Originally appeared in:
March 2014, pgs 55-58.
Used with permission.
Special Report Corrosion Control
A. ROSSI, G. ROBINSON and T. DALE,
GE Water & Process Technologies, Trevose, Pennsylvania
Consider new steam system corrosion
protection for refineries
For decades, neutralizing and filming amines have been
used to protect steam condensate in boiler systems. In refining
operations, where steam is utilized to improve fractionation,
added attention is needed to the type and amount of amines
added to the boiler/steam system to minimize amine chloride
salt fouling in the distillation column and crude overhead.
New technology in volatile filming corrosion inhibitors and
lower-salting neutralizing amines can provide cost-effective
solutions for the steam-condensate system and minimize the
risk of corrosive amine chloride salt formation. This approach
is useful for refinery operations working to maximize distil-
late production while maintaining protection of “difficult-to-
treat” steam condensate systems, e.g., reboilers using flashed
steam, and high-alkalinity makeup water sources.
Protecting steam systems. Ensuring the efficiency and
reliability of the steam plant is crucial to successful refinery
operations. Steam condensate and boiler feedwater (BFW)
protection are integral parts of maintaining the total health of
the entire steam and boiler system. By mitigating condensate
corrosion, the associated equipment and piping are protected.
Additionally, by protecting this system, the condensate can be
returned to the boiler as high-quality feedwater—thus, recy-
cling valuable water and conserving energy. Finally, minimiz-
ing the return of corrosion products greatly improves the ef-
ficiency and reliability of steam-generating equipment while
minimizing the need for deposit-control chemistry.
Traditionally, refineries have used organic amines to neu-
tralize acidic contaminants, such as carbonic acid, in the steam
condensate and raise system pH to prevent corrosion. Refin-
eries may also supplement the neutralizing amine program
with a filming corrosion inhibitor. These corrosion inhibitors,
including the subset known as filming amines, establish a te-
Distribution coefficients
nacious barrier film on the metal surface, thus inhibiting con-
tact of the corrosive contaminants (such as carbonic acid, dis-
solved oxygen and chloride salts) with metal surfaces. A key
advantage of effective filming corrosion inhibitors is that they
can be fed sub-stoichiometric to the acidic contaminant, thus
reducing total treatment costs.
In many cases, an effective filming inhibitor can reduce the
requirement for neutralizing amines by providing equivalent
corrosion protection at an incrementally lower condensate
pH than with the neutralizer alone. This can reduce treatment
costs, especially where amine feedrates are high. Historically,
HYDROCARBON PROCESSING MARCH 2014
traditional filming inhibitors, such as octadecylamine, should
be injected into the steam header because of their low volatil-
ity and limited ability to enter the steam phase from the boiler
when fed to the feedwater.
Consequently, achieving effective system coverage is often
difficult with traditional filming inhibitors of limited volatil-
ity. For example, many refineries produce and utilize lower-
pressure “flash” steam generated from higher-pressure liquid
condensate. This flashed steam, often used for critical reboil-
ers, can be heavily laden with carbon dioxide (CO2 ), thus in-
creasing the corrosion potential in the affected condensate. A
filming inhibitor with limited or no volatility will not readily
enter the flash steam from the condensate, which may leave
the downstream equipment served by the flash steam vulner-
able to severe corrosion. Consequently, satellite feed of tradi-
tional neutralizing and/or filming inhibitors to these areas is
often required for effective protection, requiring maintenance
of the remote feed system, pumps and product inventory.
Polyamine volatile filming inhibitor technology. A new
polyamine filming inhibitor technology can allow effective
steam-condensate system coverage and protection from one in-
jection location, often the deaerator storage section, as shown in
FIG. 1.1 This is in sharp contrast to the extremely low volatility of
traditional filmers discussed earlier.
An additional hurdle for steam treatment is maintaining
reliability of the equipment utilizing steam directly within the
process. A prime example is the atmospheric crude distilla-
tion tower, where stripping steam is used to improve product
12
10
8
6
4
2
0
0 200 400 600 800 1,000 1,200 1,400 1,600
Pressure, psig
FIG. 1. Steam-liquid distribution coefficients for polyamine as
measured in research boilers.
 Corrosion Control

