Managing Reboiler Steam-side Operation

Improves Equipment Reliability and Steam Quality

by Loraine A. Huchler, P. E.

MarTech Systems, Inc., Lawrenceville, New Jersey USA

presented at:
First International Conference on Practical Industrial Water Treatment Technology
for the New Millenium

Marriot Houston Westside

Houston, Texas

January 27 29, 1999

Organized by
Gulf Publishing and
HYDROCARBON PROCESSING

Published in HYDROCARBON PROCESSING, June 1999

by Gulf Publishing
Abstract

Reboilers are perceived as an integral part of the production process but not part of the
steam system since they are located far from the main boilers or powerhouse. Conse-
quently, the steam-side operation of reboilers receives minimal attention until a failure
occurs. A proactive approach of mechanical optimization and chemical treatment and
monitoring is recommended to minimize deposition and corrosion and maximize system
reliability and energy efficiency. Mechanical optimization requires an assessment of the
reboiler design and operation to ensure proper venting, correct arrangement of steam
traps on reboiler supply lines, compatibility of materials of construction, and impact of
current system operation (i.e. dry, partially or totally flooded on the steam side). Select-
ing the correct chemical treatment and monitoring program is a balance between eco-
nomics, feed considerations, process compatibility and plant preferences. Maintaining
the efficiency of the steam-side operation of reboilers is critical to improving the process
equipment reliability and maintainability.

Introduction cal operation, monitoring and chemical

treatment.
Centrally located powerhouse boilers
produce steam for refining processes
Refinery Reboiler Review
and power generation. Operators add
chemicals for water treatment and moni- Large quantity distillate products such
tor condensate quality at this central lo- as gasoline, jet fuel and diesel fuel dic-
cation. Water and steam not used in the tate basic refinery design.2 Waste
powerhouse is routed to the refinery for streams from each of these products are
waste heat boilers, reboilers or process refined to a variety of finished materials
requirements. in various process units. Process units
that commonly use steam as an indirect
Reboilers are located far from the pow-
heat source in reboilers include:
erhouse and, consequently, the steam-
side operation of these units receives Gas plants
minimal attention until a failure occurs. light ends unit
One study showed the most common vapor recovery unit
high risk failure events in a fluid catalytic Alkylation units (HF and Sulfuric)
cracking unit (FCCU) were heat ex- Sulfur recovery units
changer shell or tube leaks or ruptures.1 Aromatics recovery units
Reboilers, like heat exchangers, are BTX
equally vulnerable to tube and shell fail- benzene/cumene
ures. This paper will discuss reboiler
UDEX
design, location and operation within a
Catalytic Reformer
typical refinery and methods to maxi-
mize reliability through proper mechani- A summary of the reboilers typically
found in each process unit is shown in
Table 1.
1
Rooney, J., Turner, J., Arendt, J., Preliminary 2
Gary, J., Handwerk, G., Petroleum Refining,
hazards analysis conducted on FCCU complex,
Dekker, New York, 1984.
Oil & Gas Journal, August 8, 1988, pages 60-66.

2
 Table 1 Refinery Reboiler Summary

Process Reboiler Name/Column Purpose

Alkylation (Sulfu- Depropanizer Remove and collect propane from alkylate stream
ric) Deisobutanizer Produce low vapor pressure alkylate gasoline
Alkylation (HF) Acid Rerun Recycle acid stream to remove contaminants
3
Depropanizer Remove and collect propane from alkylate stream
Acid Stripper Remove acid from propane stream
Deisobutanizer Produce low vapor pressure alkylate gasoline
Debutanizer Remove and collect butane from deisobutanizer stream
Catalytic Re- Stabilizer Remove butane and lighter hydrocarbons from reformate
former stream
Aromatic Recov- Stripper Remove and collect aromatics from solvent hydrocarbon
ery stream
Pre-Extractor Remove and collect lighter hydrocarbons from reformate
charge
Water Still Remove water from solvent
Benzene Remove and collect benzene from aromatics stream
Toluene Remove and collect Toluene from aromatics stream
Xylene Remove and collect xylene from aromatics stream
Gas Plant Stabilizer Remove butanes and lighter hydrocarbons from gasoline
product
Stripper Remove very light hydrocarbons such as methane and
ethane
De-ethanizer / Absorber Produce low vapor pressure alkylate gasoline
(Stripper)
Debutanizer Stabilize gasoline component
Rerun (Naptha Splitter) Recycle to polish lean oil (solvent) of lighter gasoline
fraction
Depropanizer4 Remove and collect propane
Depentanizer Remove and collect pentane
Stabilizer Remove butane and lighter hydrocarbons from gasoline
stream
Sulfur Recovery Sour Water Stripper5 Remove and collect H2S and NH3 from water stream
6
Amine Regeneration Regenerate amine for recycle
Miscellaneous Vaporizer Normally found in fuel system to remove butanes
Splitter A distillation of two or more hydrocarbon fractions

3
Reboiler has critical water treatment requirements due to low pressure steam usage.
4
Reboiler has critical water treatment requirements due to low pressure steam usage.
5
Low corrosion potential due to internally generated low pressure steam.
6
Low corrosion potential due to internally generated low pressure steam.

