Water Technologies & Solutions

technical paper

novel polymer technology for boiler deposit control

Authors: Anthony Rossi and Richard Salazar, SUEZ The left side of Diagram 1 below illustrates a typical
and “healthy” boiler steam generating tube
Presented at the AWT conference of 2015
temperature profile through the carbon steel wall.
The right side shows a condition where an insulating
abstract waterside scale layer is present on the heat transfer
surface. Since the boiler operating pressure is
Waterside scale deposits in steam boilers can have a fixed, the bulk boiler water temperature is fixed at
dramatic impact on fuel efficiency, boiler structural the steam saturation temperature corresponding to
integrity, and maintenance costs for the steam plant the pressure.
operation. In severe cases, waterside scale
accumulations can cause boiler tube failures due to
overheating, restriction of effective water circulation, figure 1: impact of waterside scale on boiler tube
as well as under deposit corrosion mechanisms. The temperature & overheating failures
primary measures to prevent these failures are
effective make-up water pretreatment, internal
chemistry control, and effective chemical treatment
practices.
Regarding the most recent advances in chemical
boiler treatment, SUEZ has recently introduced a
novel terpolymer chemistry control of waterside scale
deposits in steam boilers in the low-to-intermediate
pressure ranges up to 900 psig (approximately 60
barg).

impact of waterside scale on boiler tube integrity Even a thin layer of insulating scale on the heat
transfer surface, as shown, can seriously impede
and efficiency heat transfer through the tube wall, causing
elevation of the internal temperature. This is due to
Efficient transfer of heat through the boiler tube wall the very low thermal conductivity of common boiler
from the combustion to the water side is critical to the scale forming mineral deposits – see Diagram 2 –
integrity and reliability of the tube metallurgy. The and their ability to impede efficient heat transfer.
process of boiling water and generating steam at the
heat transfer surface effectively removes the thermal
energy transmitted through the steel tube wall from
the combustion process. Steam formation cools and
maintains a tolerable temperature profile through the
carbon steel tube wall, which is essential to the
structural integrity of the boiler tube metallurgy.

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.

