ETHYLENE FURNACE TRANSFER LINE EXCHANGERS

“BOILER TREATMENT & CHEMISTRY”

James R. Attebery
Sr. Boiler Consultant
GE Water & Process Technologies
Trevose, PA

Siong Wah Hing

Regional Technical Manager – SEA
GE Water & Process Technologies
Kuala Lumpur, Malaysia

Abstract:
This paper is intended as a review of current technology options and practices for the
effective treatment of the water and steam circuits in Ethylene Furnace Transfer Line
Exchangers (TLE’s) to assure optimum reliability, longevity, and efficiency.
Common TLE designs will be briefly reviewed, as well as the benefits and concerns with the
various boiler treatment approaches, as well as an alternative practice for cold start-up and
passivation of the Boiler System.
External treatment processes, including demineralization and condensate polishing, will
be reviewed from the perspective of minimizing contaminant ingress to reduce the potential
for deposition and corrosion in the high heat flux Transfer Line Exchangers.
Current boiler water treatment practices will also be reviewed with respect to ASME and
VGB application guidelines. This will include a discussion of the choices and selection criteria
for oxygen scavengers, as well as the review of the internal treatment chemistries, including
coordinated/congruent pH/phosphate control; alkaline phosphate; and all-volatile treatment.
The application and benefit of synthetic polymeric dispersants in TLE’s will also be briefly
discussed. Brief discussion on boiler cycles and retention times are included.
Steam/condensate treatment technology based on volatile alkalizing agents will also be
reviewed, along with steam purity guidelines and issues as they relate to steam turbine
reliability and integrity.
The adverse effects of low level chloride and sodium contaminants in the feedwater will
be reviewed and the results of computer studies to show effects on both low phosphate and
all volatile treatment programs, as compared to more conventional phosphate control levels.
In closing, there will be brief review of several internal metallurgical studies that will
highlight key discussion points in relation to low level contaminant intrusion resulting in boiler
system failures.

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Introduction to Boiler System Treatment:
Auditing an Ethylene Plant Boiler system is very important to assess the system and treatment
program basics, including identifying potential conditions that may effect plant reliability,
and/or determine the root cause of a specific problem.
Ethylene Plant Boiler system chemical treatment programs are determined by a number of
factors, including: the Boiler System Steam pressure; the heat flux; circulation rate; and the
specific design of the waste heat recovery system, the Cracking Furnace and the Transfer Line
Heat Exchangers (TLE’s).
The primary objectives of boiler system chemical treatment are: system protection; failure
prevention; operating reliability; and efficiency. These objectives are achieved by the
successful application of the optimum system treatment program, resulting in effective deposit
control; corrosion minimization; and maximizing steam purity.
Because of the emphasis of designing the most effective boiler treatment program on the
process system and equipment, a successful chemical treatment program will require
knowledge and understanding of the Ethylene Plant Unit Operations and Processes. For
example this will include knowledge of: External Treatment; Deaeration; Boiler system
operation, design and metallurgy; chemical treatment concerns and restrictions; Steam uses;
such as for Steam Turbine Drivers for Pumps and Compressors; and contamination issues
related to condensate recovery.
The paper will begin with a description and explanation of a typical Ethylene Furnace System;
and review typical designs of Transfer Line Exchangers (TLE’s); and their associated steam
drums and auxiliary equipment.
Following the introduction, we will review: a typical external treatment system; typical High
Pressure Boiler Treatment programs; Boiler Treatment Guidelines; and typical Boiler Failure
mechanisms. Also included will be a comparison and review of the internal treatment
programs considered (Phosphate based and All Volatile), considering both ASME and VGB
Guidelines, and with low level contaminants present in the feedwater.
We will briefly compare Utility Power Boilers, with Industrial Boilers.
An example of Cold Start Up Rinse/Passivation Procedure of the Boiler System will be
reviewed, including the use of polymeric dispersants for boiler system iron transport.
Lastly, GE Water Metallurgical Report summaries will be reviewed for examples of the various
boiler system failure mechanisms that have been observed.

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Typical Transfer Line Exchanger (TLE) Description:
Ethylene Cracking Furnace Transfer line Exchangers (TLE’s) are designed to recover the waste
heat (energy) from the Pyrolysis Furnace “Cracked Gas” ahead of the Quench Tower and
produce high pressure steam. The TLE WHB’s in Ethylene Plants are integrated into the
process and are an absolute necessity to the process operation.
This means that boiler deposition and corrosion issues, which may lead to failures of the waste
heat boilers, could simultaneously result in process shutdown and loss of production. In this
situation, unit reliability is essential from a plant operations standpoint, and total costs
associated with a single failure can exceed the total cost of the boiler.
Transfer Line Exchanger (TLE) Waste heat Boiler designs are generally considered as firetube
boilers, with process cracked gas stream on the tube side pass, and the boiler water on the
shell side, with natural (thermal) boiler water circulation from the steam drum.
There are a number of different design styles in Ethylene Plant TLE’s. The TLE geometry can
be vertical or horizontal, depending on plant requirements. Conventional designs include:
Shell/Tube, with boiler water usually on shell side; Double Tube/Oval Headers; and one design
includes a secondary quench exchanger (SQE) shell with bayonet and scabbard tube
configuration. Note Typical Examples below in Figure 1.

Shell/Bayonet/ScabbordTubes
BW Downcomer

BW Riser BW Riser

Bayonet Tubesheet
Furnace Gas
Scabbard Tubesheet
Outlet
Gas Deflection Baffle

Bayonet Tube

Refractory Liner
Scabbard Tube

Furnace Gas Inlet

Double Tube/Oval Header Inlet Gas Distributor

Vertical Shell/Tube

Figure 1

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Typical boiler operating pressures in Ethylene Plants range from 600 to 1800 PSIG (40 – 125
Barg). Typical Boiler Feedwater makeup is mixed bed demineralized, and polished steam
condensate.
Ethylene Plant Boiler designs are based primarily on process unit considerations, while making
compromises on the waterside. Some High Pressure TLE WHB designs allow very little
tolerance for deposition, or deviations in boiler water purity.
Boiler failures in Transfer Line Exchangers (TLE’s), can be related to design; operation; water
treatment; or a combination of factors. To avoid internal corrosion, the water chemistry must
be within strictly controlled guidelines at all times. Even short-term contamination of the
feedwater, may lead to corrosion-induced failures within weeks or months, particularly if a
boiler system is considered to have deposition.

