1

Feed Water Chemistry & Control

Nalco Indonesia ~
Power Industry Seminar

Pullman, Central Park ~ Jakarta

13-14 June 2012
 2

Agenda

 Key Issues

 Guidelines for Condensate,

Feed Water, and Steam
Chemistry Control

 Practical considerations in
application and control

 New Technology
 3

Steam Cycle
 4

Key Issue #1 : Steam Turbine Requirements

 Steam purity specs can be stringent!
 Industry experts differ on specific allowed limits.
 Different manufacturers have different limits
 Limits may depend on design, service, age of unit

 Limits vary with the boiler treatment selected.

 Cation conductivity is principle measure in most plants
(< 0.15, < 0.2, < 0.3, < 0.8 mS/cm as cation conductivity)
 Na and SiO2 are more specific measures of
contamination.
 Cl- and SO4 measurement important, but not commonly found on-
line
 5

Critical Steam Cycle Chemistry Parameters

 Boiler and feedwater

chemistry driven by steam
purity requirements

 Turbine/Feedwater
 Cation conductivity (indirect
measure)
 Sodium (NaOH)
 Silica
 Chloride (HCl)
 Sulfate (H2SO4)
 Organic acids
 6

Sources of Chemicals in Steam

 Volatile Carry Over NaOH
Cu(OH)2
 Higher pressure = greater Na3PO4
volatility H2SO4 SiO2 NaCl
 Cu an issue at > 2400 psi (160 HCl
bar)
Volatile Mechanical

 Mechanical Carry Over

 Occurs in all boilers all the time
 Drops contain all boiler water
solids

 Contamination via
Attemperation
 Shortcut of feedwater to turbine
Key Issue #2 : Cation (Acid) Conductivity
 Conductivity after strong acid
ion exchange
Na, Ca, Mg : Cl salts to HCl
 Neutral salts become strong
acids
 Magnifies conductivity 3-5 times
Na, Ca, Mg : SO4 salts to H2SO4
 Targets Cl- and SO4 2-

 “De-gassed” cation conductivity

uses a small boiler or N2 sparging
Na, Ca, Mg : HCO3 salts to H2CO3
to strip off CO2 from carbonic acid

 Also removes amine and

ammonia, but not organic acids CO2 to H2CO3
 8

Key Issue #3 : High Purity Make Up

 Purity
 Generally must be as good as feedwater.
 EPRI specifications are a good target for modern plants.

Parameter EPRI Std VGB Std

Specific Cond, mS/cm < 0.1
Cation Cond, mS/cm < 0.2
Na, Cl, SO4, ppb <3
Silica, ppb < 10 < 20
TOC, ppb < 300

 Deaeration
 Few plants deaerate make up or condensate storage tanks, or hot well during
standby.
 Technically feasible – from 7 ppm to 100 ppb O2
 Vacuum deaeration, steam sparging, nitrogen sparging, membrane deaeration
Key Issue #4 : Condensate and Feed Water Quality

 Condensate
 Cogen plants must guard against contamination from steam host

 Feedwater
 Feedwater used for attemperation must meet steam purity specs.
- The LP section of most HRSGs is upstream of attemperation, and is treated
as feedwater. (AVT)
 Feedwater purity and consistency drive treatment selection.
- Minimizing corrosion and corrosion product transport is critical.
- FW heaters corrode on both shell and tube side!

 EPRI Guidelines are excellent targets, but:

 May be difficult for older plants to meet without capital investment in
system upgrades.
 All plants should develop unit specific guidelines, taking design,
pressure, service, and water quality into account.
 10

Key Issue #5 : Control of Dissolved Oxygen

 EPRI research and field study led to reduction in O2 target
 From < 20 ppb at CPD to < 10 ppb at CPD
 For all treatment programs
 Required for corrosion control

 Overfeed of passivator is not a good option

 Too strong of a reducing environment contributes to FAC
 Excess hydrazine and carbohydrazide produce ammonia
 Excess organic passivators can add to TOC, organic acids

 EPRI recommends / Nalco concurs:

 Limit air inleakage – have active detection and repair program
 Deaerate make up
 Nitrogen cap hotwell for standby
 11