TP1211EN.docx Oct-15
 figure 2: thermal conductivity of common boiler deposits
versus boiler steel
Common boiler scale deposits, such as the broad
categories listed in Diagram 2, occur at the highest
temperature surfaces in the boiler, which are the
steaming (or evaporative) heat transfer surfaces in the
radiant zone.
Carbon steel has a very well-defined, crystalline grain
structure consisting of almost pure iron grains
(referred to as “ferrite” grains) interspersed with
carbon-reinforced iron grains (“pearlite”). It is this
unique ferrite-pearlite grain structure that gives
carbon steel a much higher tensile strength than pure
iron without the carbon component.
Long-term elevation of the temperature of the carbon
steel tube above approximately 850F begins to
degrade the carbon steel grain structure. If such
high-temperature conditions persist, destruction of
the normal grain structure can reduce the tensile
strength of the tube, and its ability to resist boiler
pressure. As a result, the boiler tube undergoes
deformation (expansion in diameter) in the affected
area, and is subject to rupture.
This failure mechanism is known to boiler engineers
and metallurgists as “long-term overheating”.
Waterside scale deposits are the leading cause of this
common failure mechanism. Long-term overheating
is consistently among the leading causes of boiler tube
failure causing unscheduled outages.
An example of a water tube failure due to a hardness-
based waterside deposit from the SUEZ metallurgical
laboratory located in The Woodlands, TX is illustrated
in Figure 3.
In this case, the deposit was composed primarily of
calcium phosphate (hydroxyapatite), and the measured
deposit weight density on the waterside surfaces
exceeded 190 g/ft , a very heavy deposit.
2
Page 2
figure 3: 600 psig boiler overheating tube failure due to
water side scale
In addition to long-term overheating, other boiler
tube failures can result from excessive waterside
scale formation. Under-deposit corrosion (UDC) is
one such mechanism, and can be highly destructive
in that it is localized and very difficult or impossible
to detect via visual inspection methods.
Steam generation still occurs under a boiler deposit.
A porous or permeable deposit will allow
concentration of non-volatile dissolved solids under
the deposit, frequently at concentrations far in
excess of their bulk boiler water concentrations.
Caustic gouging is a localized form of under-deposit
corrosion frequently observed in boilers receiving
high-purity make-up, such as demineralized or
high-quality reverse osmosis pre-treatment. Acidic
contaminants, such as chlorides and organic or
inorganic acids arising from process contamination
can also cause localized UDC failures.
In Figure 4, a failure from a 400 psig water tube
boiler receiving RO-quality make-up is detailed. In
this case, a heavy, iron-dominated deposit formed
on the side of the tube facing the hot combustion
gases – termed the “hot side”. In this case, both
overheating damage and under deposit caustic
corrosion contributed to the tube failure. However,
the root cause was the waterside iron oxide deposit.
TP1211EN.docx
 figure 4: water wall tube from a 400 psig boiler receiving
RO make-up
example of metal oxide deposit-induced overheating &
under deposit corrosion
Excessive scale deposits, particularly brittle forms of
deposit, can also fracture and dislodge from tube
surfaces, often referred to as chip scale. Large
accumulations of chip scale, or large pieces of scale
can block or occlude tubes, creating restrictions that
result in loss of flow to steam generating tubes.
As mentioned, without water flow and steam formation
to remove heat, the carbon steel can rapidly overheat
and rupture. This mechanism is sometimes referred
to a “short-term overheating” or a “thin-lipped burst”
to distinguish it from long-term overheating. A case of
generating tube failure from a 700 psig water tube
boiler due to blockage of flow by iron oxide deposit
accumulations is illustrated in Figure 5.
figure 5: 700 psig boiler steam generating bank tube
blockage with iron oxide deposit
danger of tube failyre due to restricted circulation and
short-term overheating rupture
impact of waterside deposits on boiler efficiency
Excessive waterside scale can also negatively impact
boiler fuel-to-steam efficiency. Smaller package
watertube and firetube designs are particularly
vulnerable due to their limited heating surface area
TP1211EN.docx
versus larger, field-erected industrial and utility
boilers. The latter commonly have heat absorption
circuits downstream of the boiler bank or
waterwalls in the combustion path - superheaters
and reheaters, feedwater heaters and economizer
circuits, which may not be present in package units.
These circuits can often absorb the heat which is
rejected by the boiler due to the insulating effects of
excessive waterside scale.
The chart in Figure 6 is from a US Department of
Energy bulletin that summarizes the results of a
university study detailing the measured fuel energy
loss due to several types of waterside scale
deposits. In package boiler designs without
extensive post-boiler heat recovery circuits,
increases in stack gas exit temperatures are
normally the most reliable indicator of degraded
fuel-to-steam efficiency due to scale formation.
figure 6: package boiler efficiency losses due to
waterside scale
boiler deposit control technology development
Acrylic based polymers for boiler treatment have
been effective under most conditions, but some have
failed under high stress conditions such as high
contaminant levels, high pressures, and high heat
transfer surface temperatures.
The new SUEZ Boiler Terpolymer (BTP) is an
evolution of SUEZ boiler organic synthesis. The
Terpolymer provides advantages in performance of
boilers with pressures up to 900 psig, improving iron
oxide scale control, as well as improved hardness
and iron contamination transport. Importantly, BTP
has also demonstrated the ability to effectively
recover from hardness contamination upsets.
Extensive testing of BTP against commonly used
boiler treatment chemicals such as
Page 3
polymethacralate and acrylic acid was conducted on
research boilers. The testing of BTP chemistry in the
research boilers was conducted with relative steam
flow, residence times, and heat fluxes equivalent to
field boilers. This experimental procedure has
developed many water treatment programs. Utilizing
research boilers provided the opportunity to rapidly
simulate a wide variety of pressures and contaminant
levels.
Feedwater contaminant was varied by pressure with
150 psig (10 barg) tests utilizing 8 ppm Ca (as CaCO ), 2
3
ppm Mg (as CaCO ) and 1 ppm iron. Between 300 and
3
600 psig (21 and 42 barg), 4 ppm Ca (as CaCO ), 1 ppm
3 field performance
Mg (as CaCO ) and 1 ppm iron was used. Feed water
3
silica was fixed at 6 ppm (as SiO ) for all pressures.
2 Research testing results were duplicated and
Contaminate transport efficiency was measured by
comparing the level of a specific contaminant. In this
case we evaluated calcium, magnesium, iron and
silica, in the feedwater during a run to the level in the
research boiler blowdown, while considering the
degree of dissolved solids concentration due to “cycles
of concentration” in the boiler. This can be expressed
by the equation below:
Throughout the testing, BTP demonstrated the ability
to control deposit formation on heat transfer surfaces
equal or better than current industry standards at
equivalent polymer dosages or below. Relative to
standard All-Polymer dispersants, BTP was able to
maintain comparable calcium transport with
significant improvements to magnesium and iron
transport.
Figure 7 illustrates the ion transport efficiency for
various contaminants and chemistries. Based on
transport efficiency for hardness, silica and iron, the
Acrylic Acid/Sulfonate/Sulfonated ethoxylate
(AA/S/EOS) boiler terpolymer showed significant
improvements compared to commonly used
benchmark chemistries.
Page 4
figure 8: Ion Transport Comparison at 300 psig (21 bar)
validated with field trials. A Northeastern US college
was operating a simple cycle heat recovery steam
generator producing 160 psig steam from the
exhaust gas from a combustion turbine. This unit
received a combination of softened make-up and
zeolite-polished condensate as feedwater. During
the period of late 2012 into 2014, the main
condensate return line from campus was
intermittently out-of-service for excavation and
repairs.
Hardness levels in the feedwater during this period
were elevated and highly variable, averaging
approximately 3 ppm (as CaCO3). There were
frequent excursions between 5 and 30 ppm (as
CaCO3). The intermittent and highly variable pattern
of hardness contamination resulted in hardness
scale formation in the steam generator.
Prior to the introduction of BTP, the previous
chemical treatment was an earlier generation All-
Polymer that provided good results when the
hardness contaminant loading was lower. However,
with the poor quality of condensate return with high
hardness levels in the feedwater, there was
significant progressive build-up of hardness scale.
Upon inspection of the HRSG in the spring of 2013,
scale consisting of calcium, magnesium, silica, and
iron were present throughout the boiler. Figure 8
below shows the condition of the boiler during the
inspection.
TP1211EN.docx
 figure 8: 2013 inspection of 160 psig HRSG figure 9: BTP performance under varying feedrates