External Treatment System Description:

In most Ethylene plants, the External Treatment system will include: a Demineralizer System;
a Condensate and Boiler Blowdown Recovery System; Activated Carbon Filters on the return
condensate with Cation Polishers; and Mixed Bed Polishers on the combined stream of
condensate; demin makeup, and turbine condensate. The effluent from the mixed bed will be
preheated and then deaerated. A typical External Treatment System is shown in the following
drawing (Figure 2):

Olefins Unit - Condensate Polishers Vent

LP Steam
Atm vent
Demin/Condensate LP Steam

LP Condensate Mu Prehtr
O2 Scavenger
Steam Drum Flash Steam
& TLE’s
CBD Blowdown Condensate Deaerator
Flash Tank Receiver
Amine
60 M3/Hr
HP
FT

Export To
BFW
To DSG To Attemperation Steam
Waste Cond
To Waste CUF Drums
pH

DSG Condensate Cation Activated

Polisher Carbon
Filter PO4/Polymer
Demin Import Cond
130 M3/Hr
2 Trains

Mixed
Turbine 2 Trains Micron
Bed
Condensate Filter
TOC Polisher

Waste Cooling water SiO2

Figure 2.

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Note in the above Figure 2, this typical system design includes: on-line analyzers for
monitoring of: Conductivity and pH of the condensate returns; Total Organic Carbon (TOC)
monitoring of the combined outlet of the Steam Condensate Dilution Steam Generator
Condensate; the imported Demin Makeup, and the Turbine Condensate to the Mixed Bed
Polisher. The effluent from the Mixed Bed Polisher will typically include on-line Conductivity
and Silica measurement.

Ethylene Process Pyrolysis Furnace System:

An example of a typical cracking furnace, including the Deaerator; transfer line exchangers;
and steam drum system is shown in Figure 3 below.
The deaerated boiler feedwater is preheated in the first pass convection coil; the “Secondary
Quench Exchanger”; the second pass convection coil; and into the steam drum.
In this example - note that the Boiler internal treatment is injected into the BFW line
downstream of the Attemperation water take-off; and upstream of the Economizer. The HP
Steam generated in the TLE exchangers will be separated in the steam drum and then
superheated in the furnace convection coils. The steam superheat temperature is controlled
by BFW Attemperation water, injected between the first and second HP steam convection
passes. Thus, consideration for BFW purity used for Attemperation must be considered.

Cracking Furnace - Transfer Line Exchangers

Figure 3.
Demin/Cond

Cracked Gas
Steam Drum
CBD
LP Steam SQE
Deaerator
Amine
Oxygen Internal
Scavenger Treatment IBD

BFW

Attemporation

To Quench
SH HP Steam Water Tower

Feedstock Pyrolysis Furnace

TLE

Dilution
Steam

Fuel Gas
IBD (Shell & Tube TLE’s) To BD
Flash Tank

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In the typical design in Figure 3, Intermittent Blowdown is noted from the steam drum and
the bottom tube sheet area of the vertical TLE’s, as may be typical in some “shell and tube”
TLE designs. However, other TLE designs, such as the “double tube” and the
“Bayonet/Scabbard tube” TLE’s, do not have Intermittent Blowdowns on the TLE Exchangers.
TLE designs, with boiler water on the tube side of the exchanger, are generally considered less
prone to deposition and corrosion, because of the higher velocities on the tube side compared
to shell side passes.

In the following drawing, Figure 4, is an example of a boiler water/steam circuit with vertical
Shell and Tube TLE’s, and the boiler water downcomers and risers to the steam drum. Also
note that in this particular design, the steam separation internals consists only of a baffle
system on the boiler water Risers and a demister pad for steam/water separation. Note also
the vortex breaker on the boiler water Downcomers, and the location of the Continuous and
Intermittent Blowdowns:

Sat Steam
Demister
to Superheater Pad
Typical
Typical
Steam TLE
TLEQuench
QuenchCooler
Cooler&&
Drum Steam
SteamDrum
DrumSystem
System
IBD Tube Sheet
CBD
Vortex Vent
BFW Preheater
Flow Breaker (SQE)

CBD

“Transfer LineExchanger” IBD (Shell & Tube TLE’s)

TLE (4) Ethylene Furnace
Figure 4. “Cracked Gas”

Typical High Pressure Boiler Treatment Programs:

The Boiler chemical treatment programs, considered for the High Pressure Boiler Systems and
TLE’s in Ethylene Plants, will include the application of “Oxygen Scavengers” for deaeration;
“Internal Boiler treatment”, usually either phosphate based or All Volatile for corrosion and
deposition protection; and application of “neutralizing amines”, for steam/condensate
corrosion protection.

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Organic Oxygen Scavengers, are normally used because of the high purity makeup
feedwater water quality, as they do not contribute dissolved solids to the boiler water, and
most are also volatile. In addition, organic oxygen scavengers assure a reducing environment
for formation of protective magnetite to passivate and minimize feedwater iron entering the
steam drum.
Typical Organic oxygen scavenger molecules include, but are not limited to:
1. Carbohydrazide
2. Hydroxylamines
3. Hydroquinone
Boiler Internal Treatment Programs, are typically phosphate based, in most cases also
blended with dispersant polymers and caustic, to achieve a target sodium/phosphate ratio in
the boiler system - or the program is an All Volatile treatment.
1. Congruent pH/phosphate control
2. Alkaline pH/phosphate control, particularly if concerned with “acidic phosphate”
corrosion
• All Polymer programs are not typically used in Ethylene TLE Boiler System’s
All Volatile Treatment Programs and Steam/Condensate Amines Programs:
The three (3) primary physical and chemical properties used in selecting amine molecules
include:
• Neutralizing Capacity: Ability to neutralize acids (generally CO2), and is
primarily determined by the molecular equivalent weight.
• Basicity: Ability to elevate the pH of water after neutralizing the “acids”.
• Distribution Ratio: quantity of amine present in vapor phase versus liquid
phase.
1. With All Volatile (AVT) Internal Treatment Programs, usually the primary amine
molecule used will have a low distribution ratio, such as Monoethanolamine (MEA), to
protect the boiler water system.
• Typically in practice, the low distribution ratio amine (MEA) will be blended with
other amine molecules with higher distribution ratios and basicity; such as:
Cyclohexylamine; Dimethylaminiopropylamine; Methoxypropylamine (MOPA), and
Morpholine.
2. Neutralizing Amines are also used in most Boiler Treatment Programs for control and
elevation of feedwater and steam condensate for corrosion protection.
3. When internal treatment programs are based on phosphate or phosphate/polymer,
usually amine blends with higher distribution ratios and basicity are recommended to
maximize volatility in the steam to protect steam condensate systems. This includes
the amine molecules noted above.

