Documente Academic
Documente Profesional
Documente Cultură
NETRA
Cases of Acid Dew Point and Flow
Accelerated Corrosion in HRSGs and their
Remedial Measures
ASHWINI K. SINHA
AGM (NETRA)
ashwiniksinha@ntpceoc.co.in
ashwiniksinha@gmail.com
A Maharatna Company
Overview
NETRA
NETRA
A Maharatna Company
Rankin
Corresponding NH3/H2O Absorption Cycle
Temperature
7
1
8
5
6
Entropy
A Maharatna Company
Corrosion of
Turbines &
Other
Equipment
Health
Assessment of
Boiler Tubes
Failure
Investigations
NETRA
Cathodic
Protection
Chemical
Development
for CW System
Corrosion
Analysis,
Monitoring
& Control
Laboratory
Heat Transfer
Improvement
for Boilers &
HE
Corrosion
Monitoring &
Audit
Water
Management
Selection of
Anticorrosive
Coatings
NETRA
A Maharatna Company
Overview
NETRA
NETRA
Overview
A Maharatna Company
L. P. Drum
DEAERATOR
FUEL
(GAS / NAPTHA / HSD / NGL
H. P. Drum
Exhaust
COMBUSTION
CHAMBER
(SILO / CAN TYPE)
W.H.R.B.
AIR
GENERATOR
FLUE GAS
H.P.T.
CONDENSER.
GENERATOR
CONDENSATE PUMP
COMPRESSOR
GAS TURBINE
L.P.T.
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
1/2 O2
oxygen
SO3
sulfur trioxide
NETRA
A Maharatna Company
12
NETRA
A Maharatna Company
13
NETRA
A Maharatna Company
14
NETRA
A Maharatna Company
15
NETRA
A Maharatna Company
16
NETRA
A Maharatna Company
17
NETRA
A Maharatna Company
18
NETRA
A Maharatna Company
19
NETRA
A Maharatna Company
105 0C
400 0C
815 0C
1.13
6.5
3.94
pH
3.4
Phases Identified
20
NETRA
S
No.
1
2
3
4
5
6
7
8
9
PARAMETER
Temperature
pH
Conductivity
Sulphate
Sodium
Potassium
Nitrate
Water Soluble
Acid Insoluble
UNIT
Deg C
SO42-
As
As Na+
As K+
As NO3-
S
ppm
ppm
ppm
ppm
%
%
SAMPLE NO.
697/C-2084
HP EVA & ECO
Dust (1.0 %)
extract
25
2.86
2297
1040
2.9
0.3
17.2
12.00
14.3
SAMPLE NO.
697/C-2085
CPH Area
Dust (1.0 %)
extract
25
2.73
3137
2400
4.2
2.3
22.5
31.6
13.2
Description
C- 2084
HP EVA &
ECO Area
Dust
CPH Area Dust
C- 2085
Fe (%) as
Fe2O3
54.2
Na (%) as
Si (%) as
Cu (%) as
Na2O
0.9
SiO2
7.6
CuO
0.1
21
40.0
0.5
7.7
0.1
NETRA
A Maharatna Company
S. No.
1.
Sample No.
C- 2084
2.
C- 2085
Description
HP EVA & ECO Area
Dust
CPH Area Dust
Phase identified
Fe2O3, Fe+3(OH)SO4.2H2O,
FeO(OH)
Fe2O3, Fe2S2O9.5H2O
Sample
Fluoride
(ppm)
Chloride
(ppm)
Nitrate
(ppm)
Nil
3.17
7.00
Nil
Nil
43.67
Nil
1.89
0.812
Nil
Nil
2518.6
1.64
1.49
14.46
7.6
Nil
60.14
Nil
3.08
16.57
Nil
Nil
1190.8
22
NETRA
A Maharatna Company
Sl No
Data Required by NETRA
1
Flue gas composition of each HRSG at
inlet to CPH, outlet to CPH and Stack.
4
5
NETRA
S.No.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Unit No.
