DESALINATION

ELSEVIER Desalination 157 (2003) 209-216

www.elsevier.com/locate/desal

Novel antiscalant dosing control

E.H. Kelle Zeiher, Bosco Ho, Kevin D. Williams*

Ondeo Nalco Company, POB 11, Winnington Avenue, Northwich, Cheshire CW8 4DX, UK
Tel. +44 (1606) 74488; email: lo4~illiams@ondeo-nalco.com

Received 3 February 2003; accepted 10 February 2003

Abstract

Ii1this paper we identify a new technology to provide online, accurate, in-situ, reliable antiscalant dosing monitoring
for any reverse osmosis system.

Keywords: Antiscalant dosing control; Novel technology; Reverse osmosis

1. Background number of detailed texts and technical short courses

are available to those interested in learning details
In the past decade, reverse osmosis (RO)
of the RO operation [ 1]. In addition to the standard
systems have moved from being an exotic and
texts, the American Society for Testing and
vulnerable technology to being a reliable and
Materials (ASTM) offers various standards for
robust conventional technology. As such, the use
membrane operation [2].
of reverse osmosis systems has become integral
All sources agree that a consistent factor in
to the production o f pure water and ultrapure
the deployment of RO technology has been the
water in industry. In light of this, the reliability of
need to prevent the fouling and scaling o f the
the RO membrane becomes critical within the
membrane [3-5]. Fouling occurs when organic
operation of industrial systems.
or biological material collects on the membrane
Experts routinely tout the benefits of RO
surface, causing increased system AP and/or de-
system monitoring and numerous technical papers
creased permeate production. Most fouling is
extol the benefits of scale and fouling control. A
addressed by using pre-treatment techniques such
as filtration. Scaling, which is the primary focus
*Corresponding author.
Presented at the European Conjerence on Desalination and the Environment: Fresh Water for All, Malta, 4-8 May' 2003.
European Desalination Society, International Water Association.