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Boiler Treatment Guidelines:
Although there are many agencies that publish Guidelines on Boiler Treatment, the Guidelines
generally followed in the Ethylene industry are the American “ASME Consensus Guidelines
on Operating Practices”, and the German “VGB Standards”. In some cases, Boiler
Manufacturers may also issue Guidelines for Boiler Treatment.
The following Table, Figure 5, lists the ASME and VGB Guidelines for Ethylene Plants; and a
comparison to the guidelines as typically used internally by GE Water.

ASME & VGB Standards for Boiler Treatment

GE Water
ASME VGB Ethylene
Boiler Feed Water Notes:
Dissolved Oxygen <0.007 0.020 0.007 1. ASME Consensus Guidelines states: "in all
Cation Conductivity, umhos <0.20 cases where the makeup water is
pH 8.8 - 9.6 9 - 10 9.2 demineralized, and the operating pressure is
Total Hardness + CO2 ND ND 600 PSIG, or greater, the internal boiler water
TDS 0.1 0.1 max chemistry should follow either Congruent
Total Iron, as Fe <0.01 <0.020 <0.01 Phosphate-pH control; Coordinated
Total Copper, as Cu <0.01 0.003 <0.003 Phosphate-pH control; or All-Volatile
Chloride, as Cl 0.01 max Treatment. In such programs, Free
Sodium, as Na <0.010 0.01 max
Hydroxide Aalkalinity must be absent (not
Silica, as SiO2 <0.020 0.02 max
detectable) in the boiler water to prevent
Organics (non-volatile) <0.2 0.5 max
alkaline corrosion.“
Chemicals for Preboiler Protection VAM*
* Volatile Alkaline Materials
2. Alternative Guidelines: In certain boiler
Boiler Water systems, where there is primary concern with
Specific Conductivity, umhos < 80 < 50 < 50
"acidic phosphate corrosion“, GEWPT
pH 9.3 - 9.7 Congruent
recommends "Alkaline Phosphate Treatment"
Total Alkalinity, ppm as CaCO3 NS
with a 4 to 10 ppm ortho-phosphate control
Free OH Alkalinity, ppm as CaCO ND
range; pH consistent with a minimum 2.8
Phosphate, as PO4 6.0 4 - 10
Na:PO4 ratio (pH less than 10.0); and a
Silica, ppm as SiO2 PSIG Dependent maximum caustic level of 1.0 ppm as NaOH.
Continuous Blowdown, % 1 2 (Caustic corrosion is still possible with
deposition).
Steam
Cation Conductivity, umhos <0.02 <0.02
pH 8.5 - 9.2
TDS, ppm 0.1 0.08
Total Iron, as Fe <0.020
Total Copper, as Cu <0.003
Chloride, as Cl
Sodium, ppm as Na < 0.010 <0.010 <0.010 Figure 5.
Silica, ppm as SiO2 < 0.020 <0.020 0.020 max

Note, that steam purity Guidelines are included in the above Table, but are not included in the
scope of this paper for discussion. However, steam purity in Ethylene Plants is very important
in relation to steam turbine fouling and production limitations. Turbine fouling can be a result
of silica volatilization; boiler water carryover; and contaminated attemperating water. In many
cases, steam purity restrictions are specified by the “Steam Turbine Manufacturer”.

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The following Figure 6 includes the typical VGB Boiler Treatment Control Parameters for high
pressure boilers at 1500 PSIG (103 Barg), or above; and the “Low range Alkaline Phosphate
Treatment (PT)”as compared to “All Volatile Treatment (AVT)”.

Boiler Pressure Range 1500 PSIG (103Barg) or higher;

VGB Standards:
"Phosphate" or "All Volatile" Treatment
BFW BW Steam
PT AVT
Conductivity, microSiemans/cm < 0.2 < 50 <3 < 0.2
pH 9 - 10 9.3 - 9.7 8.8 - 9.5
Total Iron, as Fe < 0.020 < 0.020
Total Copper, as Cu 0.003 < 0.003
Silica, as SiO2 < 0.020 < 0.020
Sodium + Potassium, as ppm <0.010 < 0.010
Dissolved Oxygen, ppm 0.02
Ortho Phosphate, PO4 1-3

Note: Conductivity of BFW and Steam is as "Cation Conductivity"

Figure 6.

Note: Frequently, the Ethylene Plant Operator’s choice for internal treatment programs are
limited by the TLE Design manufacturer, in order for the boiler warranty to be in effect.
Therefore, there may be a requirement to follow the above VGB HP Boiler Standards.

Typical TLE/Boiler Failure Mechanisms:

Corrosion – when porous deposits are present, feedwater contaminants, transported into
the boiler, may result in evaporation and a highly concentrated alkaline (caustic gouging)
or acidic species (such as chlorides or acid phosphate) in contact with the metal surface.
This can result in dissolution of the metal, and gouging or pitting.
Concentration of trace contaminants can also occur without deposition being present, if a
liquid/vapor interface exists. This phenomenon is usually referred to as “Steam Blanketing”
or “Departure from Nucleate Boiling (DNB)”, and is also known as “Film Boiling”. This can
occur in the highest heat flux areas of the waste heat boiler. The following graph, Figure
7 is an example of DNB.

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61510
 Effect of DNB
on tube metal temperature

Figure 7.

Pitting - corrosion may be the result of dissolved oxygen in the feedwater; and/or poor
practices during “start-up” and “off-line boiler lay-up”.

Overheating – failures may occur as a result of waterside deposits; excessive heat flux;
or poor circulation, in shell/tube design exchangers.

Boiler Internal Treatment programs:

Coordinated/Congruent Control (Phosphate based treatment programs):
The introduction of Coordinated phosphate control minimized the corrosion of carbon steel by
providing elevated boiler water pH with captive alkalinity, and sufficient chemical buffering
capacity for low-level system contaminants. Phosphate demonstrated the ability to eliminate
caustic embrittlement and caustic gouging. The basis of this chemistry is:
NaOH + Na2HPO4 Na3PO4 + H2O
The risk of “free caustic” in the boiler was further reduced with the introduction of Congruent
Phosphate treatment, where the Na:PO4 ratio was controlled below 2.8. The Na:PO4 ratio for
presence of free caustic is pressure dependent and is higher when boiler pressure is less than
2000 PSIG (138 Barg) .