I
I
I
I
I
I
I
I
II
II
II
II
II
II
Reason
Planned Outage
Planned Outage
No demand
No demand
No demand
No demand
No demand
No demand
Planned Outage
Planned Outage
Planned Outage
No demand
No demand
No demand
Date
From
21.09.09
12.07.10
24.05.09
03.09.09
27.09.09
01.07.10
24.07.10
14.10.10
30.06.09
25.04.10
03.02.11
11.11.09
20.08.10
10.12.10
To
26.09.09
24.07.10
29.05.09
14.09.09
10.10.09
11.07.10
19.08.10
01.11.10
07.07.09
02.05.10
07.03.11
16.11.09
14.10.10
20.12.10
Outage
hours
116.35
290.37
105.31
266.19
325.34
240.13
635.15
424.56
167.58
156.13
761.11
110.15
1311.45
231.14
Average Relative Humidity during the year: 79.4% (Min. 22.4%, Max. 96.9%)
24
Average Temperature during the year: 27.4 oC (Min. 16.4 oC, 35.8 oC)
NETRA
A Maharatna Company
Method
Nitrogen
Desiccant
Trays
Dehumidified
Air
Advantages
- Effective
- No foreign Chemicals introduced
Disadvantages
- Low oxygen environment may be
hazardous to personnel
- Difficult to confirm that all spaces are filled
with nitrogen (not air) unless cap is installed
as pressure decays.
- Large volume of inert gas required
- Does not remove standing water
- Need to handle chemicals
- Damp chemical is corrosive if spilled in
drum.
- Air circulation through HRSG is not
accomplished naturally
- Requires frequent checking
- Equipment intensive; requires blowers,
flexible ducting
- Seal must be maintained with relative
humidity of < 30% re-established
- Constant use of blowers
- Require flush and refill
- Personnel should not enter drums until after
a flush, refill and startup
- Handling and introduction of foreign
25
chemicals
- Do not clear residual water
- Difficult to confirm dispersion throughout
HRSG
NETRA
A Maharatna Company
Gas-side layup
Gas-side corrosion can be problematic for HRSGs in cycling service. Layup of
the gas side historically has been given less consideration than it has for the
water side, but that may be changing.
As ambient temperature increases during the daylight hours, the cooler HRSG
components, with their considerable thermal inertia, lag behind, and moisture
condenses on metal surfaces. Condensation typically occurs when the relative
humidity is more than 35%.
Also, when HRSG internal surfaces are cooler than ambient temperature,
reverse draft through the stack occurs. Air entering through the stack exits via
the gas turbine, open gas-side manways, and other leakage points.
Dewpoint corrosion of tubes, fins, headers, and casing can cause many
problems including particulate emissions at restart, piping and hanger corrosion,
increased gas-turbine backpressure, and reduced heat transfer in the HRSG.26
NETRA
A Maharatna Company
27
NETRA
A Maharatna Company
28
Relationship between corrosion rate and the moisture content of air shows the
importance of maintaining relative humidity below about 40%.
NETRA
A Maharatna Company
29
The water vapour pressures from the water vapour table. A gas with 6.5 v% H2O has a
vapour pressure of 49.7 mm Hg (100 v% water has a vapour pressure of 758 mm Hg) and
a dewpoint of 38 C.
NETRA
A Maharatna Company
30
NETRA
A Maharatna Company
31
Dew points of SO3 at various water contents of the gas, calculated from the formula
of Verhoff.
NETRA
A Maharatna Company
32
Dew points of SO2 at various water contents of the gas, calculated from the formula
of Kiang. The SO2 dew points for all gasses are lower than the water dew point of
the gasses.
NETRA
A Maharatna Company
33
Dew points of HCl at various water contents of the gas, calculated from the formula
of Kiang and the water vapour table.