3
Types of Reboilers not operate at high pressures because
they must have adequate liquid/vapor
Reboilers are essentially shell and tube
separation.
heat exchangers with process fluid on
one side and steam or a mixture of
Internal or Stab-In Reboilers
steam and condensate on the other
side. Three of the most common re- A variation of a kettle reboiler is an in-
boiler designs are kettle, forced recircu- ternal or stab-in tube bundle that is in-
lation and thermosiphon. serted directly into the column (Figure
2).
Kettle Reboilers
Kettle reboilers, also known as pool
boilers, are often used for light hydro- Steam
carbons (propane, butane). These re-
boilers handle process flow fluctuations
and high heat fluxes better than other
Tower
reboiler designs, but kettle reboilers
have a greater tendency to foul on the
process side (Figure 1).
Process Flow to
tower (hot)
Steam

Steam/Condensate
Figure 2 - Stab-in Reboiler
Process Flow
Steam/ Con- from tower (cool)
densate The operating characteristics of a stab-
Figure 1 - Kettle Reboiler in reboiler are almost identical to a kettle
boiler with the exception that the units
have lower heat fluxes due to the size
A liquid condensate level must be main- restriction to fit the column and have a
tained at or near the top tube row by lower process-side fouling tendency.
means of a weir or a level controller. The capital cost of a stab-in unit is lower
Typically, the tube bundle has baffles to than the capital cost for kettle reboilers,
allow liquid movement and reduce the but maintenance is more difficult.
potential for vapor blanketing.
Forced Recirculation Reboilers
In kettle reboilers there has to be ade-
quate head-space to permit the separa- Figure 3 shows a forced recirculation
tion of the aqueous liquid phase from reboiler. This unit uses a pump to move
the vapor phase. Demisters can be process liquid through the reboiler.
used to minimize the entrainment of liq-
uid in the outlet flow. These reboilers do

4
 Process Flow These reboilers do not require a pump
to tower (hot) for recirculation and are the least likely
Tower to foul in service due to relatively high
Steam process flow velocities. Like forced re-
circulation reboilers, thermosiphon re-
boilers have sensible heat transfer fol-
lowed by nucleate boiling.
Steam/
Condensate
Steam-side Operation
Process Flow
from tower Reboilers are specially designed steam
(cool) heat exchangers that transfer heat to
the process by circulating some of the
Figure 3 - Forced Recirculation Re- process fluid through the reboiler and
boiler back to the column.
Reboiler Steam Control Strategies
Forced recirculation boilers have two
mechanisms of heat transfer: sensible A temperature control system accurately
heat transfer followed by nucleate boil- controls the steam flow and hence the
ing. Process flow is typically on the heat transfer rate.
tube side of a standard exchanger in the The most common temperature control
vertical position. At low process system consists of a flow/pressure con-
flowrates, these units are prone to foul- trol valve on the steam inlet to the re-
ing. boiler tied to the process outlet tempera-
ture as shown in Figure 5.
Thermosiphon Reboiler

Thermosiphon reboilers (Figure 4) oper-

ate using natural circulation with process T
flow on the shell side in horizontal units
and process flow on the tube or shell Tower Steam
side in vertical units. Reboiler

Steam/
Condensate
Process Process Flow
Flow to
Flow
tower (hot)
Stea
Figure 5 - Reboiler Temperature Con-
trol System
Condensate
Process Flow Process temperature fluctuations are
from tower
(cool) controlled by modulation of the steam
flow control valve.
Figure 4 - Thermosiphon (Vertical
Type) Variations in process fluid flow require
more complex process control algo-
rithms that use process flowrate or a

5
combination of process temperature and BTU/hour when the surface area ex-
flowrate to actuate the steam control posed to steam is reduced by 50%.
valve. Figure 6 shows how the process
flow control valve would operate based
Process Flow Steam Area =
on a process variable signal. to tower (hot) 2 0 0 ft2