0011-9164/03/$- See fi'ont matter © 2003 Elsevier Science B.V. All rights reserved
PII: $001 l - 9 1 6 4 ( 0 3 ) 0 0 4 0 0 - 4
210 E.tf. Kelle Zeiher et al. / Desalination 157 (2003) 209 216
of this paper, occurs when sparingly soluble
minerals present in the feedwater precipitate on
the membrane surface, usually at the tail end of an
RO system. Scaling can be avoided or minimised
using a variety of methods, including pre-treat-
ment and addition of scale inhibitors.
2. Scale tbrmation and prevention
Scaling occurs when sparingly soluble salts,
present in the feedwater, are concentrated by
virtue of the RO process. Table 1 shows how the
water chemistry changes from the feed to the
reject stream in a typical RO system. Common
scales include silicates, sulphates, phosphates, and
carbonates. Calcium carbonate is the most common
potential scalant in brackish water industrial RO
systems. Although lmmerous techniques are known
to avoid scaling, it remains a serious problem in
RO operation. A significant number of membranes
sent for destructive (autopsy) analysis still have
extensive carbonate scale on them [6]. Many RO
operators consider scale formation to be unavoid-
able. Thus, a need exists for advanced monitoring
and control techniques to prevent scale formation
and the problems it creates.
To review, the most common scale control
techniques are
Table I
Scaling potential changes as water passes through a RO
system
Feedwater Rejectwater
(75% recovery)
Calcium, ppm CaCO3 150 558
Bicarbonate, ppm CaCO3 100 389
pH 7.9 8.4
Temperature, °C 20 20
LSI -0.08 1.69
Scaling No Yes
Antiscalant required No Yes
LSI, LangellierSaturation Index is used to predictcalcium
carbonate scale formation accountingfor the contributory
chemical factors, calculatedusing ROl 2 program [15].
• Lime softening
• Ion exchange softening
• Acid dosing
• Speciality antiscalants
Although well understood, hot and cold lime
softening has largely been supplanted by ion
exchange softening in recent years.
Sodium regenerated ion exchange softeners
technically offer a good method for scale control.
However, the significant capital and operational
expense involved with using these softeners make
other alternatives more attractive. In addition,
brine regenerate discharge can be an issue [7].
Acid dosing is often used to prevent CaCO 3
scale because acid is inexpensive on a weight basis
and the dosage can be monitored easily with the
use of a pH probe. This makes it ideal for use in
systems in which remote monitoring is employed.
The disadvantages of acid are high cost in high
alkalinity waters, the handling and safety issues,
and CO 2 production that increases permeate con-
ductivity (thus making a degassifier necessary in
certain applications). In addition, many commer-
cially available acids are contaminated with
metals that can accelerate lnembrane fouling.
Antiscalant dosing is known to be very effec-
tive at preventing scale formation [8]. It is an
attractive option because it has the demonstrated
advantages o f operational and capital cost
reduction, environmental acceptability and safety
when compared to the alternative technologies.
The disadvantage ofantiscalant dosing in the past
has been the fear of product overdosing and the
inability to easily confirm that product is present
in the system. Unlike acid dosing, which is easily
monitored by pH, or softening, which can be
monitored by use of ion selective electrodes, anti-
scalant monitoring involved cumbersome labo-
ratory techniques that were poorly suited to rapid,
on-site evaluation [9].
The key to the effective performance of a n y
scale prevention technology is that it has to function
100% of the time due to the dynamic nature of
the water condition within the RO system. If the
 E.H. Kelle Zeiher et al. / Desalination 157 (2003) 209-216
technology is off-line, because, for example, the
salt has not been replenished for an IX softener
or the antiscalant dosing pump has failed, then
there are no mechanisms in place to prevent the
formation of scale crystals within the operating
RO system.
Scaling conditions form in the RO system as
permeate water is removed from the bulk water
stream, leaving behind the dissolved solids. As
the volume of the bulk water continues to be
reduced, the concentration of solids begins to
exceed the solubility limit of certain salts. The
result is scale formation and precipitation. A
simplified explanation of scale formation (crystal-
lisation) is shown in Fig. 1.
This process is continuous within the mem-
branes and is driven towards the crystal formation
with greater intensity close to the membrane
surface (the boundary layer) and in the final mem-
brane of the RO system's final stage. The failure
to provide the inhibiting mechanism will allow
this process to continue without restraint.
Antisealant technologies work by delaying
the growth phase of crystallisation, thus inhibiting
the formation of crystals (Fig. 2). In order to be
effective, the proper dose of antisealant must be
present in the system at all times. Underdosing
(or dosing interruptions) can lead to immediate
scaling in waters with high salt concentrations.
It is generally recognised by industry experts
that a proper monitoring program is essential to
operating any water treatment unit process,
including a reverse osmosis system. Diligent
monitoring improves the reliability and perform-
ance of RO systems and will significantly improve
the life cycle cost of operating this unit process.
Lira itations in technology, combined with insuffi-
cient plant resources have often left RO systems
under monitored and under protected.
One area which has not been adequately
monitored is antiscalant concentration. The industry
standard for antiscalant dosage monitoring, timed
draw down, only gives an average concentration
over time. Since the hydraulic holding times of
211
!011 Protonuel Crvst
Oro
Fig. 1. Stages of crystallisation.
Threshold Agents (Anti-precipitants)
Protonuclei • Crystals
tons
Ordering Growth ~ : ~ ~
Delay the Ordering Process
Fig. 2. Effect of antiscalants (threshold agents) on crystalli-
sation.
RO systems are short compared to other unit pro-
cesses, the variability inherent in timed draw down
measurements can be unacceptably high. If, in
addition to standard system performance moni-
toring, the antiscalant dosing could be monitored
and controlled, it would provide confidence that
the system was being treated and would alert the
system operators to treatment interruptions or
system flow dynamics that could lead to increased
cleaning and maintenance costs.
By employing fluorescent molecule monitoring
[10], which has been successfully used in boiler
and cooling water systems, a new technology has
recently been developed for monitoring and con-
trol of the RO antiscalant, and it is now possible
to realise these advantages. Patent applications
have been filed for this novel technology. An
overview of this exciting new technology and its
applications in field systems is given below.
212 E.H. Kelle Zeiher et al. /Desalination 157 (2003) 209-216