NETRA
A Maharatna Company
34
Dew points of NO2 at various water contents of the gas, calculated from the formula
of Perry and the water vapour table
NETRA
A Maharatna Company
35
NETRA
A Maharatna Company
36
NETRA
A Maharatna Company
Condensate Pre-heater (CPH), HP Evaporator and Stack liner of HRSGs are getting
affected by Corrosion by Condensed gases (SO2, H2O, NO2).
Corrosion products consists of iron oxides, sulphate , nitrate, and acid
insolubles and the products are acidic in nature.
Naptha contains around 0.01% sulphur and at around 6.5% moisture in flue gas,
the expected acid dew point is around 95 oC.
The flue gas temperature at CPH outlet is around 125 oC (rated 120 oC). This
suggests that flue gases are above acid dew point temperature during normal operating
period. However; the exit gas temperature is higher than the rated temperature,
suggesting that there is lesser heat transfer than the design in CPH region perhaps due
to fouling of tubes.
The deposit analysis indicates presence of sufficient quantity of sulphates (ranging
from 1000 -2500 ppm on boiler tubes & 58 ppm on stack liner), nitrates are
ranging from 4 ppm on stack to 22 ppm on boiler tubes and pH of 1% solution of
the deposit in water is ranging between 2.7 to 3.4.
The acid dew point of SO2 under the present conditions of operation is around 95
37
oC and dew point of NO2 is around 38 oC. These conditions can occur only when
the units are shutdown and the equipment are exposed to relative humidity of >
40% and ambient temperatures leading to corrosion from condensation of flue
gases.
NETRA
A Maharatna Company
Control Measures
Application of Novolac Vinyl Ester Glass Flake coating 1000 1200 microns
DFT on Structures of CPH and Stack Liners to improve life of the
structures.
To improve the performance of the HRSGs, there is a need to remove the
deposited corrosion/flue gas condensation products from the boilers. Some
methods of cleaning are indicated further.
There is a need to revisit the lay up strategy for the HRSGs (Gas Side) so that
ingress of atmospheric moisture can be prevented.
NETRA
A Maharatna Company
Cleaning
Method
Water
Washing
Grit Blasting:
CO2 Blasting
Magnesium
Hydroxide
Washing
(NETRA)
Pros
Cons
1. Low Cost
1. Water reacts with ammonia salts
2. Can be performed by plant O & M
to form sulphuric acid
2. Water waste must be removed
and treated
3. Water can leak into the internal
insulation
1. Low Cost
1. A small portion of metal is
2. Can be performed by plant O & M
removed along with the coating
2. High amount of waste has to be
vacuumed
1. Cleaning process causes no tube
1. Higher Costs?
or fin damage?
2. Must be subcontracted
2. No cleanup except for what was on 3. Environmentally friendly
the tubes?
1. Neutralizes the acidic materials.
1. Waste water needs to be removed
2. Forms a passivating layer on the
2. Water can leak into internal
boiler surfaces which gets
insulation (may need to place
removed after firing of boiler.
polyethylene sheets on the joints
39
3. Being in a slurry form can move
to prevent water ingressing into
along the boiler surfaces and
insulations)
remove the acidic deposit
NETRA
A Maharatna Company
Fuel
GT load
Frequency
WHRB-3
(Without
washing)
WHRB-4
(After
washing)
Unit
MW
Hz
Gas
124.744
50.21
Gas
122.811
50.21
deg. C
deg. C
123.500
471.59
102
100.300
471.59
102
deg. C
150
150
40
MW
4.725
4.725
MW
MW
-2.11640625
0.16734375
2.28375
NETRA
A Maharatna Company
MW
KWHr
KWHr
Rs.
Rs.
2.28375
54810
16004520
1.4
22406328
( say Rs, 2.241crores)
sm3/kwhr
Kwhr
sm3
Rs.