If the process flow increases beyond the Tower

reboiler design, liquid condensate will 50 psig
Steam
accumulate, a condition known as @1179 BTU/lb
flooding. Accumulation of condensate
in reboilers increases the risk of corro-
sion. Chemical treatment of steam to Condensate
reduce the condensate corrosion poten- Process Flow @268 BTU/lb

tial is discussed in the Chemical Treat- from tower (cool)

ment and Monitoring Section. Figure 7 - Reboiler Operating at De-
sign Conditions
F

Process Flow Steam Area = 100 ft2

to tower (hot) Q = 2500 BTU/hr

Tower Steam Tower

Reboiler
50 psig
Steam
@1179 BTU/lb
Steam/
Condensate
Condensate
Process Flow @268 BTU/lb
Flow
Process Flow
from tower (cool)
Figure 6 - Reboiler Flow Control Sys-
tem Figure 8 - Reboiler Operating Above
Design Conditions
Impact of Changing Process De-
mands
To avoid flooding a reboiler under condi-
The demands of the process flowrate
tions of increased process flow the plant
and heat exchange requirements control
might consider using the flow control
the steam-side operation of the reboiler.
shown in Figure 6. Reboiler control is-
Refineries frequently modify their proc-
sues are unique and each system should
esses in response to market require-
be analyzed accordingly.
ments, changing the process flowrates
and the heat exchange requirements. Reboilers are designed to operate with
Consequently, reboilers may be oper- no liquid condensate level. Uninten-
ated very differently from the original tional condensate flooding of reboilers
design conditions shown in Figure 7. results in a greater risk of corrosion
For example, when flooding occurs, since corrosion processes occur in the
(Figure 8), the heat transfer rate de- liquid phase. Uncontrolled corrosion
clines from 5000 BTU/hour to 2500 can lead to reboiler failure and un-
planned shutdown. Plant personnel

6
rarely track changes in the steam-side
operation of reboilers, resulting in many [CO2]= 49.6 ppm
reboilers operating with reduced energy [Amine] = 52.4 ppm
efficiency and reduced reliability. pH = 6.3

[CO2]= 5 ppm
Impact of Steam Pressure Reduction [Amine] = 11.65
Strategies ppm
10% flash
pH = 8.5
50 psig
The steam pressure in reboilers de-
pends on the process temperature and [CO2]= 0.044 ppm
heat exchange requirements. The
[Amine] = 7.3 ppm
steam pressure is typically less than 300 pH = 9.7
psig and often less than 100 psig. The
pressure of the steam supplied from the Figure 9 - Flash Tank
utility boilers or from waste heat boilers
is usually reduced using either a flash If the steam pressure is reduced using
tank or a pressure-reducing valve let-down stations (pressure reducing
(PRV). The method of steam pressure valves (PRV)), then the concentration of
reduction will influence the corrosion po- contaminants and treatment chemicals
tential of the steam. in the high pressure and the reduced-
The concentration of the more volatile pressure steam is the same. The corro-
contaminants and treatment chemicals sion potential of the condensate is un-
in the flash tank will be higher in the changed by the pressure reduction
flashed steam than in the inlet steam process.
and bottoms or liquid phase. Thus, the Treatment of the steam to minimize cor-
flashed steam will have a high concen- rosion is recommended as described in
tration of carbon dioxide and typically a the Chemical Treatment and Monitor-
low pH. When the steam condenses, ing section.
the condensate will have a very high
corrosion potential. Reboiler Optimization
Figure 9 shows how a flash tank con- Optimizing reboiler operation requires
centrates some common contaminants attention to both mechanical operation
and treatment chemicals. The carbon and steam side operations and chemical
dioxide concentration is over one thou- water treatment and monitoring pro-
sand times as high in the vapor phase gram.
(49.6 ppm) as the liquid phase (0.044
ppm). The pH of the vapor or steam Mechanical Operation7
phase is 6.3 and the pH of the liquid
There are several mechanical opera-
phase is 9.7.
tional issues that will limit the heat trans-
Any equipment that receives steam from fer efficiency of a reboiler, including va-
this flash tank is vulnerable to corrosion por lock, flooding, and poor heat trans-
when the steam condenses, since cor- fer. The solutions for these problems
rosion occurs in the liquid phase, not the
7
vapor phase. G. C. Shah, Heat Transfer, Troubleshooting
Reboiler Systems, Chemical Engineering Proc-
ess, July 1979, pages 53-58.