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However, in some boiler systems, at less than 2000 PSIG (138 Barg) pressure, failures were
not completely eliminated. With shell and tube design TLE’s, the high heat flux on the tube
side and low boiler water circulation rates on the shell side, may result in phosphate hideout.
As a result, these shell and tube design TLE’s are more susceptible to “acidic phosphate”
attack, resulting in severe localized corrosion on the boiler water tube shell side of the TLE’s.
The chemical reaction considered with acidic species is as follows:
HCl + Na3PO4 Na2HPO4 + NaCl
• Although hydrogen damage may be suspected from acidic phosphate corrosion, GE
Water is not aware of cases in Ethylene Plants where hydrogen damage has been
reported. In GE metallurgical examinations performed to date, we have not identified
hydrogen damage in Ethylene Plant TLE’s.
In high heat flux zones, boiler water is likely to concentrate due to evaporation in contact with
the magnetite surface, and phosphate species may exceed their solubility limits and precipitate
– and/or “hide-out”.
In phosphate based treatment programs, the presence of iron oxides, at temperatures of 320
C (608 F) and above - and particularly if phosphate hideout is observed; increases the
possibility of phosphate salt precipitation, and therefore increases the potential for under
deposit corrosion (UDC) of “any” kind. Therefore, the more oxides present, the greater the
probability of corrosion.
The exact corrosion mechanism, at a given bulk boiler water pH or Na:PO4 mole ratio, is
difficult to assess because of many variables, such as deposit accumulations; feedwater
contamination; heat flux; and steam/water ratios that may be involved.
However, because of the evaporation/concentration factor present in high heat flux zones, this
may result in locally induced precipitation that changes the Na:PO4 ratio. Therefore, this
increases the possibility of localized corrosion damage, because of the boiler operator being
unaware that localized pH levels are “different” from those in the bulk boiler water.

Acid Phosphate Corrosion and Phosphate Hideout Discussion:

Unfortunately, most published Technical Papers; Studies; and Research have been conducted
on High Pressure, Fuel Fired, Drum Type Utility Power Boilers, with ultra-pure makeup water,
and generally with only about 1% mixed bed quality makeup, and 99% condensate returns
(that will most likely be mixed bed polished).
Therefore, the results and applications discussed in these published technical papers, are
usually not directly applicable to High Pressure, Industrial Waste Heat Boilers; usually with
high heat flux; poor boiler water circulation on the shell side of shell and tube exchangers;
lower feedwater makeup water purity; high makeup water quantities (lower condensate
returns); and frequent low-level organic and inorganic contaminants in the feedwater and
condensate returns

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Comparison of Utility and Industrial Boilers:

HP Utility Power Boilers:

1. Acid PO4 corrosion (PO4 reacting with Fe and Fe3O4) can occur:
a. with temperature greater 320 C (608 F) and Na/PO4 ratio less than 2.8
b. with temperature less than 320 C (608 F) and Na/PO4 ratio less than 2.2
c. Acid PO4 corrosion can occur in absence of PO4 hideout, with low boiler water
pH levels.
2. Equilibrium PO4 Treatment (EPT) was developed to prevent PO4 hideout and
acid PO4 corrosion in HP Utility Power Boilers.
a. The idea behind EPT is to avoid as much as possible, phosphate precipitation and
hideout. Therefore, with EPT, phosphate will either be deposited and/or come
back into solution when the boiler water phosphate level is either above – or
below the equilibrium phosphate value. Experience has shown that tube
corrosion, with accompanying hydrogen embrittlement, often occurs whenever
feedwater contamination is encountered with EPT treatment.

Industrial Boilers:
With Industrial fired and waste heat boilers (including TLE’s), the questions are not as
easy to answer since an “effect” does not always follow a “cause”. With the presence of
magnetite (Fe3O4); phosphate hideout; and boiler water temperature above 320 C (608 F); a
solid precipitate will not always form, and/or a reaction occur:
1. PO4 hideout does not necessarily mean acid PO4 corrosion, or caustic
corrosion will occur:
a. When PO4 hideout occurs, with temperature greater than 320C (608F) and
Na/PO4 ratio less than 2.8, acid PO4 corrosion is possible, but does not always
occur.
b. With PO4 hideout at greater than 2.8 Na/PO4 ratio, caustic gouging corrosion is
possible, but does not always occur.
2. PO4 hideout can change the boiler bulk water Na:PO4 ratio (up or down)
thereby affecting bulk water pH.

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 3. PO4 hideout is promoted with iron oxide deposition and high heat flux,
because of the thermal energy present to form the solid, and the absorption
in the iron oxides.
4. PO4 hideout potential increases with increasing - boiler operating pressure;
PO4 residual level; and with iron oxide laden tubes or boilers.
a. PO4 hideout and corrosion mechanisms are minimized and/or eliminated, when a
clean, passive surface is present in the boiler.

Phosphate Hideout Study during Decoke Cycle:

If phosphate hideout is suspected, it is possible that hideout may be verified or identified
during a study of boiler water pH; phosphate; and conductivity during a de-coke cycle.

Alkaline Phosphate Treatment Program:

Alkaline Phosphate, as practiced by GE Water, is considered the treatment of choice, if or
when concerned with “acid phosphate” corrosion. The application is very similar to congruent
phosphate control, with the following control parameters as generally practiced:
• Boiler Water phosphate: 4 to 10 ppm
• pH consistent with a minimum of 2.8 Na:PO4 ratio
• BW pH < 10
• Maximum caustic level of 1.0 ppm as NaOH.

The VGB TLE low range phosphate treatment program for HP Boilers, noted earlier in this
paper, is also considered to be “alkaline phosphate” control - with the ortho-phosphate control
range specified to be 1.0 to 3.0 ppm with the boiler water pH in the range of 9.3 to 9.7.
In addition, the very low level of phosphate in the VGB program requires very pure boiler
feedwater at all times; as low ppb levels of contamination will most likely result in either
“acidic phosphate corrosion”, or “caustic gouging”. Therefore, feedwater purity must be
closely monitored and controlled.
Comparisons of the theoretical control of the VGB low alkaline phosphate versus the typical
congruent pH/phosphate program as practiced by GE Water, will be shown and discussed in
the next section, including a discussion of the same concerns when using AVT.