0.215
16004520
3440971.8
4307.78
NETRA
A Maharatna Company
HRSG manhole
HRSG
42
NETRA
A Maharatna Company
Hanger Rod
NETRA
A Maharatna Company
44
NETRA
A Maharatna Company
45
NETRA
A Maharatna Company
Duct Balloons for isolating the gas path from atmosphere & humidity
46
NETRA
A Maharatna Company
47
Corrosion Monitoring
NETRA
A Maharatna Company
V = I*R
Electrical
resistance
probe
R = *l/A
Corrosion Monitoring
A Maharatna Company
NETRA
Corrosion Monitoring
NETRA
A Maharatna Company
Although still a time averaged technique, the response time for ER monitoring is
far shorter than that for weight loss coupons. The graph below shows typical
response times.
Corrosion Monitoring
NETRA
A Maharatna Company
A Maharatna Company
NETRA
A Maharatna Company
NETRA
Parameters
unit
Value
pH
2.55
Conductivity
S/cm
2890
Total
Hardness
ppm as
CaCO3
Nil
Cl
ppm as Cl-
Nil
M-alk
ppm as Cl-
Nil
EMA
1500
Acidity
450
Unit
S/cm
ppm
%
ppm as Na
ppm as K
ppm as CaCO3
ppm as CaCO3
ppm as CaCO3
ppm as Clppm as Clppm as SO42ppm as NO3-
Value
4.3
213
107
0.1
1
0.7
Nil
Nil
Nil
Nil
1
58
6
53
A Maharatna Company
Overview
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
OSHA Safety Hazard Information Bulletin - Potential for Feed Water Pipes in Electrical
Power Generation Facilities to Rupture Causing Hazardous Release of Steam and Hot
Water (Excerpts from OSHA Bulletin 19961031)
October 31, 1996
MEMORANDUM FOR:REGIONAL ADMINISTRATORSFROM:STEPHEN J. MALLINGER
Acting
Director
Directorate
of
Technical
SupportSUBJECT:Hazard
Information
Bulletin(1): Potential for Feed Water Pipes in Electrical Power Generation Facilities to Rupture
Causing Hazardous Release of Steam and Hot Water. The Directorate of Technical Support
issues Hazard Information Bulletins (HIBs) in accordance with OSHA Instruction CPL 2.65 to
provide relevant information regarding unrecognized or misunderstood health hazards,
inadequacies of materials, devices, techniques, and safety engineering controls. HIBs are
initiated based on information provided by the field staff, studies, reports, and concerns
expressed by safety and health professionals, employers, and the public. Bulletins are
developed based on a thorough evaluation of available facts in coordination with appropriate
parties
The Chicago Regional Office has brought to our attention the potential for feed water pipes in
electrical power generation facilities to rupture causing hazardous release of steam and
hot water. During an investigation of a multiple fatality accident at an electrical power
generation facility in an industrial plant, the Appleton Area Office uncovered at least three
other feed water pipe failure incidents in other power plants. In two of the three incidents,
six additional fatalities had occurred. In all cases, the feed water pipe failures were attributed to
wall thinning as a result of single-phase erosion/corrosion, leading to rupture of the pipes under
high working pressures
A Maharatna Company
NETRA
The rupture of feed water pipes due to wall thinning creates the potential for serious burns,
massive property damage, and power outages in electrical power generation plants. These feed
water pipe failures could not be linked to any specific aspect of system designs, materials, or
operating histories to support a conclusion that single-phase erosion/corrosion was distinctive
to these particular power plants. This suggests that these may not be isolated incidents but a
problem that may be widespread in the industry.
Several factors affect the rate of erosion/corrosion in piping. These factors include material
composition of carbon steel piping, temperature, low water pH, low dissolved oxygen content,
pipe geometry, and fluid velocity. The flow path through elbows, bends, tees, orifices, welds,
valves, and backing rings creates turbulence in flow which, with fluid velocity, has the potential
to react with the protective oxide layer of carbon steel piping, contributing to the
erosion/corrosion process.
Feed water pipes are addressed in the standard boiler inspection. Generally only a visual
inspection with the pipe insulation in place is done or required. Since this will not reveal pipe
thinning, employers may not have actual knowledge of the pipe wall thinning that could be
occurring.