7
include proper venting, installation and stream and routing it to the sewer. An
maintenance of steam traps, selecting example of the impact of air vent traps
the correct metallurgy, properly sizing on a system is shown in Table 2.8
the steam inlet control valve and select-
ing the correct process control algo-
Table 2 - Effect of Vent Air Traps on
rithm.
Condensate Quality
Venting With Without
The operational efficiency of some re- Air Vent Trap Air Vent Trap
boilers is improved with the addition of pH 5.72 6.45
vents. Venting non-condensable gases
such as carbon dioxide (CO2), ammonia Fe 0.44 ppm 0.22 ppm
(NH3) and air from the reboiler will im- CO2 30 ppm <10 ppm
prove the heat transfer efficiency. In the Vent 5 ml/min 200 ml/min
case of CO2, venting also reduces the Rate
risk of corrosion if liquid condensate ac-
cumulates in the reboiler. The energy
Vents are particularly important during
improvements can be dramatic: as little
system start-up to purge non-
as 0.05% by volume of air can reduce
condensable gases that may have ac-
the heat transfer rate by 50%. Air and
cumulated during downtime. Some re-
carbon dioxide concentrations are not
boilers have a balance line that equalizes
normally high enough to cause severe
the pressure across the reboiler during
heat transfer problems except during
start-up or shutdown. The balance line
start-up. Process leaks can cause high
may result in vapor lock by recycling non-
concentrations of vapors, creating a
condensable gases from the bottom to
condition know as vapor lock during
the top of the reboiler. Plants often in-
normal service. Vapor lock causes a
stall a vent on the balance line that is
significant reduction in heat transfer effi-
opened only during start-up or shutdown
ciency.
to prevent vapor lock.
Vents should be located at or near the
top of the tubesheets in vertically- Steam Traps9
oriented reboilers and downstream of Steam traps drain the condensate from
the discharge pass in horizontally- the reboiler, preventing flooding. Flood-
oriented reboilers. Vents should be lo- ing severely reduces the heat transfer
cated in the vapor space as close to the efficiency since the submerged surface
liquid level as possible in both vertical transfers only sensible heat, while the
and horizontal reboilers that operate tube surfaces in contact with steam
with a liquid level. The maximum vent- transfer both the latent heat of vaporiza-
ing rate is between 0.2% and 0.5% of tion and the sensible heat.
the inlet flow. For safety or energy con-
servation, some plants have installed 8
Unpublished Course Notes, Advanced Boiler
traps on these vent lines. Vent traps Training, Betz Water Management Group, circa
tend to limit the venting rate and are not 1990.
9
recommended. If live vents are not ac- Radle, J., Select the Right Steam Trap,
ceptable, consider condensing the vent Chemical Engineering Progress, January, 1992,
pp. 30-47.

8
The correct location of steam traps is on alloy is significantly lower than mild steel
the reboiler steam outlet line. Properly- alloys, and the overall energy balance
sized equipment is critical since under- for the column will be affected. The re-
sized traps, drain lines and discharge placement of the mild steel tube bundle
lines will result in condensate collecting with stainless steel will significantly limit
in the reboiler vessel, i.e. flooding. production when reboilers are operating
Greatly oversized traps may cause wa- at maximum throughput.
ter hammer problems when the pres-
sure differential between the trap and Properly Sized Inlet Steam Control
the condensate return line is large. The Valves
most commonly used trap designs in- Steam control valves may be incorrectly
clude the inverted bucket (IB) and the sized due to operational changes in the
float and thermostatic (F & T). Inverted column from changing production re-
bucket traps should not be insulated to quirements. An oversized steam control
allow steam to condense at the inlet and valve can limit the process efficiency if
prime the trap. Float and thermostatic the pressure in the reboiler is signifi-
traps are unsuited for high pressure sys- cantly lower than the pressure in the
tems. A surge chamber can be installed steam supply line. Thermodynamically,
upstream of an F&T trap to reduce hy- the control valve is an adiabatic system,
draulic hammer. Additional information i.e. the pressure will decline across the
on steam traps is provided in Reference control valve without a change in tem-
1 perature. When the pressure drops and
Reboilers should have dedicated traps. the temperature remains the same, the
When there is one condensate collection steam becomes superheated. Because
vessel or pot serving several reboilers superheated steam is much less effi-
on the same column, the plant should cient in transferring heat than saturated
provide separate condensate drain lines steam, the reboiler heat transfer rates
from each reboiler to the pot. Reboiler will decline.
flooding can occur when condensate If the process flows are dynamic, large
drain lines are connected to a common changes in heat transfer requirements
drain line. may result in the steam control valve
being both under and over-sized, de-
Materials of Construction pending on the operating conditions. In
The selection of materials of construc- these systems, a more complex set of
tion for reboilers is similar to the meth- control valves must be installed as de-
odology used for standard heat ex- scribed in Reference 2.
changers. Mild steel alloys have excel-
lent heat transfer efficiency and good Chemical Treatment and Monitoring
service life. Copper alloys are typically The objective of chemical treatment for
not used due to process compatibility reboilers is to minimize the corrosion
concerns. Occasionally the plant will processes in the condensate, reduce
replace mild steel tube bundles with the quantity of iron returned to the boil-
stainless steel tube bundles reduce the ers, reduce the risk of equipment failure
failures due to corrosion. The heat and unplanned shutdown, thereby in-
transfer efficiency of the stainless steel creasing system reliability. Condensate