3. Fluorescent molecule (TRASAR ®) technology operation ensured that the chemical concerns were
fully satisfied and that the TRASAR molecule is
Fluorescence is a property of certain organic
compatible with the antiscalant and the membrane
molecules in which the molecule adsorbs light at
materials of construction. Extensive use of the
one frequency and emits light at a different
TRASAR molecules (over the past l 5 years) in
frequency. When such molecules are combined
boiler and cooling water systems have demon-
with antiscalant chemicals in a known proportion,
strated that it is environmentally acceptable and
they act as a "bar code" on the antiscalant, allow-
very cost effective.
ing the concentration ofantiscalant to be monitored
via simple, on-line equipment. The molecules
typically chosen for fluorescent tracing can be
detected at very low concentrations, typically on 4. Trial site 1 report
the order of ppb or ppt in systems. In addition,
This is an industrial system producing ultra-
they are chosen to fluoresce at wavelengths not
pure water for high-pressure steam boilers. Addi-
visible to the human eye. TRASAR technology
tional treatment is mixed bed ion exchange (IX).
is based on the use of a fluorescent molecule that
The system (Fig. 4) is configured with either one
provides a clear and identifiable fluorescence that
of the RO units or both RO units operating to meet
can be separated from the natural background.
the demand for treated water. Each unit produces
Fig. 3 shows a simplified diagram of the fluoro-
approximately 20 m~/h of permeate water. There
meter used to detect the presence of the TRASAR
had been reliability problems due to fouling and
molecule on line.
scaling, despite use of proprietary antiscalants.
When adding anything to a membrane anti-
The initial troubleshooting investigation began
scalant, several factors must be considered. The
with substituting the current antiscalant with
material must be:
TRASAR antiscalant. Timed drawn down mea-
• Compatible with the membrane surface
surements of antiscalant concentration indicated
• Compatible with the antiscalant chemistry
that the dose was constant and correct for the
• Environmentally acceptable
system. The continuous real-time results, however,
• Cost effective
showed a different story and provided the key
The laboratory studies based on industry stan- diagnostic aid. Tracking of the feedwater anti-
dard tests [11-13] such as soak tests and field scalant dose showed a much more consistent dose

t Detector
Z 2 ....... , d
Excitation
Filter
Emission Filter

~tbe

g vXJ Flow Cell

Light
Sollrce

tt Water Sample In Fig. 3. Fluorescence monitoring equipment.

 E.H. Kelle Zeiher et al. /Desalination 157 (2003) 209-216 213

~ Secondary RO
Permeate to boiler
Cartridge H.P. feedwater tank
filter Pump
Well water source 9,'. i ~ ~ O n Primary
> RO
Feedwater
sample point centrate
q/water sample
Chemical point
injection
point Fig. 4. System overview trial site 1.

50

45

_.~ 4 0
o~
¢o
35
30
E
~_ 25
=-
.o_ 20

o~15
810
5

o o o o o ~:~ o o o
Fig. 5. TRASAR'~' monitoring demon-
Time, minutes strates best operating conditions.

ofantiscalant when two RO units were operating
then when only one unit was operating (Fig. 5).
The feedwater for the RO system was pumped
from a borehole. The borehole pump was found
to be stopping and starting very frequently when
only one RO was running. The hydraulic shock
from pump starting and stopping caused erratic
feeding of the antiscalant from the dosing line,
giving intermittent mini slug-doses and the wide
fluctuation. The problem was uncovered with the
use of traced antiscalant and corrected by recom-
mending that both RO units operate simulta-
neously to more effectively use the water produced
by the borehole pump.
Using the preferred operating protocol, chemical
dose still varied by about 4-2 ppm of the target
antiscalant dose. Further improvements were
made by using automatic control to dose the
antiscalant. An automatic controller, installed on
the TRASAR detector, was activated and used to
automatically change the chemical feed pump
stroking rate so that the appropriate amount of
chemical was delivered at all times. Using the
automatic control, the antiscalant dose was within
4-0.5 ppm of the target dose at all times (Fig. 6).
The results show that the extremes of under-
dosing and overdosing were removed, which means
that the RO membranes were more effectively
protected against scaling and fouling.
The long-term results of this trial were:
• Operating costs reduced
• RO system now reliable
214 E.H. Kelle Zeiher et al. /Desalination 157 (2003) 209 216