Corrosion ~ Iron ~ Deposition ~ Corrosion

For high purity boiler systems, iron is the focus of

performance
CORROSION leads to IRON
IRON leads to DEPOSITION
DEPOSITION leads to CORROSION (again) & OVERHEAT
 12

Corrosion ~ Iron ~ Deposition ~ Corrosion

NaOH

Magnetite

Steam Out

NaOH
NaOH
Water In

Fe3O4
porous deposit

NaOH
 13

Chemically Influenced BTFs

2001 survey 1997 survey
results results
Organizations having
81% 61%
chemically influenced BTFs
•Hydrogen damage 57% 37%
•Acid phosphate corrosion 25% 17%
•Corrosion fatigue 45% 43%
•Pitting 40% 7%
•Stress corrosion cracking 28% 18%
•Caustic Gouging 11% 11%
Source: 2002 EPRI Study, “ Priorities for Corrosion R&D”

13
 14

Boiler Tube- Hydrogen Damage

14
 Key Issue #6 : Metal Passivation
 Passivation:
 Iron oxides to magnetite (reducing environment)
- Passivation Reactions: Hydrazine
N2H4 + 6Fe2O3  4Fe3O4 + N2 + 2H2O

N2H4 + 4CuO  2Cu2O + N2 + 2H2O

- Passivation Reactions: Carbohydrazide

12 Fe2O3 + (N2H3)2CO --- 8Fe3O4 = 3H2O + 2N2 + CO2

8CuO + (N2H3)2CO --- 4Cu2O + 3H2O + 2N2 + CO2

 Or magnetite / hematite mix (neutral or oxidizing environment)
 Copper oxides to cuprous form (Cu2O)
- Less protective cupric oxide surfaces have 30 times the Cu release!
- Cuprous oxide will oxidize to cupric within 10 hours in O2 environment!
 Iron Oxide Passive Layer
~ Reducing Environment

Source: EPRI, Cycle chemistry Guidelines for Fossil Plants, Phosphate Continuum and Caustic Treatment, 2004.
 17

Iron Oxide Passive Layer

~ Neutral-Oxidizing Environment

Source: EPRI, Cycle chemistry Guidelines for Fossil Plants, Phosphate Continuum and Caustic Treatment, 2004.
Key Issue #7 : Flow Accelerated Corrosion

 Over half of utilities report FAC

 Two failure mechanisms –
single-phase and two-phase
 Occurs in
- Condensate and Feedwater
- Piping around BFP
- Piping to Economizer Inlet Header
- Economizer Inlet Header Tubes
- Deaerators
- Heater Shells and Drains
- Steam Turbine Exhaust
- LP Evaporators

 Second-most common failure

mechanism
 What is FAC ?
 Dissolving of protective
magnetite layer (Fe3O4)

 Influenced by several factors:

 Velocity
 Flow geometry
 Two phase flow
 Temperature
 pH
 Oxygen concentration
 Overfeed of Passivators
 Metallurgy

that contribute to magnetite

solubility
 Factors Affecting FAC - Temperature
 Extremely temperature dependent:
 Occurs in HRSG IP & HP Economizer tubes & headers, and in LP
evaporators & drums.
 Occurs in cold re-heat return lines, FW heater drip lines.

Tendency for Saturation

Temperature
FAC Pressure
Deg C Deg F psia
Moderate Range 80 176 7
150 302 70
Severe Range 150 302 70
180 356 146
Moderate Range 180 356 146
230 446 409
Factors Affecting FAC – pH
 Factors Affecting FAC
~ Oxidizing & Reducing Environment

Source: EPRI, Cycle chemistry Guidelines for Fossil Plants, Phosphate Continuum and Caustic Treatment, 2004.
 FAC Solution
 Material upgrade to 1 or 2% chrome

 Maintain pH in proper range with ammonia or amines

- Higher end of range is better!
- Pay attention to amine distribution ratio in multi-pressure HRSGs

 Avoid a highly reducing environment!