9
is returned to the central powerhouse leak. Unless the reboiler operation
from each process unit through an ex- compromises the production process,
tensive condensate-return piping sys- the reboiler remains in service. The re-
tem. Since corrosion occurs only in the boiler will be cleaned and repaired dur-
presence of liquid, not vapor, efforts to ing the next scheduled outage.
measure and control corrosion focus on The condensate system has a large sur-
chemical treatment of the condensate. face area of steel pipe that is exposed to
a corrosive environment. Even at low
Contaminants
corrosion rates, a large quantity of iron
The primary sources of reboiler corro- is returned to the powerhouse boilers.
sion are acidic contaminants in the con- As shown in Table 3, for a medium-
densate such as carbon dioxide, acidic sized system operating in conformance
process intrusions or dissolved oxygen. to the ASME guidelines, 1051 pounds
Carbon dioxide is present in condensate per year of iron corrodes from the con-
in systems that use softened water densate system and is deposited into
make-up in the boilers. The softening the boiler.
process removes the hardness ions but
does not remove the naturally occurring Table 3 - Feedwater Iron Calculations
alkalinity. In the boiler, the heat breaks
down the alkalinity to form carbon diox- Boiler Operating Pressure 150 psig
ide, a gas, which will leave the boiler Utility Steam Production 600,000 pph
with the steam. In the condensate, car- Maximum Boiler Feedwa- 100 ppb
bon dioxide will dissolve in water to form ter [Iron]10
carbonic acid, a corrosive species. A
higher feedwater alkalinity will result in a Percent of Condensate 50%
higher condensate carbon dioxide con- Return
centration. Maximum Condensate 200 ppb
[Iron]
Dissolved oxygen is rarely present in
condensate systems, except during sys- Quantity of Iron moved 1051
tem start-up, intermittent operation or from Condensate System pounds/year
when air is being educted through mal- to Boiler
functioning condensate transfer pump
seals.
Iron in the boilers will cause deposits on
Acidic process fluids can leak into the high heat transfer surfaces, increasing
steam or condensate, resulting in depo- the risk of a tube failure and reducing
sition of the process materials as well as the boilers reliability and availability.
corrosion. Plants usually do not treat to
10
control deposition until there is a large Consensus on Operating Practices for the
process leak or a failure occurs. Proc- Control of Feedwater and Boiler Water Chemis-
ess leaks and contaminated steam will try in Modern Industrial Boilers, prepared by the
Feedwater Quality Task Group of the industrial
cause deposits and reduce the heat Subcommittee of the ASME Research and
transfer efficiency of the reboiler. Technology Committee on Water and Steam in
Chemical treatment is evaluated on an Thermal Power Systems, The American Society
individual basis when there is a process of Mechanical Engineers (ASME), New York,
NY, 1994, p. 22.

