the
resin choice must be tailored to the water source as
the colloid will only be absorbed into a narrow
range of pore sizes. One of the biggest problems
with this is that if the feed water composition
changes the plant can become inefficient and unreliable.
Colloidal silica can also contaminate cation resin
within a mixed bed as a result of poor separation
this can lead to an increase in silica content to the
boiler feed water.
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 %
rejection values of Reverse Osmosis, utilizing Poly
Amide thin film composite membranes (PA).
1. Reactive Silica > 80%
2. Colloidal Silica > 99.8%

Pretreatment of Reverse Osmosis on

High Silica Waters
Silica is a sparingly soluble compound, pretreatment of the RO feed must therefore be considered
when designing a system to run on high silica
waters. Two ways to effect the concentration of silica sustainable in the feed are to increase the temperature or the pH. Increasing the temperature of
the feed may be impractical when considering the
energy cost and also polyamide RO membranes
have upper temperature limits of ~100F (38C).
Increasing the pH however is a viable as polyamide
membranes have a wide tolerance for pH. In theory,
it is predicted that at a pH of 10 the level of silica

TP1058EN

Figure 1: Graph of pH against dissolved silica

concentration

Other options include the use of Antiscalents, which

promote super-saturation of silica and hence
increases its solubility, or limiting the % recovery of
the unit and hence the concentration factor. The
later is rarely used due to environmental constraints
and raw water cost.
It is important to note at this stage that Silica fouling of membranes is practically irreversible as there
is no known method to clean RO membranes once
they are scaled with silica. Hence, as this occurrence is only rectified with membrane replacement,
the choice of pretreatment when running an RO
on high silica water is one that should not be
taken lightly!

Design Choices
Due to the composition of the feed water available
at the refinery, there were limitations on the configuration of the equipment GE could use:
Antiscalent / RO
Although there was adequate performance data for
the Antiscalent system we did not pursue this
option due to the inability to actually monitor the
concentration of antiscalent present in the system
on-line. The only way to control the concentration
of antiscalent in the system is by proportional dosing. The problems identified here were the possibility of the dosing pump losing prime and it not being
detected, or changes in feed water composition to
which proportional dosing would not be able to
react to. The result of either of the above situation
would be catastrophic; there would be no way the
unit could be stopped except manually.
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Softener > NaOH addition > Reverse Osmosis

The system is made up of the following components:

After evaluating all options, it was decided that the

most reliable way of pretreating the RO and 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 reason.

Activated Carbon Filtration

To utilize the system above, it was necessary to

eliminate any hardness in the feed water with softener pretreatment. If pH is increased to above 9.5
without softener pretreatment, the system would
not work due to the inevitable fouling of membranes due to large concentrations of hard ions
which would form scaling compounds such as
CaCO3 etc. Although this can be cleaned off the
membranes, the presence of such high levels of
hardness in the feed water would have led to cleaning on an all too frequent basis, which was both
inefficient and uneconomic. The RO would also be
unable to tolerate even the smallest amount of
hardness over a long duration due to possibility of
irreversible silica scale forming on the bed of
reversible hardness scale. To combat this we
installed a polishing softener unit downstream of
the softener unit to reduce the total hardness in the
feed water of the RO to below 0.1 ppm. Again this
could be monitored with an in-line hardness monitor linked to the control panel of the RO, making the
system full proof in the event of hardness leakage
from the softeners.