- Do not allow excess feed of reducing agents!
- Cycling units: do not feed high levels of reducing agent to compensate for
high O2 at start up.
- Monitor feedwater ORP, consider control of passivator to ORP

 Monitor with soluble iron tests before and after suspect areas
- Need proper sample points!
Key Issue #8 : Use of Organic Amines & Passivators
 EPRI & VGB recommend Ammonia and Hydrazine
 Stuttgart Conference on Organics – June 2005
 Co-Sponsored by EPRI and PowerPlant Chemistry
 Organic Amines
- Used safely for many years
- No factual evidence of contribution to turbine corrosion
- Some breakdown to organic acids, contributing to cation conductivity
- Ammonia counter ion neutralizes the acids
- Many feel okay to continue use
 Organic Passivators
- Some breakdown to organic acids, contributing to cation conductivity
- No alkaline counter ion
- Most believe should not use
 Carbohydrazide
- Produces CO2 on breakdown. Excess carbohydrazide will produce ammonia.
- CO2 not believed to cause any significant corrosion in steam cycle
- Estimate that 20 ppb Carbohydrazide contributes 10 ppb CO2, and creates 0.08 mS/cm cation
conductivity from the CO2.
- Most believe carbohydrazide is okay to use
Organic Amine & Passivator – CO2 Myth
 CO2 is not solid so it won’t be deposited in the LP blade and creating
localized acidic condition

 It is required ~ 200 ppb of CO2 to drop the pH of pure water from 6.5 to
< 6.0

 At low pressure, V/L of CO2 is quite the same with Ammonia and
higher than neutralizing amines. It is mean all of CO2 will be neutralizing
by proper dosing of ammonia/amines.

 There are some literatures from independent parties that clearly

explained that CO2 won’t depress pH of initial condensation in the level
that we commonly found boiler operation (<2 mS/cm) and when the
alkalizing agent is exist (Robert Svoboda and Alstom)
 Nalco 1250 (ELIMIN-OX)
• Active Content : CARBOHYDRAZIDE (CHZ)
• ALL VOLATILE & NON-SOLIDS Contribution in
Steam Cycle
• It is used as a METAL PASSIVATOR
• Much SAFER than HYDRAZINE
• NOT A SUSPECT CARCINOGEN
• Slight increase in cation conductivity from CO2
20 ppb CHz contributes 10 ppb CO2, which contributes 0.08
mS/cm cation conductivity (But 0 degassed cation
conductivity)
O
II

NH2-NH-C-NH-NH2
CARBOHYDRAZIDE
 MECHANISM REACTION of ELIMIN-OX

At LOW Temp.
(T  1350C)

1 ppm Elimin-Ox
29 ppb (,or
0.029 ppm) CO2
& NO IMPACT to
STEAM & CON-
DENSATE
corrosivity

Practically, it is very simple to check @ BFW sample, as residual of

10 – 30 ppb (as N2H4) ~ local (site) BFW sampling w/t T > 1800C
 Passivation Better than Blank
at All Temperatures
Increasing Passivation
Blank
* Carbohydrazide
Methlyethylketoxime

* *
*

150 200 250 300 350 400

Temperature (oF)
28
 Passivation Better than Blank
at High Temperatures
Increasing Passivation
Blank
* Hydrazine
Erythorbic Acid
*

*
*
150 200 250 300 350 400
Temperature (oF)
29
 Passivation Equal to Blank
Increasing Passivation
Blank
* Sulfite
DEHA
Hydroquinone

*
* *
150 200 250 300 350 400
Temperature (oF)
30
Feedwater Iron Reduction in 1500 psig boiler
with ELIMIN-OX

31
Feedwater Copper Reduction in 1500 psig boiler
with ELIMIN-OX

32
Reaction and/or Breakdown Products
Chemical/Formula %C Reaction and/or
(wt.) Breakdown Products
Hydrazine 0 Nitrogen, water, ammonia
N2H4
Carbohydrazide 13.3 Hydrazine, nitrogen, water,
(N2H3)2CO ammonia, carbon dioxide
Hydroquinone 65.5 Benzoquinone, light alcohols,
C6H4(OH)2 ketones, low molecular weight
species, carbon dioxide
Diethylhydroxylamine 53.9 Acetaldehyde, acetic acid,
(CH3CH2)2 NOH dialkylamines, ammonia, nitrate,
nitrite
Methylethylketoxime 55.2 Methylethylketone,
(CH3)(CH3CH2)C=NOH hydroxylamine, nitrogen, nitrous
oxide, ammonia, carbon dioxide
Erythorbic Acid 40.9 Dihydroascorbic acid, salts of
C 6H 8O 6 lactic and glycolic acid, carbon
dioxide