10
Thus, control of corrosion in the con- low-based or soya-based amines, toler-
densate system has a direct impact on ate a wider system pH (6.5 to 9.5).
the reliability of the steam generating When filming amines are fed into the
system. boiler feedwater, only a small proportion
volatilizes into the steam phase and is
Chemical Treatment Options available in the steam. The majority of
Depending on the contaminants in the the filming amine chemical remains in
system, there are three technologies the liquid phase and leaves with the
that can be used individually or in com- blowdown stream. The most effective
bination to control corrosion. Application locations to feed these products are the
of these three technologies results in steam header at the powerhouse or the
five chemical treatment programs.11 steam supply line at the reboiler. Film-
ing amines must be fed continuously at
1. Filming amines a constant concentration, not in propor-
2. Filming amines with neutralizing tion to the contaminant concentration.
amines For systems with high contaminant con-
centrations, this feed strategy results in
3. Neutralizing amines
a lower cost treatment program than
4. Passivating agents programs such as neutralizing amines
5. Neutralizing amines with passivating that are fed in direct proportion to the
agents. contaminants.
Overfeed of filming amines or a high
1. Filming amines condensate pH can have disastrous
Filming amines are long chain hydrocar- consequences. When the system pH
bons that have one hydrophobic end exceeds the maximum control pH, the
and one hydrophilic end. Filming film is rapidly removed from the tube
amines form a film on the tube surface, surfaces, a process known as strip-
creating a physical barrier on the tube ping. This causes gunking wherein
surface that prevents the corrosion large quantities of filming amine are
agents from reaching the steel tube sur- transported with the condensate flow,
face. The integrity of this chemical film plugging steam traps, valves, and other
is strongly dependent on the pH of the equipment. Ultimately these insoluble
aqueous phase. The most common materials return to the boiler with the fe-
filming amine is octadecylamine, for edwater and mix with the calcium, mag-
which the condensate pH must be main- nesium, and iron in the boiler to form
tained between 6.5 and 7.6 to prevent rather harmless, sticky, deposits known
solubilization of the amine and subse- as gunk balls. Overfeed of filming
quent removal of the protective chemical amines can result in similar problems
treatment on the tube surfaces. The with insoluble materials trapped in the
newer, proprietary materials such as tal- system.

11
L. A. Huchler, Select the Best Boiler-Water
Chemical Treatment Program, Chemical Engi-
neering Progress, August 1998, pp. 45 50.

11
 result in condensate pH above 7. As
2. Filming amines with neutralizing
shown in Figure 11, the corrosion rate of
amines
iron in an aqueous system is lowest be-
Often filming amines are used in combi- tween a pH of 8.5 and 12.7.
nation with neutralizing amines to ele-
vate the pH to the desired control range.
These programs are similar to the film-
ing amine programs that require system
pH controlled to a narrow range and
good feedrate control. Filmer/neutralizer Relative
programs are ideal for complex systems Corrosive
12.7 pH
such as refineries. The neutralizing Attack
8.5 pH
amine will concentrate in the vapor
phase of a flash tank while almost all of
}Safe Range
the filming amine will remain in the liquid 1 3 5 7 9 11 13
phase. pH

Filmer/neutralizer programs are more

expensive than filming amines alone, Figure 11 - Minimum Iron Corrosion
but cheaper than a neutralizing amine Rate
program. Because they form a chemi-
cal barrier that is impenetrable to dis- Because it would be uneconomical and
solved oxygen, passivating agents are chemically impossible to control the
not necessary and are not used in com- condensate pH to 12.7, the control
bination with filming amine treatment range for neutralizing amine treatment
programs. programs is at a pH between 8.8 and
9.2.
3. Neutralizing amines
Because neutralizing amines are fed
Neutralizing amines are the most widely stoichiometrically or in direct proportion
applied corrosion control treatment to the concentration of acidic contami-
chemicals in steam condensate sys- nants, the chemical feedrate and costs
tems. There are several advantages, increase as the concentration of con-
including ease of feeding, simple control taminants increases. For example, a
methods and compatibility with many system with high carbonate alkalinity in
other boiler treatment chemicals. the feedwater will have a high concen-
A chemical reaction or neutralization re- tration of carbon dioxide and require a
action occurs between neutralizing high concentration of neutralizing
amines and the acidic species in the amines.
condensate. All of the acidic contami- Many different neutralizing amine
nants will be neutralized when the con- chemicals are commercially available.
centration of neutralizing amine The most widely used materials are
stoichiometrically matches the concen- cyclohexylamine, morpholine and di-
tration of acidic contaminants. At this ethylaminoethanol amine (DEAE).
neutralizing amine concentration, the pH These amines are used singly or in
of the condensate will be 7. Higher combination to take advantage of each
concentrations of neutralizing amine will