separation. In this instance, it is imperative that the neutralizing An integrated approach. A collaborative effort between
amines used for steam condensate treatment be chosen to mini- water and process engineering teams discovered a unique so-
mize the risk of contributing to unwanted amine chloride salt lution to ensure maximum reliability of crude unit distillation
fouling and subsequent corrosion. As refiners decrease tower top processes while providing superior condensate protection.
temperatures to increase distillate production, the risk of amine Proprietary modeling software was used in the development
chloride salt formation inside the distillation column increases. and application of the new technology.2 Utilizing low-salt ionic
Amine chloride salt fouling depends on a number of factors equilibrium modeling in combination with condensate model-
including: chloride levels, operating temperatures/pressures ing software, many potential steam neutralizing amines were
of the distillation column, other sources of unwanted or tramp evaluated for their compatibility with the refining process and
ammonia/amines, and even amines used to protect the over- their effectiveness in managing corrosion in complex conden-
head and associated exchangers, as shown in FIG. 2. sate systems.2 This study included a rigorous examination of
These problems are more directly related to steam-treat- the potential for forming amine chloride salts under different
ment additives in systems where higher levels of neutralizing contaminant loadings and operating conditions in the atmo-
amine are required to maintain condensate corrosion protec- spheric crude unit tower. TABLE 1 lists comparative salt-point
tion. This is often the case in utilizing high-alkalinity BFW temperatures of typical neutralizing amine blends used in re-
and/or a lower-percentage condensate return. The problem is fining steam condensate treatments.
compounded in fractionation towers operating at lower tem- Additionally, it was critical to uphold the required critical
peratures where the amine chloride salt point can potentially parameters of neutralizing amines used in steam-condensate
be driven into the distillation column. treatments, which include the neutralization capacity, basicity,
Unless crude oil selection, additives and impurities, and steam-liquid partition coefficient or distribution ratio, and ther-
operating parameters are consistently favorable, it is recom- mal stability at boiler and steam temperatures. A key component,
mended to use steam-condensate protection that will provide the polyamine volatile filming corrosion inhibitor is typically in-
minimum impact on refinery operations. There are new steam- cluded with the low-salting amines to further enhance system
condensate corrosion inhibitor technologies now applied to coverage and reduce the traditional neutralizing amine required
use lower-salting neutralizing amines for steam treatment. In for corrosion protection. Consequently, the total “tramp” amine
combination with the volatile polyamine filming technology, contribution from the stripping steam can be reduced.
this approach can potentially provide a lower-cost and more- Because the modeling program can be used to simulate
reliable steam-condensate program. the potential for ammonia or amine chloride salt formation in
crude atmospheric towers and to optimize the model amines
TABLE 1. Calculated amine blend salt point in crude unit and contaminants in complicated steam systems, a more com-
overhead at 8.7 psig (˚F) prehensive approach to refinery system reliability can be taken.2
Original amine Industry standard GE Low salt/ The combined modeling approach allows the refiner and spe-
Chloride, ppm blend amine blend polyamine cialty chemical supplier to work together to optimize refinery
10 228 212 184
operations while maintaining the required process and water
treatment reliability.
20 244 224 198 For example, by modeling a refinery’s steam condensate sys-
40 261 237 212 tem, the refinery operator and process chemical supplier have a
better understanding of the amount and type of amines present
70 275 247 223
in the stripping steam. Using that information, combined with
100 284 254 231 an understanding of the other ammonia/amine sources and con-
130 291 259 237 taminants (e.g., chlorides), a more accurate model of the atmo-
spheric tower can be derived. This model will then enable the
160 297 263 241

Neutralizer Water wash

Amine sources include:
Overhead neutralizers
Steam neutralizers
Crude oil Accumulator
Slop oil Amine
Alkanolamine unit recycle
Sour-water strippers
H2S scavengers Amine Tower top reflux
Cold-wet reflux
Amine
recycle
Desalter

Fractionation Stripping steam

Tank farm column

Wash water
FIG. 3. Nonwettable surface provided by polyamine filmer
FIG. 2. Amine sources with a refinery and recycle loops. on corrosion coupons.