25
20 ¸
o Traced antiscalant was used to treat the system.
15;
[3_
B-
5 frequency to assure a continuous dose of 12 ppm
0 200 400 600 800 1000
Consecutive minutes of operation
Fig. 6. Effect ofTRASAR"' control.
• The maintenance supervisor reported that"The
system has been running very smoothly which
we have not experienced for quite a while."
Overall, the expected cost savings for this system
is about 6 140,000-170,000 per year depending
on labour costs. This is t~ 780-950/1000 m 3.
5. Trial site 2 report
The second trial site also used RO product
water for feed to high-pressure steam boiler
(Fig. 7). Following the primary RO, the water was
further treated by passing the permeate through a
second RO to produce ultrapure water for the
boilers.
The customer was seeking to improve control
of the RO system and supported the r e m o t e
monitoring possibilities offered by T R A S A R
Technology.
The product was monitored by means o f a fluoro-
meter that measured the dosage of antiscalant in
the concentrate line o f the RO. A controller
automatically adjusted the dosing pump stroke
of antiscalant in the concentrate stream.
All RO system parameters, including the anti-
1200
scalant concentration, calculated percent recovery,
percent rejection and normalised permeate flow,
were logged and recorded using advanced moni-
toring capabilities [14]. During the early stages
of the trial, a data download from the performance
monitor indicated that the dosage level o f anti-
sealant had fallen below the 12 ppm set point in
the concentrate stream. Prolonged operation without
antiscalant, or with an inadequate dose o f anti-
scalant, could lead to severe fouling conditions. The
customer was alerted, and inspection of the chemical
feed system revealed a crimped feed line. Although
the pump was working at full speed, very little
chemical was able to reach the RO feedwater due
to the blocked line. The situation was corrected
and chemical treatment reached the appropriate
dosage within minutes (Fig. 8). The system has
now been fully automated to provide alarms at a
local control room for the direct attention o f the
site engineering staff.

Antiscalant

Permeate to Post-
Cv~tYer~ ~ ~ - ~ © , Treatment and
Boilers

Bisulfite
~, Sample Point

Concentrate to
Cooling Towers Fig. 7. Systemoverviewtrial site 2.
 E.H. Kelle Zeiher et al. /Desalination 157 (2003) 209-216 215

5O

..... Conc

45 ~Set Point

+ Control Limits
4o

_ _ 3. Crimped
35 1. ChemicalFeed Falls Below Set
Feed Line
Point, Indicating Problems Repaired,
30
- Control
,<

ft.
25

15
/ 2. ControllerTries to Bring
Feed Back to Set Point
Value
Reestablished

10
t
.......... ii:
i i:i ....
5

0 • i r --

25 30 35 40 45 50 55 60 65 70 75

Time

Fig. 8. TRASAR" monitoring identifies crimped chemical feed line.