12
chemicals physical and regulatory Chemical Feed Issues
properties such as volatility, neutralizing
All of the condensate treatment chemi-
capacity, distribution ratio, process
cals are fed continuously, using conven-
compatibility or approval for use in regu-
tional chemical feed equipment. How-
lated environments such as food plants
ever, there are two chemical feed issues
or steam humidification applications.
that merit special attention: process
Neutralizing amines may be fed with compatibility of treatment chemicals and
other steam system chemicals (except satellite chemical feed strategies.
oxygen scavengers) and can usually be Because steam is often injected directly
fed into the feedwater circuit with mini- into the process stream, the compatibil-
mal chemical losses through the boiler ity of the treatment chemicals with the
blowdown. With the exception of regu- catalysts and the various processes is
lated systems, the only consequences important. In refineries, there are no
of overfeed is additional cost. For regu- common incompatibilities between the
lated systems, the consequences of treatment chemicals with the catalysts
overfeed are non-compliance and pos- and processes. In other petrochemical
sible health effects in non-ventilated processes, there are some known in-
spaces. compatibilities with amines such as latex
manufacturing or certain catalysts. The
4. Passivating Agents plant should conduct a laboratory study
In systems where dissolved oxygen is a prior to the use of condensate treatment
contaminant, oxygen scavengers are in previously untreated systems, unless
added to reduce corrosion and protect a case history from a similar system is
or passivate the metal surfaces. These available. Each process compatibility
oxygen scavengers are known as pas- issue must be evaluated individually.
sivating agents because the chemical Typically, the refinery will add corrosion
reaction between the scavenger and the control chemicals at the powerhouse. At
dissolved oxygen is an electrochemical each process unit, the steam will be
reduction reaction similar to the reduc- mixed with steam generated locally by
tion reaction of iron oxide with dissolved waste heat boilers and reboilers, diluting
oxygen to form magnetite.12 In most the corrosion control chemicals. Conse-
systems, passivating agents will reduce quently, there may be an inadequate
the iron concentration in the conden- concentration of corrosion control chemi-
sate. cals in units that are located the furthest
from the powerhouse or in low pressure
5. Neutralizing Amines with Passiva-
reboilers. Often additional chemical feed
tors
is needed at the unit, a procedure known
Frequently passivating agents are as satellite feed. The reduction in the
blended with neutralizing amines in fully iron concentration and condensate cor-
formulated products. The feedrate is rosion rates in refineries using satellite
controlled by system pH, similar to a feed of chemicals has been modeled us-
neutralizing amine program.

12
Huchler, L., Passivation: The Known and the
Unknown, NACE Corrosion 94.

13
ing a complex computer based program tration as derived from the maximum
as well as empirically determined.13, 14 feedwater iron concentration is shown in
Table 4.
Corrosion Monitoring15
The most direct method of measuring Table 4 - Determination of Maximum
the corrosion rate by installing corrosion Condensate Iron Concentration
coupons in the critical reboilers is rarely
used in reboiler steam systems. Unlike Boiler Operating Pressure 150 psig
the other methods discussed herein, Maximum Boiler Feedwater 100 ppb
corrosion coupons provide a direct [Iron]*
measurement of the corrosion rate in a Percent of Condensate Re- 50%
system, and should be used in critical turn
locations or for confirmation of findings
from other analytical methods. Maximum Condensate 200 ppb
[Iron]
As an alternative, some plants evaluate
the corrosion rate indirectly by measur- The feedwater is comprised of two
ing the concentration of iron in the con- sources of water: condensate and
densate from a specific reboiler. To ac- make-up. The make-up water is as-
curately measure the concentration of sumed to have no iron contaminant
insoluble iron in condensate, the sample concentrations. The condensate equals
must be cooled and constantly flowing fifty percent of the feedwater, and there-
at 1000 ml/min. This method can be dif- fore will be diluted by a factor of two.
ficult since most plants do not have Therefore, prior to dilution by make-up
condensate sample points downstream water, the condensate can have twice
of each reboiler. When there is a cooled as much iron as the maximum feedwa-
condensate sample available at a spe- ter concentration, or 200 ppb.
cific reboiler, the pH can be routinely
measured. The simplest process con- Although the ASME guidelines are used
tamination monitor is condensate con- in this example, the maximum concen-
ductivity. tration of iron will vary based on boiler
There are no published guidelines for operating pressure, boiler design, his-
reboiler condensate quality, however, torical experience, plant monitoring ac-
control limits have been derived from curacy and control conformance and the
the ASME guidelines. An example of boiler manufacturers recommendations.
the maximum condensate iron concen-
pH Monitoring
13
Beardwood, E.S., Operational Steam Con- The most common method for monitor-
densate Corrosion Control of Reboilers & Re-
heaters, 1997 International Water Conference, ing corrosion is to routinely monitor the
IWC-97-25. pH of the combined condensate return-
14
Reggiani, G., Predict and Optimize Boiler ing from all of the units. Unfortunately,
Cycle pH Control Using Advanced Computer the corrosion potential of individual re-
Simulation, 1997 International Water Confer- boilers cannot be evaluated from this
ence, IWC-97-26.
15
Chen, T., Batton, C., Cicero, D., Port, R., single, composite pH measurement. To
Condensate Corrosion in Steam Generating accurately measure pH, the plant must
Systems, NACE Corrosion 98, Paper 718.