HYDROCARBON PROCESSING MARCH 2014

 Corrosion Control

refiner to better understand their operat- 10 0.025

ing limitations and allow them to maintain Standard amine Standard amine
optimal reliability and economics. 9.5 Low-salt amine 0.04 Low-salt amine

Low-salt boiler amine and polyamine 9.0

0.03
technologies. Low-salt boiler amine and

Fe, ppm
8.5

pH
polyamine technology can provide an
opportunity to further optimize refinery 0.02
8.0
boiler and process system reliability and
economics.3 Several refiners have report- 0.01
7.5
ed encountering limited optimizing eco-
nomics due to tramp ammonia/amines, 7.0 0
often when trying to maximize mid-distil- SRU BFW pH FCC average condensate pH SRU average Fe FCC average condensate Fe
late production and running at lower frac-
FIG. 4. pH and iron levels controlled by a low-salting amine treatment program.
tionation tower top temperatures.
In some cases, it is the amine in the
stripping steam that can be the limiting factor, and low-salting 13% flow pH = 6.1
amines were recommended to reduce/eliminate the bottleneck.3 Flashed steam to reboiler 108 ppm CO2
84 ppm Amine
Two refining cases reported small amounts of traditional amines
used in steam-condensate treatment, cyclohexylamine and me-
thoxypropylamine (MOPA), were limitations in maximizing
profitability. A compilation of abbreviated case studies are docu- Condensate Flash tank
mented in this article. pH = 8.9
14 ppm CO 2
34 ppm Amine
Case 1: Low-salting boiler amine with no polyamine.
One particular refinery was having concern around a particular
steam-treatment amine. This refinery had suffered some amine
chloride deposits in a crude unit top pumparound circuit. Prior Flash-tank bottoms pH = 10
to implementing the polyamine technology, its goal was to use 0.7 ppm CO2
87% flow 27 ppm Amine
a low-salting boiler amine to achieve the same pH and conse-
quently, the same iron level achievable with industry-standard FIG. 5. Model of amine and CO2 distribution and pH in a flash tank.
amines in use. The refinery implemented the low-salting boil-
er amine blend to replace the higher salting amine from the
steam.3 Condensate system modeling was done to predict the on the refining operations. In these situations, it is often best
required feedrates based on water chemistry and system op- to provide a filming technology.
erating parameters and targets. The low-salting boiler amine
achieved the required system pH levels as predicted. As a con- Case 2. A European refinery was experiencing severe cor-
sequence, the steam-condensate pH and iron levels remained rosion of reboilers/exchangers on a desulfurization unit that
approximately the same, as illustrated in FIG. 4. Although used steam with a pH < 6. Due to the corrosion problems, the
satisfied with the initial change to low-salting boiler amine refiner was replacing unit bundles about every 18 months.
chemistry, this refinery converted to a low-salt polyamine Traditional neutralizing amine treatment would require very
technical to further optimize performance and economics. high feedrates and be deemed uneconomical. As a result, a
polyamine-neutralizing amine blend was applied at about 10%
Studies with polyamine and standard amines. Refiner- of the theoretical “neutralizing amine blend only” feedrate. Al-
ies utilizing BFW with high levels of bicarbonate/carbonate most immediately after initiating the chemistry, the measured
alkalinity can generate significant CO2 in the steam and, con- total iron levels at the reboiler dropped significantly:
sequently, elevated levels of corrosive carbonic acid in the con- Reboiler total iron prior to polyamine-amine > 500 ppb
densate. These refineries are often challenged to feed enough Reboiler total iron after polyamine-amine < 50 ppb
neutralizing amine to achieve the required steam-condensate
pH levels to protect the condensate piping and equipment. More importantly, during the last scheduled maintenance
The use of condensate flash tanks to generate low-pressure on one of the reboilers, the refinery was set to replace the
flashed steam, often for nonvented reboilers carrying liquid bundle per its normal schedule. However, the inspection de-
levels, can also operate under highly corrosive conditions be- termined that no bundle replacement was needed because of
cause of the very high volatility of CO2 to the flashed steam, as the improved corrosion control.
illustrated in FIG. 5.
Under these circumstances, it can become very difficult Case 3. A similar application at a Southeast US chemical plant
and expensive to maintain corrosion protection by relying showed a tremendous reduction in mild steel condensate cor-
only on carbonic acid neutralization and boosting the pH. In rosion rates with the addition of the polyamine to the BFW.
addition, the high use of amines can have an adverse impact This particular plant had high-alkalinity BFW contributing