Based on research testing, the application of the BTP With continued hardness excursions and the proper
all-polymer program would allow the flexibility to BTP chemical treatment dosage based on feedwater
continue to use the higher hardness make-up water demand, the inspection the following year showed
while protecting the internal heat transfer surfaces great improvement. Figure 10 shown below was
from deposition and scale, while minimizing the taken in May 2014. This photo is from the same
amount of contaminants building up in the system. HRSG inspection as Figure 8, and shows the tubes
and drum are visibly cleaner with much less
The SUEZ Boiler Terpolymer (BTP) was introduced in deposition than in 2013.
early spring 2013 a few weeks prior to the inspection.
During the initial trial of BTP, we gradually increased figure 10: 2014 inspection of 160 psig HRSG
the feedrate of the BTP. This temporarily resulted in a
significant underfeed of the treatment during the
initial phase.
As shown in Figure 9, during the initial startup of the
trial, BTP was fed at less than 10% of feedwater
demand due to the intermittent hardness excursions.
During this period, transport levels were maintained in
the 40 to 50% range for hardness, iron, and silica.
Once the treatment dosage was reset based on
feedwater demand, the contamination rejection rates
increased dramatically. As shown in Figure 9, the
calcium rejection measured had been maintained for
more than 6 weeks above 250%.

A second field evaluation was performed in a D-type

watertube package boiler with a rated capacity of
28,000 pounds of steam per hour, operating at
approximately 170 psig and receiving deaerated
feedwater comprised of a combination of 20%
softened municipal make-up water and 80%
returned condensate.