14
install sample coolers on each conden- ducted off-site at an analytical labora-
sate return streams. tory. The advantage of this method is
that iron and other contaminants can be
Millipore Method easily measured. In most refineries
There are several test methods used to atomic absorption is used as an occa-
monitor iron: Millipore, colormetric/ sional measurement of condensate con-
spectrophotometric, atomic absorption, taminants.
turbidimeter, particle counter, particle
monitor. The Millipore method is a Turbidimeter
semi-quantitative method developed by A turbidimeter uses visible light reflected
the Babcock and Wilcox Company. This from surface of a sample to evaluate the
method is easily done in the wet lab at insoluble particulates, including iron.
the process unit. It consists of passing This analyzer does not measure soluble
one liter of sample through a 0.45 mi- iron concentrations and is not useful in
cron membrane filter. The color and in- tracking the corrosion rate. Turbidime-
tensity of the filter is visually compared ters are on-line analyzers installed in the
to a standard chart that correlates iron condensate system to monitor conden-
concentration with the filter appearance. sate quality during start-up, but they are
not typically used in reboiler conden-
Colormetric/Spectrophotometric sate.
The colormetric/spectrophotometric
methods use a chemical digestion to Particle Counters and Particle Moni-
solubilize particulate iron followed by a tors
reaction that forms a soluble metal ion Particle counters and particle monitors
complex. That metal ion complex has a are two very different analyzers that use
strong absorbance in a specific wave- light to measure insoluble particulates.
length that is correlated to the iron con- Particle counters are typically laboratory
centration. This method is easily com- instruments that measure particle quan-
pleted in the process unit wet lab and tity as a function of their size. Particle
has been adapted as an on-line ana- monitors are installed on-line in the con-
lyzer. Like all on-line analyzers, this densate system and provides a particle
analyzer requires a sample conditioning index. This particle index is not a
panel and a maintenance support to measure of the number of particles, but
routinely calibrate, refill the reagents, rather a relative measurement of the
and maintain the equipment in working concentration of insoluble particulates.
order.16 Like the turbidimeter, particle counters
and particle monitors are very useful to
Atomic Absorption track condensate quality during start-up
Atomic absorption uses a precise wave- but they are not typically used for re-
length to evaluate soluble concentra- boiler condensate.
tions. This method is typically con-
Chemical Treatment Monitoring
16
The success of a corrosion control pro-
Huchler, L., Herbert, W., Keys to On-line gram is typically described by measuring
Monitoring in Steam Generating Systems, 1998
International Water Conference, IWC-98-19. the cost of the chemical treatment ver-

15
 sus the corrosion rate. First, the reboil- Summary
ers that have the most severe service
Reboilers are found throughout refiner-
are identified as critical reboilers.
ies and are critical to reliable plant op-
Typically these reboilers are units that
eration. Regardless of the reboiler de-
receive the lowest pressure steam or
sign, the equipment requires proper me-
are located far from the powerhouse.
chanical and chemical treatment to
Second, the optimal condensate chemi- maximize reliability and performance
cal treatment rate must be identified. As and minimize outages. The dynamic na-
the condensate chemical concentration ture of the petrochemical markets and
is increased, the treatment cost in- the uniqueness of each process require
creases and the corrosion rate de- individual system audits to evaluate
creases. The most cost-effective proper mechanical operation and
chemical treatment cost is at the inter- chemical treatment and monitoring.
section of the two curves. The costs
There are several key monitoring tools
shown in Figure 12 are relative costs.
that can be used to evaluate the risk of
To evaluate a specific system, the ac-
corrosion and deposition problems in
tual costs and corrosion rates would
reboilers. Consistent monitoring and
need to be evaluated at a variety of
corrective action will prevent failures,
chemical feedrates.
reduce operating costs, significantly im-
Chemical treatment monitoring is often prove system reliability and extend sys-
combined with corrosion monitoring, tem life.
since corrosion control is the primary
objective of most chemical treatment
programs. To monitor the correct appli- References
cation of the chemical treatment pro- 1. Radle, J., Select the Right Steam
gram, the plant should routinely meas- Trap, Chemical Engineering Pro-
ure the pH and conductivity of the criti- gress, January, 1992.
cal reboiler condensate streams.
2. Beardwood, E.S., Operational
Steam Condensate Corrosion Con-
1.2 100
trol of Reboilers & Reheaters, 1997
Reboiler International Water Conference,
1.0 80
Corrosion
IWC-97-25.
0.8 (ppb iron)
60
0.6 Relative
Program 40
0.4 Cost
20
0.2
0
0
6 7 8 9 10
pH

Figure 12 - Cost/Benefit of
Neutralizing Amine Treatment

16
17