6. Conclusions
• Effective monitoring and control is provided
by the T R A S A R technology.
• Costs can be minimised with timely and accurate
alarms to warn o f low antiscalant dosing
° The use o f R O T R A S A R h a s demonstrated that
the automated monitoring and control o f anti-
scalant dosing works effectively and effici-
ently.
Antiscalant dosing is cost effective, environ-
mentally acceptable, and safe.
Automated antiscalant monitoring and control
eliminates a major drawback to antiscalant use:
the fear o f overdosing or underdosing. In addition,
remote m o n i t o r i n g and control o f antiscalant
dosages is now possible.
Taken together, these advantages make
antiscalant use a clear choice for consistent, safe,
effective scale control in RO plants.
References
[1] A variety of courses are offered by David H. Paul,
Inc, including (a) Reverse Osmosis Water Treatment,
Short Course, July 24, 2002, Chicago; (b) Scaling
Fouling & Chemical Cleaning, Short Course, July 24,
2002, Chicago; (c) Membrane Training Camp, June
15-19, 1998, San Diego.
[2] Relevant standard from ASTM International include:
(a) ASTM D4194-95, 01-Ju1-1995 Standard Test
Methods for Operating Characteristics of Reverse
Osmosis Devices; (b) ASTM D4516-00, 01-Aug-2000
Standard Practice for Standardizing Reverse Osmosis
Performance Data; (c) ASTM D4692-87, 01-Aug-
1987 Standard Practice for Calculation and
Adjustment of Sulfate Scaling Salts (CaSO4, SrSO4,
and BaSO4) for Reverse Osmosis; (d) ASTM D4472-
89, 01-Nov-1989 Standard Guide for Recordkeeping
for Reverse Osmosis Systems; (e) ASTM D4195-88,
01-Nov-1988 Standard Guide for Water Analysis for
Reverse Osmosis Application; (f) ASTM D4993-89,
01-Nov-1989 Standard Practice for Calculation and
Adjustment of Silica (SiO2) Scaling for Reverse
216 E.H. Kelle Zeiher et al. /Desalination 157 (2003) 209-216
Osmosis; (g) ASTM D4692-01, 01-Nov-2001 Stan-
dard Practice for Calculation and Adjustment of
Sulfate Scaling Salts (CaSO4, SrSO4, and BaSO4) for
Reverse Osmosis and Nanofiltration; (h) ASTM
D3739-94, 01 -Jul-1994 Standard Practice for Calcula-
tion and Adjustment of the Langelier Saturation Index
for Reverse Osmosis; (i) ASTM D4582-91, 01-Jul-
1991 Standard Practice for Calculation and Adjust-
ment of the Stiffand Davis Stability Index for Reverse
Osmosis; (j) ASTM D3923-94, 01-Ju1-1994 Standard
Practices for Detecting Leaks in Reverse Osmosis
Devices; (k) ASTM D4516-00, 0l-Aug-2000 Stan-
dard Practice for Standardizing Reverse Osmosis
Performance Data; (1) ASTM D4189-95 01,-Nov-
1995 Standard Test Method for Silt Density Index
(SDI) of Water; (m) ASTM D4194-95 01,-Ju1-1995
Standard Test Methods for Operating Characteristics
of Reverse Osmosis Devices.
[3] D.C. 13randt, G.F. Leitner and W.E. Leitner, Reverse
osmosis membranes: state &the art. Reverse Osmosis
Membrane Technology, Water Chemistry, and
Industrial Applications, Z. Amjad, (Ed.), Chapman &
Hall, New York, 1993, p. 18.
[4] T. Matsuura, Future trends in reverse osmosis mem-
brane research and technology. Reverse Osmosis
Membrane Technology, Water Chemistry, and
Industrial Applications, Z. Amjad, (Ed.), Chapman &
Hall, New York 1993, p. 58.
[5] A. Buckley, C.J. Brouckaert and C.A. Kerr, RO appli-
cations in brackish water desalination and in the treat-
ment of industrial effluents. Reverse Osmosis Mem-
brane Technology, Water Chemistry, and industrial
Applications, Z. Amjad, (Ed.), Chapman & Hall, New
York 1993, p. 281.
[6] F. Max and E.G Darton, Statistical review of 150
membrane autopsies, 62nd Annual International Water
Conference, Pittsburgh, Pennsylvania, USA, October
21-25, 2001.
[7] 13. Andrews and J. Mazur, The impact of eliminating
softeners as pretreatment for reverse osmosis systems.
Proe. 61st Annual International Water Conference,
Pittsburgh, Pennsylvania, USA. October 22-26, 2000.
[8] W. Byrne, Reverse Osmosis. A Practical Guide for
Industrial Users, 2nd ed., Tall Oaks Publishing Inc.,
2002, p. 179.
[9] W. Byme, p. 358 cites several examples of analytical
methods for determining scale inhibitor concentra-
tions. Most of these methods involve multi-step
laboratory manipulations, making them poorly suited
for field applications.
[10] M.J. Chmelovski, Fluorescent-traced chemical prog-
rams not just a feed and control program, but a
problem-solving tool, 58th Annual International Water
Conference, November 3-5, 1997.
[11] C.A. Buckley, C.J. Brouckaert and C.A. Kerr, RO
applications in brackish water desalination and in the
treatment of industrial effluents. Reverse Osmosis
Membrane Technology, Water Chemistry, and Indust-
rial Applications, Z. Amjad, (Ed.), Chapman & Hall,
New York, 1993, p. 285-290.
[12] FilmTec Corporation memorandum, Compatibility
Approval of Antiscalant.
[13] Hydranautics Corporation, Technical Service Bulletin,
TSBII5.03, May 1998.
[14] The RO-Eye TM Performance Monitor, available from
Ondeo Nalco, was used to track RO perforlnance.
[15] PermaCare RO 12 software, Ondeo Nalco, May 2002.