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All Volatile Treatment Programs (AVT):
All Volatile Treatment (AVT) programs are commonly used in many Ethylene plants. IF the
makeup water is always high purity water, AVT will result in acceptable treatment results in HP
Boilers.
However, AVT does not provide any “buffering” in the cycled boiler water to reduce the impact
of low-level contamination, and/or provide any deposit control. Contaminants are always
possible in the feedwater as a result of slippage of acidic or alkaline ions from the external
treatment system, and/or cooling water leaks into turbine condensate.
• There are distinct advantages in the use of AVT, as long as high purity make-up water
can be assured. For example, the injection of “all volatile” treatment programs does
not require sophisticated chemical feed equipment and can be injected into the
Deaerator storage or the common boiler feedwater, even ahead of Attemperation water
take-offs.
• In contrast, with phosphate based programs, the chemical feed systems are often
complex and expensive; require significant operator attention and monitoring; and
generally must be fed to each individual cracking furnace steam drum. However, the
phosphate-based programs are significantly more forgiving and protective of the boiler
system corrosion rate, with low-level contaminant intrusion, than All Volatile
Treatement.
Recall in the VGB Standards, that AVT programs are specified with a pH range of 8.8 to 9. 5
in the boiler water. This means that amines with low distribution ratios will be necessary for
as much amine as possible to remain in the boiler water, and also have a high basicity, which
is the ability to elevate pH after the boiler feedwater is neutralized. The amine molecule most
effective at achieving this is MEA, and the MEA may be blended with amine molecules with
higher distribution ratios to also protect the steam and condensate system.

Boiler Cycle and Retention Time Discussion:

Another very important monitoring practice and control parameter in Ethylene HP Boilers is in
boiler water cycle control, and knowledge of the system residence time.
The ASME Consensus Guidelines, specifically states that Industrial Boilers with high purity,
demineralized makeup water should be operated with a minimum of 1% blowdown (100
cycles of feedwater concentration), to avoid excessive concentration of trace contaminants and
the possible formation of deposits in the boiler.
However, in many industrial boilers, it becomes very difficult to accurately calculate, or predict
the boiler water cycles. Generally, the residence time in the boiler system is unknown.
Attempting to calculate boiler water cycles based on conductivity and/or silica usually results in
large errors.
The low level of feedwater conductivity present is usually volatile, and the conductivity in the
boiler water most likely will be a result of the chemical treatment program.

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Generally, the analytical results for low-level silica in the feedwater are not accurate, and the
volatility of silica is not taken into consideration in the boiler cycle calculations.
In application of phosphate-based programs, the most accurate cycle calculations are usually
determined by: steam or feedwater flow; the chemical product feedrate; phosphate residual;
and/or a tracer that has been added to the treatment program. Some facilities also have fairly
accurate blowdown flow meters.
In some cases, the on-site boiler water analytical results are questionable; and/or too variable
with time, in relation to the calculated boiler residence time. Causes may include sample
systems not having adequate cooling or a continuous flow; or because of excessive time lag in
the sample system.
From a technical standpoint, it is usually of value to know the “residence time” in the boiler
system, in relation to boiler cycles. Frequently the boiler system volume is known, or can be
determined. By knowing the system mass volume, calculations can be performed to
determine residence time; including decay by a molecule such as phosphate or a tracer; and
elapsed time between measurements. An example of a curve developed in an Ethylene Plant
Boiler system is shown below in Figure 8.

Ethylene Plant
Retention Time Calculations
Time Constant & Retention Time, Hrs

80
Basis:
70 Boiler PSIA = 1522
Steam, M Lb/Hr = 95
BW Density, Lb/Ft3 = 42.37
60 Mass Volume, M Lbs = 67

50

40

30

20

10
25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
Boiler Water Cycles

Time Constant, Hrs Retention Time (50%)

Figure 8.

Note: In this system example and referring to 75 cycles in the graph, the Time Constant
(Mass/Blowdown) is about 52-hours and the Retention time to 50% decay of the initial
concentration would be about 37-hours. The time lag in the boiler blowdown sample system,
if known, should also be taken into consideration.

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Comparison of Alternate Treatment Programs:
This section will compare the theoretical boiler chemistry results, and the effects of low level
feedwater contaminants in comparing the VGB phosphate control in the 1 to 3 ppm range,
with the more traditional phosphate control in the 4 to 8 ppm range. Also compared will be
the effect of the low level contaminants on an All Volatile Treatment.

Boiler Computer Modeling System:

GE Water developed a proprietary Boiler “Computer Modeling System”, that makes it possible
to simulate both the “bulk water” and “concentration cell” chemistry, for either “phosphate
based” or “all volatile” treatment programs. This allows accurate predictions of “under
deposit” pH and contaminant concentrations, as compared to bulk water. The conditions and
ionic species present, can be determined both “at temperature” (corresponding to the boiler
pressure); and at the “sample cooler” (ambient temperature).
Computer modeling studies were performed specifically for this paper, to demonstrate the
potential adverse effects and concerns of low-level contaminants in the feedwater. This is a
particularly serious issue when using internal treatment programs with minimal buffering, and
no deposit control.
The results of the computer modeling in the following graphics will show the comparisons
between the “VGB low level Alkaline phosphate program”, with phosphate control range from
1.0 to of 3.0 ppm of phosphate, as compared to the congruent control pH/phosphate program
range of 4 to 8 ppm, as recommended by GE Water.
The computer modeling will also demonstrate the potential corrosion concerns in boiler
systems with “All Volatile” treatment programs, regardless of the type of amine molecules
used.

The Basis for the boiler system Computer Modeling for the discussion in this paper
was as follows:
• Demineralized/Condensate Makeup, Mixed Bed Polished, at 6.5 pH to the Deaerator
• Boiler Pressure at 1500 PSIG (103 Barg), and Boiler Cycles at 50
• Boiler Concentration Cell (based on the FW) at 1000 cycles (Considered a conservative
estimate of potential under-deposit concentration mechanism, as this is only boiler
water cycled by 20X).
• In the computer model, all studies with both phosphate based and all volatile treatment
programs; the HP Boiler steam produced was controlled at a constant pH level of 9.0,
with an MEA/Diamine amine blend.
• Computer Model Studies with chloride or sodium contaminant concentration levels,
were determined in increments from 0 to 30 parts per billion (ppb).