TP1211EN.docx Page 5
During the summer of 2014, this boiler was treated
with SUEZ Boiler Terpolymer (BTP) technology. An
upset in the condensate returned to the feedwater
tank caused a temporary excessive amount of
hardness in the condensate and feedwater. The
hardness levels for the condensate and feedwater
ranged from 5 to 100 ppm (as CaCO3) from 8/10/14
thru 9/20/14 shown in figure 11.
figure 11: hardness in feedwater of package boiler
Inspection photos from Fall 2013 and Fall 2014 are
shown in Figures 12 and 13, respectively. The
distinguishing feature of the inspection photos show
that despite the elevated hardness in condensate and
feedwater, the steam drum surface in the 2014
inspection was essentially clean except for some
slight trace deposits.
figure 12: 2013 inspection of steam drum
Page 6
figure 13: 2014 inspection of steam drum
The last field trial of the terpolymer was undertaken
to evaluate performance in a system with high levels
of hardness contaminant, where effective deposit
was critical and challenging. This metals refining
facility operates a series of large firetube boilers at
90 psig, producing approximately one million pounds
of steam per day for the refining process.
The feedwater consists of an average of 30%
deaerated, softened make-up and 70% returned
condensate. Due to the process, the condensate is
consistently contaminated with high levels of
hardness, which averaged slightly above 5 ppm (as
CaCO ) during the trial period, as shown in Figure 14.
3
figure 14: northeast metal refiner boiler feedwater
contaminant levels
averages for Oct. 2012 – Sep. 2013
TP1211EN.docx
The incumbent treatment program consisted of an All-
Polymer treatment based on a synthetic carboxylated
polymer, and for additional deposit control, was
augmented with a chelant/polymer/phosphate
program. As shown in Figures 15 and 16, although
there was significant waterside deposition, this
previous program maintained the boilers in
operational condition despite the high and continuous
influx of hardness.
figure 15: firetube boiler 4 – May 2013 – prior to Solus AP
program
figure 16: boiler 4 – May 2013 – prior to Solus AP program
The Solus* AP All-Polymer was initiated following the
May 2013 outage and inspection. In order to track and
compare performance to the previous program,
feedwater and boiler water samples were collected on
both programs on a regular basis for analysis at the
SUEZ customer service laboratory in the Woodlands,
TX. Hardness, iron and silica levels were tracked,
along with average boiler cycles of concentration.
TP1211EN.docx
From this data, time-averaged levels of transport of
these contaminants through the boiler to the
blowdown were calculated. Data was collected over
a period of almost two years for both programs, and
the summary is presented in Figure 17.
figure 17: northeast metal refiner
average contaminant transport levels
feedwater to boiler blowdown
During the Solus AP (BTP) trial period (without the
supplemental chelant/polymer/phosphate product),
the new terpolymer provided significantly improved
transport of magnesium and silica, and slightly
enhanced transport of iron and calcium.
Two photos of the waterside surfaces of Boiler 4
taken during the May 2014 inspection, 12 months
after start of the Solus AP program, are shown in
Figures 18 and 19. This is the same boiler shown in
Figures 15 and 16 from the May 2013 – prior to the
Solus AP program implementation.
Due to the high level of incoming hardness,
accurately judging boiler cleanliness after
approximately one year on the new program is
somewhat subjective. There was, however, visible
evidence of reduced overall deposition.
As illustrated in Figure 19, there was consistent
evidence of partial removal of the layered scale
accumulations from heavily encrusted lower
firetube passes. The remaining scale observed in
the lower pass tubes was relatively soft and non-
adherent, and much of it could be removed easily by
hand.
Page 7
 figure 18: firetube boiler 4 – May 2014 – 12 months after
start of Solus AP program
figure 19: firetube boiler 4 – May 2014 – 12 months after
start of Solus AP program
summary
The results of field trials of the patented SUEZ
Boiler Terpolymer (BTP) program have been very
successful, and correlated well with the results of
the research-scale laboratory boiler evaluations.
The new All-Polymer program provided not only
improved control of iron oxide and hardness
deposition versus the benchmark programs against
which its performance was compared, but
importantly, improved tolerance to very high stress
conditions, including elevated hardness levels for
extended periods. Solus AP (BTP) met both the
performance and economic expectations of the
customers, and is now in continuous use at each of
the trial sites discussed.
* Solus is a trademark of SUEZ. May be registered in one or more
countries.

references
1. D. Meskers, A. Rossi, K. Person “Evaluation of
Terpolymer for Deposit Control in Hardness and
Iron Dominated Boiler Systems”
2. D. Meskers, A. Rossi, K. Person “Solus* AP
Advanced Boiler All-Polymer Technology”
3. D. Meskers, et. al., U.S. Patent 8,728,324

Page 8 TP1211EN.docx