33
 Comparison of Acute Toxicology of
ELIMIN-OX and 35% Hydrazine
Study Performed ELIMIN-OX 35% Hydrazine
Acute oral LD50 - >5000 mg/kg 370 mg/kg
rats
Acute dermal LD50 >2000 mg/kg 420 mg/kg
- rabbits
Primary eye Non-irritating Irritating (26.5/110)
irritation - rabbits (0.33/110)
(24 hr)
Primary dermal Mild irritant Severe irritant
irritation - rabbits (0.23/8.0) (7.0/8.0) May be
corrosive. (Most
suppliers ship as a
corrosive liquid)

34
 35

References of Nalco 1250/Elimin-Ox

 Steam & Condensate Equipment
Steam Turbine – Advantages of Amines

 If not neutralized, organic acids may Species Relative Destination

drop the pH in initial condensation V/L
zone & cause corrosion in steam turbine Carbonic High Final
Acid condensation
 Low V/L Amine is a better choice than
NH4OH to neutralizeI organic acids in
Acetic & Low Early stage of
this particular area
Formic Acid condensation

Ammonia High Final

condensation

Amines Low or Early & final

high stage of
condensation

(initial condensation)
 Nalco 5711
 Minimum contribution of cation conductivity. Deliver <0.2 mS/cm cation
conductivity in system with no contamination (0.1-0.3 mS/cm lower than amine
available in the market)

 Containing low V/L amine that will increase the pH in early condensation zones
in the LP turbine, feedwater heaters and extended steam distribution system

 Low V/L amine will also improve pH in the LP section of multi pressure HRSG
and minimize potential of FAC

 Increase the pH with relatively same dosage with 19% NH3

 Has higher boiling point. Safer to handle, easier to pump without off gassing,
and produces fewer odor
Reference : PT. Freeport Indonesia
 N5711 Dosage vs Ammonia

Amine Product Concentration vs. pH in pure water

15
14
19% NH3
13
12 1800
Amine Product, mg/L

11
CA-300C
10
9 356
8
5711
7
6
5
4
3
2
1
-
8.6 8.7 8.8 8.9 9.0 9.1 9.2 9.3 9.4 9.5 9.6
Condensate / FW pH
Condensate, FW, and Steam Guidelines
EPRI Guidelines
Indus- Caustic
Parameter PC(L) PC(H) AVT(O) AVT(R) OT
trial Treat
pH (all steel) 9.0–9.6 9.2–9.6 9.2–9.6 9.2–9.6 9.2–9.6 D 9.0–9.6
9.2–9.6
(Cu alloys) 8.8-9.2 9.0-9.3 9.0-9.3 9.0-9.3 9.0-9.3 O 8.0-8.5
Cat Cond, mS/cm < 0.3 < 0.2 < 0.3 < 0.2 < 0.2 < 0.2 < 0.15

Na, Cl, SO4 ppb <5 <2 <3 <2 <2 <2 <2

Silica, ppb < 20 < 10 < 10 < 10 < 10 < 10 < 10

Fe, ppb @EI < 10 <2 <2 <2 < 2 (1) <2 < 2 (0.5)

Cu, ppb @EI < 10 <2 <2 <2 <2 <2 <2

Oxygen, ppb
< 20 < 10 < 10 < 10
@CPD
Oxygen, ppb @EI D 30-50
< 10 < 10 < 5 (< 2) O 30 -
150
Reducing Agent yes no yes no

ORP, mV @DA In -300 to - 100 to

+/- 50
350 150
Condensate, FW, and Steam Guidelines
NALCO Guide for Implementation
Indus- Caustic
Parameter PC(L) PC(H) AVT(O) AVT(R) OT
trial Treat
pH (all steel) 9.0–9.6 9.2–9.6 9.2–9.6 9.2–9.6 9.2–9.6 D 9.0–9.6
9.2–9.6
(Cu alloys) 8.8-9.2 9.0-9.3 9.0-9.3 9.0-9.3 9.0-9.3 O 8.0-8.5
Cat Cond, mS/cm
< 0.3 < 0.2 < 0.3 < 0.2 < 0.2 < 0.2
W/ organic amine < 0.15
< 0.6 < 0.4 < 0.6 < 0.4 < 0.4 < 0.4