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62217
 • Bulk Boiler water pH levels were determined in the computer modeling both at “boiler
water temperature” and at “25 deg C (77 deg F)” - the ambient sample cooler outlet.
• Boiler water phosphate residual levels for control range were:
o VGB Standards = 1 to 3 ppm Phosphate
o Conventional Phosphate = 4 to 8 ppm
Steam
Concentration Cell
Simplified Diagram of Cycles = 1000
Computer Modeling System Conc Blr Cell
Cell pH 10.70
pH at T 8.84
Cndn OPO4 60.05
Sodium 46.33
Steam
Chloride 5.00
Demin MU
Steam
Organic Na Cl
Acid Deaerator
PO4 Boiler Cycles = 50

Amine Blr BD
Boiler pH 9.61
pH at T 7.53
CMS Modeling OPO4 3.00
BFW Cndn BFW Blr BD Blr Cell Steam Sodium 2.32
Lb/Hr 921506 9308 1020506 20408 1000000 Chloride 0.25
PSIG 1508 1508 1508
umhos 0.067 0.80 0.06 16.15 252 2.41
pH 7.0 5.7 7.2 9.6 10.7 9.0
pH at T 7.35 8.84
M Alk 2.5 2.5 2.5 6.92 66.1 3.3
OPO4 3.0 60.1
MEA 0.59 1.51 1.48 0.58
Diamine 0.30 0.07 0.06 0.30
Free CO2 0.001 0.411 0.001 0.001
NaHCO3 0.006 0.089 0.001 0
CO3 0 0 0 0
Na 0.003 0.003 2.32 46.33
Cl 0.005 0.25 5.0

Boiler Feedwater Acidic Contamination with Chlorides:

Note in the following graph, Figure 9, the very acidic condition of the boiler water, particularly
with the 20 to 30 ppb chloride slippage in the 1 to 3 range of phosphate; compared to the
continued acceptable pH control in the range of 4 to 8 ppm phosphate.

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 Boiler Water pH at Temperature
Chloride Contamination
Boiler Water pH @ Temperture
8.00

7.50

7.00 GE Water

6.50

6.00

5.50 VGB

5.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
Ortho-phosphate, ppm
Chloride Level 0 ppb 5 ppb 10 ppb 20 ppb 30 ppb

Figure 9.

Note in the following graph, Figure 10, the same pH depression “at temperature” in the
boiler concentration cell in the 1 to 3 ppm phosphate range, as compared to the acceptable
control when in the 4 to 8 ppm phosphate range.

Boiler Chloride Concentration Cell

“At Temperature”
9.50
Concentration Cell pH @ Temperature

9.00
8.50
8.00
GE Water
7.50
7.00
6.50
6.00
5.50
VGB
5.00
4.50
4.00
3.50
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
Ortho-phosphate, ppm
Chloride Level 0 ppb 5 ppb 10 ppb 20 ppb 30 ppb

Figure 10.

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62419
Note in the graph below, Figure 11, the same pH depressions in the boiler water
concentration cell when using AVT. With AVT, and only 5 ppb of chloride contamination, the
boiler water pH “at temperature” is well below an acceptable pH range

BW Chloride Concentration Cell with

All Volatile Treatment (AVT)
10.0
9.5
9.0
8.5
8.0
VGB Control Zone
7.5
Cell pH

7.0
6.5
6.0
5.5
5.0
4.5
4.0

0 5 10 15 20 25 30
Chlorides, ppb
25 Deg C At Temp

Figure 11.

Boiler Feedwater Alkaline Contamination with Sodium:

Note: in, the graph below in Figure 12, the effect on pH level “at temperature”, even with 0
ppb sodium slippage for the 1 to 3 ppm phosphate range, versus the acceptable range in 4 to
8 ppm phosphate.

Boiler Water pH “at Temperature”

With Sodium Contamination
8.20
8.10
8.00 VGB
7.90
Boiler Water pH at

7.80
Temperature

7.70
7.60
7.50 GE Water
7.40
7.30
7.20
7.10
7.00
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
Ortho-phosphate, ppm
Sodium Level 0 ppb 5 ppb 10 ppb 20 ppb 30 ppb

Figure 12.

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62520
Note, in Figure 13 below, in the concentration cell, the elevated pH and alkaline conditions
with sodium.

Boiler Sodium Concentration Cell

“at Temperature”
9.50
9.40
9.30 VGB
9.20
Concentration Cell pH at

9.10
Temperature

9.00
8.90
8.80
GE Water
8.70
8.60
8.50
8.40
8.30
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5
Ortho-phosphate, ppm

Sodium Level 0 ppb 5 ppb 10 ppb 20 ppb 30 ppb

Figure 13.

Note below in Figure 14, with AVT, any sodium contribution will elevate the boiler water pH
above the VGB control zone. Thus, most likely there will be free caustic present.

Boiler Water Sodium Concentration Cell

with All Volatile Treatment (AVT)
11.5
11.0
10.5
VGB Control Zone
Congentration Cell pH

10.0
9.5
9.0
8.5
8.0
7.5
7.0
0 5 10 15 20 25 30
Sodium Contaminant, ppb
25 Deg C At Temp

Figure 14.

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62621
These studies demonstrate, that with low level feedwater contamination, there is negligible
buffering in the boiler water, and operation will be in the “acid phosphate” corrosion range
with chloride slippage and the “free caustic” zone with sodium slippage.

Cold Startup Rinse/Passivation Procedure Example:

In most cases, pre-operational Chemical Cleaning procedures will have been performed prior
to startup; the boiler system flushed; and laid up under a nitrogen atmosphere in preparation
for start-up.
The typical Ethylene Plant most likely has a procedure in place for Cold Startup of the TLE
Boiler system, after a shutdown. In many cases, when a phosphate based treatment program
is being used, the cold startup may include shot feeding of the phosphate based product into
the steam drum prior to initiating the startup.
The purpose of this brief description is to provide basic information and the benefits of using
an alternative Rinse/Passivation Procedure during the Ethylene Cold TLE Start-up Procedure,
utilizing a polymethacylate, or phosphonate based polymer, during the procedure. .
This general write-up is guideline to provide basic information. A Specific Procedure will be
need to be developed for the individual Ethylene Plant site, and will depend on the normal
procedure to prepare and fill the boiler for start-up.