HYDROCARBON PROCESSING MARCH 2014

 Corrosion Control

ment and corrosion data were evaluated

on both the water and process chemistry.
Computer modeling of the systems was
conducted to predict, select and validate
the specific type of low-salt and poly-
amine chemistry that would be appropri-
ate to improve the reliability and econom-
ics for the refinery.
With implementation of the program,
the amine salting potential was improved
by removing nearly all of the higher salt-
point amines from the boiler steam treat-
FIG. 6. Field study using a polyamine treatment program. ment. The steam-condensate pH and iron
levels were regularly tested to ensure that
corrosion metrics were being met. After
70 several weeks of onsite iron testing and offsite iron corrosion
Industry standard amine blend product (ICP) testing, the low-salt polyamine feedrate was
60 Low-salt polyamine blend decreased further. This change also further reduced the total
Total iron ppb, (acid-digested ICP iron)

amine contribution from the stripping steam in the crude tower,

50
while improving economics around chemical spend (TABLE 2).
40 However, as modeling had predicted, this action would lower
condensate pH levels in the steam condensate system. It in-
30 cluded carrying a lower pH at some critical, nonvented reboilers
in the system. Now, more of the corrosion protection responsi-
20 bility was placed on the polyamine filmer. Chemical usage was
minimized, while increasing reliability in steam condensate and
10 refinery process via low-salting amines and filmer protection.
0 After several more weeks of analysis, the corrosion protec-
Main BFW Splitter condensate Plant 1 condensate Plant 2 condensate tion was maintained per on-site data and more accurate ICP
off-site iron data indicated an improvement. Four of the five
FIG. 7. Comparative amine impact for corrosion in various refining units.
samples in the system, including a nonvented reboiler, showed
less-than-detectable iron and copper levels (FIG. 7). Another re-
TABLE 2. Steam treatment cost comparison boiler had very low iron (< 2 ppb per ICP) at about 0.75–1 pH
units lower than initial treatment.
Cost to treat, Final
$/MMlb of steam Steam pH condensate pH
NOTES
Industry-standard x 8.38 9.67 1
GE has recently incorporated a new, more volatile polyamine filming inhibitor
amine blend technology allowing for effective steam-condensate system coverage.
2
Utilizing GE LoSalt Ionic Equilibrium modeling in combination with GE
Equivalent steam 0.953 8.38 9.33
Condensate modeling software, many potential steam neutralizing amines were
pH to standard, evaluated for their compatibility with the refining process and their effectiveness
low-salt/polyamine in managing corrosion in complex condensate systems.
Lower pH/cost to 0.793 7.84 9.29
3
Steamate LSA is a patent-pending technology that can provide an opportunity to
standard, low-salt/ further optimize refinery boiler and process system reliability and economics.
polyamine
ANTHONY ROSSI is a 35-year veteran of GE Water and Process Technologies
and serves as the global boiler product manager overseeing research and
new technology development for the boiler water product line. He has also been
over 20 ppm of CO2 to the steam and no appreciable conden- the global boiler engineering manager and a research chemist at GE. He is a
sate return. Consequently, the amine requirement for neutral- joint or sole inventor of record on four US patents related to boiler water
izing the carbonic acid and increasing the pH was significant treatment technology innovations. Mr. Rossi holds a BS degree in chemistry
and uneconomical. A plan was developed to add polyamine from LaSalle University.
and begin reducing the neutralizing amine. FIG. 6 illustrates GREGG ROBINSON has worked as an engineer for GE Water and Process
the results regarding the corrosion rates and mild steel coupon. Technologies for over 15 years managing applications in boiler, cooling, water/
The plant continues to optimize, and has reduced neutralizing waste, RO/demineralization and refining process chemistry. He specializes in
amine by over 70% while improving the mild steel and the cop- the refinery and power plant industries with a focus on optimum condensate
treatment of refining, chemical and power plant steam systems. Mr. Robinson
per corrosion rates. has a BS degree in chemical engineering from Penn State University.

Case 4: Low-salt polyamine blend. A Western US refinery TREVOR DALE has worked as a scientist in research and development for GE
Water & Process Technologies for four years. He has a PhD in physical organic
was in the scenario of having high condensate corrosion po- chemistry and has worked on new product development for corrosion and scale
tential and ammonia/amine chloride salt fouling in the crude inhibitors with an emphasis on the refining and petrochemical industry. Dr. Dale
and coker operations. To improve operations, key system treat- is an inventor or co-inventor on five granted patents/patent applications.

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