Na, Cl, SO4 ppb <5 <2 <3 <2 <2 <2 <2

Silica, ppb < 20 < 10 < 10 < 10 < 10 < 10 < 10

Fe, ppb @EI < 10 <2 <2 <2 <2 <2 <2
Cu, ppb @EI < 10 <2 <2 <2 <2 <2 <2
Oxygen, ppb
< 20 < 10 < 10 < 10
@CPD
Oxygen, ppb @EI D 30-50
< 10 < 10 <5 O 30 -
150
Reducing Agent Yes, if
yes yes no
cycling
ORP, mV @DA In -250 to - 100 to
+/- 50
350 150
 The Nalco Latest Technology to
Monitor/Control Corrosion Tendency of Feedwater Systems
What is ORP ?
 Corrosion = REDOX Reactions
H2 Precipitation of Red Oxide
Reduction of Oxygen
(CATHODE)
Fe2O3
o
O2
O
H
-
o
RED OXIDE  REDOX Reactions  Electron
BLACK OXIDE Flow
MAGNETITE o MAGNETITE
Fe3O4
o
Precipitation of Black
Oxide (CATHODE)

o
FeOH++ + Fe(OH)+2  Electron Flow = ORP
Oxidation and
o Hydrolysis (Oxidation Reduction
H++FeOH+
Hydrolysis of
Potential)
Evolution Dissolved Iron
of Hydrogen lowers pH
(CATHODE)
Fe+2
Acid Pit Solution with
e- Lower Oxygen

Fe
Content
 ORP = bulk FW corrosivity
Oxidation of Iron
ANODE  ORP indicates the potential of
bulk water to corrode
 ORP provide the best way to
control BFW corrosion stress
 42

Corrosion and corrosion product transport varies

significantly in condensate and feedwater systems.
 Corrosion varies with: Monitor corrosion stress with
 Metallurgy At Temperature ORP
 Flow velocity (FAC) (AT ORP)
 Temperature
 pH
 Dissolved oxygen
 Conductivity Two
 Stability of oxide layer / Cycling Shifting
passivation

 Corrosion product transport Base

varies with: Load
 Load / flow velocity
Monitor corrosion product
 Expansion / contraction
transport with
 Vibration Chemtrac Particle Monitor

Nalco, the logo, 3D TRASAR, and AT ORP are trademarks of Nalco Company.
Chemtrac is a trademark of Chemtrac Systems, Inc.

ORP1 and At Temperature ORP (AT ORP)
 ORP correlates to the corrosion
stress of the aqueous environment
More oxidizing - can be more
+ corrosive
Potential difference between
measuring and reference
0 electrodes
More reducing – can be more
passive
- industry goal.
 ORP is influenced by temperature,
pH, O2, dissolved solids, etc.
43
 RT ORP is measured on a cooled
sample at room temperature.
 AT ORP is measurement of ORP at
the temperature and pressure of
the condensate / feedwater
system.
 Greatly improves sensitivity and
response. Allows AT ORP to be used
for feedback control.
 Development of AT ORP has been an
 Nalco is the first to develop a
practical AT ORP system.
 Developed by Dr. Peter Hicks of Nalco.
Work began in 1992, commercial
production from 2008.
 Over 50 AT ORP units currently
installed in Power plants globally.
1. ORP and Oxidation / Reduction Potential are used in this presentation to
have the same meaning as Redox Potential.
 44

EPRI Cycle Chemistry Guidelines for Fossil Plants:

Phosphate Continuum and Caustic Treatment, Jan 2004,
Appendix B.

“Thus ORP should be used to control the oxidizing power of the feedwater in all-
ferrous systems or, and more importantly, the reducing power of the feedwater in
mixed-metallurgy feedwater systems.”