Benefits of the Polymer rinse include:

1. Reducing the iron and suspended solid levels remaining in the boiler, to minimize
the iron transport into high heat transfer areas of the boiler during the operation.
2. Provide a cleaner boiler system; passivate the metal surfaces; and increase intervals
between chemical cleaning.
The dispersant rinse procedure can utilize either Polymethacrylate (PMA), or a more effective
polymer, containing an organic phosphonate based polymeric dispersant polymer (PIPPA).
The polymer product will be injected into the boiler feedwater piping, upstream of the BFW
Economizer (and downstream of any Attemperation water take-offs). This will allow the rinse,
passivation, and removal of iron and solids in the feedwater piping; the BFW Economizer; and
the Secondary Quench Exchanger; and into the TLE Steam Drum and Transfer Line Exchanger,
where they are then removed in the continuous and intermittent boiler blowdowns.
The polymeric dispersant will assist in keeping the iron and suspended solids in boiler water
solution where they can be removed in the boiler blowdown during the Cold Startup
Procedure. If the phosphonated polymer is used, the major decomposition product of the
product (temperature dependent) is ortho-phosphate, the same molecule used for the internal
Congruent pH/Phosphate control program in the boiler during normal operation.

Page
62722
The best guide for Operations to monitor the iron levels in the system, and the startup
progress, may be by comparing Millipore filters to the Babcock & Wilcox Charts. However,
determining the iron levels in the various forms such as: suspended (particulate); soluble; and
total iron; will be very valuable, from a technical and reference standpoint, and is
recommended during the procedure.
Typically, the filling of the boiler system with deaerated boiler feedwater and charged with
polymer, is accomplished prior to initiating the normal Ethylene Plant Cold Start-up.
The boiler system valving will be lined up for a normal boiler fill using the procedure
established by the Customer Site. It is intended that this fill procedure, using boiler feedwater
containing the polymer product, will flush through the economizers; the Secondary Quench
Exchanger; into the TLE Steam drum and TLE’s.

Typical Ethylene Plant Cracking Furnace System:

Following is a typical drawings of the Ethylene Plant Cracking Furnace, Figure 15:

Typical Ethylene Plant

HTP2 Rinse/Passivation
Demin/Cndn Strip Stm
Sat Steam
O2 Scav
to Superheater

Deaerator
Amine BFW
Preheater Demister
Pad Steam
Drum
PO4
Injection PIPPA
BFW
LCV
Econ Vortex
CBD
Breaker
Flow
CBD
Attemporation Tube Sheet
Supr Htr Vent

SH HP Steam To Quench
Water Tower
Feedstock
TLE

Pyrolysis Furnace
Dilution
Steam
IBD

Ethylene Furnace Figure 15.

“Cracked Gas”

Page
62823
Note: the polymer product used in the rinse/passivation will be added downstream of the
attemperating water takeoff to the Cracking Furnace being started up, as other Units are in
operation during this period. Therefore, the polymer dispersant product will only be injected
into this system, downstream of the steam drum level control valve and Attemperation water
take off.

Typical Blowdown System:

Note in Figure 16, that the Continuous blowdown from other Ethylene Cracking Furnace
Steam Drums may be routed to a common High Pressure, and Low Pressure Flash Drums. In
addition, frequently boiler blowdown may be recovered to the Dilution Steam Generation
System, and/or routed back to the condensate recovery. Therefore, the blowdown piping and
practices will need to be carefully reviewed, and the blowdowns from the Unit being started-up
routed to the sewer.

Vent

Example:
FI To Superheater
Continuous &
To SQE
Intermittent Blowdowns
Steam Drum
To DSG

Riser CBD from other steam drums

CBD

BFW BW LP
TLE
SC steam

Downcomer
IBD
HP
Cracked gas IBD Fl Tk
To
(Shell & Tube)
Atm

LP
Fl Tk Condensate

Sewer
To Figure 16.
MB Polish

Typical Procedure:
• Pump in the required quantity of the designated polymer dispersant product from the
Chemical Dosing Unit to achieve the target level of active polymer in the boiler system
when the boiler is at normal liquid level. This will require knowledge of the approximate
boiler system volume.

Page
62924
• The quantity of chemical required will be based on the known or estimated system volume
to normal operating level. This will include volume in the piping to the boiler; the BFW
Economizer; the Secondary Quench Exchanger; and the Steam Drum to about 30% level;
and the shell side of the TLE Exchangers.

o NOTE: Typically, an Excel workbook calculator program will be included with a

specific Cold Start-up Rinse/Passivation procedure to aid in the calculation of the
initial charge of the product required for the Customer Site Boiler System, and for
estimating the level of polymer remaining in the boiler system at any time.
• After the necessary quantity of product is added to the Boiler System, the Cold Startup
Procedure will then be followed. As noted previously, a specific procedure will be written
for the monitoring of boiler chemistry and iron levels and determining the duration of the
pressure holds during the start-up.

• During the Cold Start-up, the boiler water will be monitored for pH, iron, silica, phosphate;
and suspended solids, to determine the level of contaminants present, and of Polymer
remaining. If these parameters are within the limits, the Boiler steam pressure can be
slowly brought up to design operating pressure, according to the normal startup procedure
and curves.
• As the Steam pressure is increased to normal operating levels, initiate high blowdown rates
by alternating between Bottom blows and Continuous blowdown valves. As the Boiler
pressure increases, if the phosphonated polymer product is used, the molecule will begin to
dephosphorylize into ortho-phosphate.
• As Boiler pressure increases, continue to check Boiler chemistry for pH; iron; silica; and
phosphate; targeting the boiler water control parameters. The level of polymer remaining
in the boiler may be determined from the Boiler water analysis.
o At some point in the usual startup sequence, it may be necessary to begin the
transition from the supplemental polymer product to the normal phosphate based
product to begin bringing Boiler Water phosphate levels and chemistry within the
target control parameters. Most polymeric dispersants are compatible with
phosphate.

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63025
 Brief Review of Dispersant Polymer Molecules considered:

Comparison of Polymethacrylate (PMA) with the Phosphonated

polymer (PIPPA):
The PIPPA Polymer was designed specifically to disperse metal oxides, the primary
contaminant in high purity boiler water systems. The polymer was also designed to maintain
effectiveness up to 1800 PSIG (124 Barg), and the long residence times encountered with high
boiler water cycles and low blowdown rates.
As with Polymethacrylate, PIPPA was designed with a “methyl group” on the polymer
backbone, reducing any significant corrosion potential from overfeed, and a “phosphonate
group” replacing the carboxylate group in the molecule, to enhance the iron oxide dispersion.