To minimize the potential for personal injury or loss of life, property damage, and power
interruptions resulting from feed water pipe failure, it is recommended that employers of
electrical power generation facilities establish a flow-assisted corrosion (FAC) program:
to identify the most susceptible piping components/areas and establish a sampling protocol
consistent with engineering principles and practices;
use appropriate nondestructive testing (usually ultrasound) to determine the extent of pipe
thinning (if any); and,
where thinning is identified, establish a preventative maintenance program and replace piping
in accordance with ASME recommendations.
A Maharatna Company
NETRA
A Maharatna Company
Difference
Erosion?
Erosion,
FAC,
Erosion-Corrosion,
and
NETRA
Cavitation
Erosion- is defined as the damage resulting from water, steam, particles, or the
combination thereof on the material at hand. It can be seen as etching, defined lines, or
the wallowing out of a certain area. Often this can be misdiagnosed as Flow Accelerated
Corrosion. Chemistry as well as velocity can be a factor.
Flow Accelerated Corrosion (FAC) - EPRI defines FAC, Flow Accelerated (or Assisted)
Corrosion, as A process whereby the normally protective oxide layer on carbon or lowalloy steel dissolves into a stream of flowing water or a water-steam mixture. It can
occur in single phase and in two phase regions. EPRI has stated that the cause of FAC is
water chemistry. Two phase FAC can be differentiated between Cavitation by the evidence of
tiger stripes or chevrons. FAC has often been classified as Erosion-Corrosion. FAC is a
term originating with EPRI for a condition that the industry has previous labeled with the more
generic term Erosion-Corrosion.
Erosion-Corrosion (EC) - EPRI defines this as Degradation of material caused by both
mechanical and chemical processes. FAC is often mislabeled as Erosion-Corrosion, even
though FAC is caused by chemical and mass transfer effects. The term Erosion-Corrosion
includes many erosion and corrosion mechanisms while FAC is very specific. It is not incorrect
to call FAC, erosion corrosion however; FAC refers to a specific set of erosion corrosion
conditions. FAC is a term originating with EPRI for a condition that the industry has previous
labeled with the more generic term Erosion-Corrosion. Although there is industry practice in
calling FAC erosion corrosion, there are no mechanical processes associated with FAC.
A Maharatna Company
Difference
Erosion?
Erosion,
FAC,
Erosion-Corrosion,
and
NETRA
Cavitation
A Maharatna Company
Difference
Erosion?
Erosion,
FAC,
Erosion-Corrosion,
and
NETRA
Cavitation
Flow-accelerated corrosion (FAC) and erosion corrosion (EC) are often used interchangeably
to describe similar material degradation processes. As a result, confusion exists regarding the
identification of FAC and the differences between FAC and EC. Both types of damage
involve destruction of a protective oxide film on the surface of a material (usually a
metal or metal alloy). The elimination or removal of the oxide film is generally referred to
as the "erosion" process. This is followed by electrochemical oxidation, or corrosive
attack of the underlying metal. Both processes involve a fluid that flows across or impinges
on a metal surface. The differences between FAC and EC involve the mechanism by which
the protective film is removed from the metal surface. In the EC process, the oxide film is
mechanically removed from a metallic substrate. This most often occurs under
conditions of two-phase flow (i.e., water droplets in steam, solid particles in water, or
steam bubbles in water). It is also possible, but less likely, for erosion to occur under single
phase flow conditions. For this to happen, the fluid velocity must increase the surface shear
stress to a level that causes the oxide film to breakdown. In addition to shear stress, there
must also be variations in the fluid velocity
In the FAC process, the protective oxide film is
oxide is dissolved or prevented from forming,
surface. Thus, flow-accelerated corrosion may be
transfer, between a dissolving oxide film and a
dissolving species.