System Configuration
The unit at the refinery is designed to produce a
flow of up to 14,500 gpm (55 m3/h) on a continuous
basis, with a 95% service factor. The quality of water that the unit is designed to produce is a >95%
rejection of the Average Feed TDS, which can be
calculated as follows.
Average feed TDS = (RO incoming feed TDS + RO
Concentrate feed TDS) / 2
Page 4

Two five-foot diameter activated carbon vessels

were placed in parallel upstream of the unit to
eliminate any oxidants in the water, along with any
hydrocarbon contamination occasionally found in
the ground water supply.
Primary Softener unit
The softener unit comprises of six five-foot diameter
vessels loaded with cation resin in the sodium form.
These units are set up in parallel and run as two
streams of three vessels, which allowed us to operate one stream in service with the other in regeneration / standby mode. The unit was designed to
run at a flow rate of 110 m3/h constantly with a
feed total hardness of up to 400 ppm. The unit is
regenerated automatically on a counter and can be
regenerated manually in emergencies.
Polishing Softener
The polishing unit comprises of two five-foot diameter vessels loaded with cation resin in the sodium
form. These units are set up in parallel and are
designed to run at a flow rate of up to 24,000 gpm
(90 m3/h), it is regenerated manually and has a run
length of ~52 million gallons (~195,000 m3) based
on an inlet feed hardness of 1ppm. The unit is
reduced to 50% production for the regeneration of
the polishing softeners, which takes 1 hour per vessel
and takes place every three months.
NaOH Addition
NaOH is added to the system using a controlled
feed system linked to incoming pH of the feed
water to maintain a pH of 9.5 in the RO concentrate.
The pH monitor is linked to a shutdown system
should the pumps or lines fail in any way.
Reverse Osmosis
The Reverse Osmosis unit on site contains Poly
Amide thin film membranes in a 4 x 2 array. The unit
is designed to run at a minimum recovery of 63%,
although as we gain experience treating the water
at the refinery we hope to increase this to the
maximum 70% recovery.

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Operational Data

Table 2: Product Concentrations

The system has now been supplying the refinery for

the past 8 months. In that time we have seen a
slight increase in the pressures in the system over
the baseline data. This increase is approximately
6%, not enough to require cleaning, there has been
no reduction in permeate flow or recovery of the
unit. Currently we are recording around a 64%
recovery for the reverse osmosis unit at site. Below
are the ranges of operational performance.
Reverse Osmosis % Recovery

60% to 65%

Reverse Osmosis % Rejection

94% to 97%

Feed water pH after NaOH addition = 9.5 to 10.5**

**Dependent

Table 3: Concentrate Concentrations

on silica content of feed water

Tables 1, 2 and 3 represent the feed, product and

concentrate concentrations from the system. Also a
graph of differential pressure is presented and
in-out recovery. (Figure 3)

Figure 2: Recovery and Rejection (March to June)

Conclusion
Table 1: Feed Concentrations

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Since installing the unit at the refinery, Pilipinas

Shell has benefited both technically and economically. They have eliminated the troublesome HPS
softener as a pre treatment 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 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 77F (25C).

Page 5

Another benefit to the refinery was the fact that the

water produced by the RO system was of a much
higher quality than that produced by the HPS plant.
As the TDS of this water was much lower than the
HPS water the run lengths of the Demineralizer
were increased dramatically which led to major
cost savings on commodity chemicals. This was due
to a reduction of chemicals such as H2SO4 and
NaOH, which are used for demineralizer regenerations. There was also a reduction in maintenance
costs of the demineralizer unit due to reduction in
its workload, and the fact that there was no more
carry over from the HPS, which sometimes blocked
the beds and damaged the resin. Other cost savings, as said earlier were through energy savings,
these were substantial and were the major factor in
influencing the refinery to install the reverse osmosis system. Now, the feed water had only to be
heated once before the boiler, instead of the previous set up which involved heating the water for the
HPS process (which utilized steam), cooling the
water down to meet the demineralizer temperature
specification 100F (38C), and finally reheating
before the deaerator.
Page 6

Last but by no means least, one of the major benefits that has been recognized by the refinery is the
increased reliability of the new technology. After
eliminating a particularly troublesome piece of
equipment, which at times caused reduction in the
production capability of the plant, the refinery now
enjoys the benefit of increased inventories of
treated water. Pilipinas Shell Petroleum Corporation
have entered the new millennium knowing that this
precious resource is in the hands of a first class
water treatment company.

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