The comparison of the PMA and PIPPA polymers are shown in Figure 17, below:

Polymethacrylate
CH 3 (PMA)

CH2 CH
C O
CH3
O-
CH2 CH
O P OH
Poly(isopropenylphosphonic acid)
(PIPPA)
O
Figure 17.

Page
63126
Iron Transport Study:
The boiler system in the following study was a 1500 PSIG (103 Barg) vertical TLE with an
existing treatment program based on Congruent pH/Phosphate - without polymer.
• 1st Trial Step was to obtain baseline data iron transport with PMA for 16-day period
with active polymer at levels shown in graph in upper left corner of Figure 18 (15 to
90 ppm).
• 2nd Step was performed with PIPPA for 20-days at active polymer levels shown in
graph in lower right corner of Figure 18 (12 to 40 ppm).
Typical Iron Transport Levels during the Study:
• No polymer – less than 5%
• PMA polymer – less than 20%
• PIPPA Polymer – Greater than 80%

Figure 18 below shows the results of iron transport in a boiler system with PIPPA versus
PMA:

Percent Iron Transport with PMA

Percent Iron Transport

30%
25%
Iron Transport
20%
PMA vs. PIPPA
15%
10%
5%
0%
15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
Active PMA Polymer, ppm

Percent Iron Transport with PIPPA

250%
Percent Iron Transport

200%

150%

100%

50%

0%
Figure 18. 10 15 20 25 30 35 40
Active PIPPA Polymer, ppm

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 GEWPT Metallurgical Report Summaries:

1. Malaysia
• Plant operated for several years prior to the first failure. The TLE failures were
associated with poor boiler chemical control from chemical feed system; and
feedwater contaminant as a result of slippage from Cation and Mixed Bed
Condensate Polishing. Failures appeared to be related to “acidic” corrosion gouging
with corrosion products primarily iron oxide, with some phosphorus present. No
evidence of over-heating was found. Failed TLE’s were either replaced or repaired.
Boroscope inspections during next turnaround indicated no new corrosion problems.
• Shortly after Turnaround startup, and a short period of operation, TLE failures
occurred again as result of low-level acidic contaminant slippage from the mixed bed
demineralizers. The slippage was associated with Mixed Bed Condensate Polisher
failures (loss of resin) and depressed feedwater pH. (Mixed Bed Regeneration with
HCl and NaOH). Again no overheating was evident in the metallurgical examination.
Iron oxide, sodium, and phosphorus was present in the deposit; and Maricite
(NaFePO4) was identified as being present in the deposit by x-ray diffraction.

2. Australia:
1. TLE failures appeared to be the result of acidic corrosion, with iron oxide and
significant level of chloride present, possibly associated with chloride intrusion.
2. A second failure was compounded by excessive chip scale from upstream of TLE
breaking loose during start-up and obstructing flow through bottom of Shell and
Tube TLE. The chip scale was primarily iron oxide, and again included significant
quantities of Chloride present.

3. Texas:
• Failure was in the horizontal BFW convection coil, rather than a TLE. Low flow is
very conducive to steam blanketing in horizontal tube passes. No evidence of over-
heating was noted. This corrosion mechanism may have been either acid or
alkaline. Iron, sodium, and phosphate were found, but not in the ratio expected for
maricite. The pattern of longitudinal gouging indicates the stratification of the
steam and water phases, and the evaporation above the water line concentrated the
normally soluble salts, forming a localized aggressive environment.

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4. Louisiana:
• Failures were in a vertical Shell and Tube TLE near the inlet tube sheet. The deposit
within the gouged area was primarily iron, sodium, and phosphorus in a ratio
consistent with Maricite (NaFePO4). Therefore, the corrosion mechanism was
considered to be “acid phosphate” attributed to “under-deposit corrosion” (UDC) and
“departure from nucleate boiling” (DNB). No evidence of overheating damage.

5. Sweden:
• A number of failures of TLE Exchangers and Auxiliary Boiler Tubes occurred during a
9-month period. Treatment program was “All Volatile Treatment (AVT)”. Failures
were believed to be as a result of chloride intrusion. Although alkaline conditions
were reported to be maintained in the boiler water, the ability of AVT programs to
neutralize contaminants locally in a “concentration cell” is limited. Sources of
chloride ingress needed to be identified and eliminated.
• It was also suggested that chlorinated high MW organics might pass through the
demin plant and breakdown in the boiler to give higher than normal levels of
chlorides. AVT program cannot cope with suggested high BW chloride levels.

Page
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References:
1. American Society of Mechanical Engineers. “Consensus on Operating
Practices for the Control of Feedwater and Boiler Water Chemistry in Modern
Industrial Boilers”, 1994 with 1998 Editorial Corrections.
2. American Society of Mechanical Engineers. – “A Practical Guide to Avoiding
Steam Purity Problems in the Industrial Plant, 1995
3. “Considerations for High Pressure Boiler Chemical Treatment”, Setaro, Daniel
M., – Equipment and Chemistry, AIChE 2006.
4. “HTP-2, A New Iron Dispersant for Medium to High Pressure Industrial
Boilers”; Scott M. Boyette & Frederick A. Elliot; International Water
Conference, 1992
5. Internal GE Water Metallurgical Reports
6. “On-line Cleaning of Boilers Using a Novel Polymer Technology to Avoid
Acid”, Carter W. Brown, Mark A. Moore, Saleh A. AlBenHamad, and Michel
Didden; 4th Middle East Refining & Petrochemicals Conference and Exhibition,
October 2003, Kingdom of Bahrain
7. “Optisperse HTP-2 Polymer”, GEWPT Boiler Technical Marketing, Nov- 2006
8. Protection Against Caustic Embrittlement by Coordinated Phosphate pH
Control”, Whirl, S.F.; Purcell, T.E.; “International Water Conference,
(Engineers’ Society of Western Pennsylvania), Pittsburg, PA, 1945
9. “Tube Failures in Waste Heat Boilers: Case Histories”. NACE 05437,
Corrosion 2005, Hargrave, Robert, GE Water & Process Technologies. .
10. VGB Guidelines for Feedwater, Boiler Water and Steam Quality for
Power Plants/Industrial Plants; 2004.

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