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
LP Feed Pipe
NETRA
A Maharatna Company
LP Feed Pipe
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
The FAC problem is most pronounced in carbon steels. In these materials, even small
concentrations of chromium, molybdenum, and copper can improve FAC resistance. Where
FAC problems cannot be resolved by changing water chemistry, carbon steels often are
replaced by low-alloy steels, such as P11 and P22
FAC is a mass-transfer process in which the protective oxide (mostly magnetite) is
removed from the steel surface by flowing water. Material wear rate depends on (1) steel
composition, temperature, flow velocity and turbulence, (2) water and water-droplet pH, and
(3) the concentrations of both oxygen and oxygen scavenger.
Temperature has a pronounced effect on the FAC wear rate and when a system is
inspected, components in the 250-400F range get a priority. Flow velocity has a strong
effect, which makes wet steam systems very susceptible to FAC. Reason is that the velocity
of the steam usually is much higher than that of the water.
Water chemistry effects on FAC often are not well interpreted. The pH of feedwater and
steam droplets must be kept above a certain threshold, which depends on the pH agent
used and on temperature. For ammonia and amines, their effect diminishes with
temperature. For feedwater treatment with ammonia, a room-temperature pH above 9.5
is desirable.
Oxygen actually is good for preventing FAC. Experience indicates that 5 ppb of oxygen
in feedwater can practically stop FAC, while excessive concentration of oxygen scavengers
accelerates it. In most CC units that do not have copper-alloy tubing, oxygen concentrations
can be as high as 20 ppb without causing any problem.
A Maharatna Company
NETRA
A Maharatna Company
NETRA
A Maharatna Company
NETRA
1. Flowing water increases material loss rate exponentially with flow velocity. Data are for
neutral 580-psig/356F water with an oxygen content of less than 5 g/kg. Exposure time is
200 hr
A Maharatna Company
NETRA
A Maharatna Company
NETRA
Fe(OH)2 + H2 (1)
This reaction is then followed by the Schikorr reaction where precipitated ferrous
hydroxide is converted into magnetite:
3Fe(OH)2
A Maharatna Company
NETRA
Control of FAC:
An effective FAC control program should include the assessment of the propensity of
different plant systems and components to FAC, the use of available software with
water and steam chemistry corrections and periodic inspections. Monitoring of iron
concentration around the steam cycle is also useful; elevated concentrations may
indicate ongoing damage in a specific subsystem. FAC and cavitation evaluation
procedures used include the combined effects of:
Component geometry
Flow velocity
A Maharatna Company
NETRA
Notes: EI - economizer inlet, CPD - condensate pump discharge, DAI - deaerator inlet,
D - drum unit, O - once-through unit
* - Copper alloys may be present in condenser.
+ - These ORP values are meant to be indicative of a reducing treatment where a reducing agent
is added to the feedwater, after the CPD, and oxygen levels are less than 10 ppb at the CPD.
However, ORP is a sensitive function of many variables and may under these conditions be as
high as 80 mV.
For HRSG plants with all-ferrous feedwater systems the feedwater chemistry should be AVT(O)
to avoid single-phase FAC in the feedwater and LP evaporator circuit.
For both fossil and HRSG plants, the basic idea of AVT is to minimize corrosion and FAC by
using deaerated high purity water with elevated pH. The pH elevation should be achieved by the
addition of ammonia. The actual pH range depends on the cycle metallurgy. The use and application of AVT(R)
in either type of plant with all-ferrous feedwater systems can result in FAC
A Maharatna Company
NETRA
A Maharatna Company
Effect of pH on FAC
NETRA
A Maharatna Company
NETRA
Recommendations:
1. AVT (O) water treatment should be continued with tighter control on water
chemistry parameters.
2. Turbulences should be minimized by proper design.
3. For new replacement and for new units material of construction may be
changed to P11 or P22.
4. NETRA has developed CHEMAnalyzer, implementation of the same (after
suitable modifications to meet HRSGs requirement) should be considered.
For this necessary instruments need to be procured & installed.
5. Regular inspection of susceptible components by ultrasonic (UT)
examination needs to be undertaken to prevent any catastrophic failure.
TRANSFORMING LIVES
NETRA
A Maharatna Company
83
83