“The future direction should be to develop the technology to measure ORP in-situ
in feedwater, and to extend the mixed-potential model for use at the elevated
temperatures, where components are actually in contact with high temperature
water, such as in the boiler.”
 45

Advanced Monitoring: At Temperature ORP

 Oxidation / Reduction Potential
(ORP) can now be measured and
controlled in condensate and
feedwater systems:
 At system temperature and pressure.
 On-line in real time.
 To make corrosion events visible.
 To allow the plant to correlate corrosion stress to
plant operational and chemistry changes.
 To respond with appropriate magnitude and
sensitivity for feedback control.
 To control chemical feed to maintain the system
within an AT ORP control specification range.
Nalco Europe AT ORP
- Reducing or oxidizing agent Control Equipment
- Feed on demand and eliminate over or under feed.
 46

Why is it important?
AT ORP can help the plant to maintain a more
consistent oxidation state on the metal surfaces.
 Reduce condensate / feedwater system corrosion
 Extend feedwater heater life
 Reduce FAC in LP section of HRSGs

 Reduce corrosion product deposition in boilers

 Reduce boiler tube failures
 Reduce boiler start up chemistry holds
 Reduce frequency and duration of boiler chemical cleaning

 Prevent turbine efficiency loss from deposition of corrosion

products (Cu, Fe)
 Lower heat rate, higher generation
 47

AT ORP Monitoring and Control Equipment

Control PLC,
Communications

AT ORP Electrode

Optional Sample
Conditioning

EPBRE
(External Pressure
Balanced Reference
Electrode)
 48

AT ORP Electrodes:
Pt measuring electrode, Ag/AgCl Reference Electrode
 Sensor design limits
 133 bar, 260 oC
 Sample: 250-500 ml/min
 Typical install is after condensate
heating, but before feedwater pump.
 Installation (prioritized)
 Deaerator inlet or LP drum inlet
 Condensate after chemical feed
 LP drum or other point of interest
 Existing sample may be routed
through AT ORP and then to:
 Sample panel instruments
 Sample conditioning and Particle
Monitor or drain
 49

Advanced Monitoring : Chemtrac® Particle Monitor

• Corrosion product released in “crud bursts”.

– Occur every time there’s a thermal,
chemical, or hydraulic shock to the system.
– Usually invisible, as not monitored on line.
• On-line monitoring makes visible
• Particle monitor helps to:
– Correlate crud bursts to specific events.
– Correlate particle counts to ppb iron levels.
– Correlate particle counts to AT ORP.
– Correlate to metal passivation over time.
Introducing:

Nalco Corrosion Stress Monitor

Nalco Corrosion Stress Monitoring (NCSM)
with @T ORP Technology
What Types of System Stresses NCSM
can address ?
 Mechanical  Chemical
 Dearator Performance  Dissolved oxygen
 Pump Leaks  (All) Oxygen scavenger/
passivator dosage
 pH
 Condensate treatment
 Operational recycle
 Load changes
 Startup and shutdown
 Condensate flow


Makeup flow
Process leaks
NCSM
 Temperature
 What Types of Corrosion
NCSM can Minimize ?

Oxygen Pitting Corrosion

Flow Accelerated Corrosion

(FAC)
 NCMS is superior to conventional
measurements
Scavenger Corrosion
Feature NCSM Residual DO Test DO Monitor Monitor RT ORP
Response
Time V. Fast Slow Slow Med Slow Slow
Sensitivity V. High Med Med Med Poor Low
Accuracy High Med Med High Poor Low
Precision High Med Med High Poor Low
Dosage
Control High Poor Poor Poor Poor Poor
Corrosion
Control High Poor Poor Med Poor Poor
NCSM Respond to Small Increase of
Dissolved Oxygen
NCSM Responds Air In Leakage in
Condensate Pump
NCSM Responds to Small Changes of
pH/Amine Feed Problem
Nalco Corrosion Stress Monitoring (NCSM)
3DTfB for Power
 Nalco 3DT Corrosion Stress
Monitoring (NCSM) Package
 One @ T ORP controller per boiler,
2 probes each
 One Particle Monitor per boiler, w/ 2
sensors

 Nalco analytical support program

 Nalco service / consulting support
program
 NCSM with
Nalco 3D TRASAR Platform Technology
Measure

Response

Detects

Communicate
 NCSM with
Nalco 3D TRASAR Platform Technology
Measure
Control Your Boiler
Response
24/7
from Anywhere ….
Detects

Communicate
Thank You