1

Feed Water Chemistry & Control

Nalco Indonesia ~
Power Industry Seminar
Pullman, Central Park ~ Jakarta
13-14 June 2012

Agenda

Key Issues

Guidelines for Condensate,

Feed Water, and Steam
Chemistry Control

Practical considerations in
application and control

New Technology

Steam Cycle

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 online

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

Sources of Chemicals in Steam

Volatile Carry Over

Higher pressure = greater
volatility
Cu an issue at > 2400 psi (160
bar)

Mechanical Carry Over

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

Contamination via
Attemperation
Shortcut of feedwater to turbine

Cu(OH)2
H2SO4

SiO2

NaOH

Na3PO4

NaCl

HCl

Volatile

Mechanical

Key Issue #2 : Cation (Acid) Conductivity

Conductivity after strong acid

ion exchange

Neutral salts become strong

acids

Magnifies conductivity 3-5 times

Cl-

and SO4

2-

Targets

De-gassed cation conductivity

uses a small boiler or N2 sparging
to strip off CO2 from carbonic acid

Na, Ca, Mg : Cl salts to HCl

Na, Ca, Mg : SO4 salts to H2SO4

Na, Ca, Mg : HCO3 salts to H2CO3

Also removes amine and

ammonia, but not organic acids

CO2 to H2CO3

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
Specific Cond, mS/cm

EPRI Std
< 0.1

Cation Cond, mS/cm

VGB Std
< 0.2

Na, Cl, SO4, ppb

<3

Silica, ppb

< 10

TOC, ppb

< 300

< 20

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
results

1997 survey
results

Organizations having
chemically influenced BTFs

81%

61%

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
FAC
Moderate Range
Severe Range
Moderate Range

Temperature
Deg C
80
150
150
180
180
230

Deg F
176
302
302
356
356
446

Saturation
Pressure
psia
7
70
70
146
146
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 wont 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 wont 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 & CONDENSATE
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

Increasing Passivation

Passivation Better than Blank

at All Temperatures

Blank
Carbohydrazide
Methlyethylketoxime

150

200

250

300

350

400

Temperature (oF)
28

Increasing Passivation

Passivation Better than Blank

at High Temperatures

Blank
Hydrazine
Erythorbic Acid

*
*
150

200

250

300

350

400

Temperature (oF)
29

Increasing Passivation

Passivation Equal to Blank

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
Hydrazine
N2H4

%C
(wt.)

Reaction and/or
Breakdown Products

Nitrogen, water, ammonia

Carbohydrazide
(N2H3)2CO

13.3

Hydrazine, nitrogen, water,

ammonia, carbon dioxide

Hydroquinone
C6H4(OH)2

65.5

Benzoquinone, light alcohols,

ketones, low molecular weight
species, carbon dioxide

Diethylhydroxylamine
(CH3CH2)2 NOH

53.9

Acetaldehyde, acetic acid,

dialkylamines, ammonia, nitrate,
nitrite

Methylethylketoxime
(CH3)(CH3CH2)C=NOH

55.2

Methylethylketone,
hydroxylamine, nitrogen, nitrous
oxide, ammonia, carbon dioxide

Erythorbic Acid
C 6H 8O 6

40.9

Dihydroascorbic acid, salts of

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 rats

>5000 mg/kg

370 mg/kg

Acute dermal LD50

- rabbits

>2000 mg/kg

420 mg/kg

Primary eye
irritation - rabbits
(24 hr)
Primary dermal
irritation - rabbits

Non-irritating
(0.33/110)

Irritating (26.5/110)

Mild irritant
(0.23/8.0)

Severe irritant
(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

drop the pH in initial condensation
zone & cause corrosion in steam turbine
Low V/L Amine is a better choice than
NH4OH to neutralizeI organic acids in
this particular area

Species

Relative
V/L

Destination

Carbonic
Acid

High

Final
condensation

Acetic &
Formic Acid

Low

Early stage of
condensation

Ammonia

High

Final
condensation

Low or
high

Early & final

stage of
condensation

Amines

(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

1800

Amine Product, mg/L

12
11

CA-300C

10

356

9
8

5711

7
6
5
4
3
2
1
8.6

8.7

8.8

8.9

9.0

9.1

9.2

Condensate / FW pH

9.3

9.4

9.5

9.6

Condensate, FW, and Steam Guidelines

EPRI Guidelines
Industrial

PC(L)

PC(H)

Caustic
Treat

AVT(O)

AVT(R)

OT

9.09.6
8.8-9.2

9.29.6
9.0-9.3

9.29.6
9.0-9.3

9.29.6
9.0-9.3

9.29.6

9.29.6
9.0-9.3

D 9.09.6
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
@CPD

< 20

< 10

< 10

< 10

Parameter
pH (all steel)
(Cu alloys)

Oxygen, ppb @EI

Reducing Agent

ORP, mV @DA In

< 10

< 10

< 5 (< 2)

D 30-50
O 30 150

yes

no

yes

no

+/- 50

-300 to 350

100 to
150

Condensate, FW, and Steam Guidelines

NALCO Guide for Implementation
Industrial

PC(L)

PC(H)

Caustic
Treat

AVT(O)

AVT(R)

OT

9.09.6
8.8-9.2

9.29.6
9.0-9.3

9.29.6
9.0-9.3

9.29.6
9.0-9.3

9.29.6

9.29.6
9.0-9.3

D 9.09.6
O 8.0-8.5

< 0.3
< 0.6

< 0.2
< 0.4

< 0.3
< 0.6

< 0.2
< 0.4

< 0.2
< 0.4

< 0.2
< 0.4

< 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

<2

<2

Cu, ppb @EI

< 10

<2

<2

<2

<2

<2

<2

Oxygen, ppb
@CPD

< 20

< 10

< 10

< 10

Parameter
pH (all steel)
(Cu alloys)
Cat Cond, mS/cm
W/ organic amine

Oxygen, ppb @EI

Reducing Agent
ORP, mV @DA In

< 10

< 10

<5

D 30-50
O 30 150

yes

Yes, if
cycling

yes

no

+/- 50

-250 to 350

100 to
150

The Nalco Latest Technology to

Monitor/Control Corrosion Tendency of Feedwater Systems

What is ORP ?
H2

Reduction of Oxygen
(CATHODE)

Corrosion = REDOX Reactions

REDOX Reactions Electron

Flow

Electron Flow = ORP

(Oxidation Reduction
Potential)

ORP = bulk FW corrosivity

Precipitation of Red Oxide

Fe2O3
o
O2

O
H

RED OXIDE

BLACK OXIDE
o

MAGNETITE

MAGNETITE

Fe3O4

Precipitation of Black
Oxide (CATHODE)
FeOH++ + Fe(OH)+2
Oxidation and
Hydrolysis

o
H++FeOH+
Evolution
of Hydrogen
(CATHODE)

Hydrolysis of
Dissolved Iron
lowers pH
Fe+2
Acid Pit Solution with
Lower Oxygen
Content

eFe

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:

Metallurgy
Flow velocity (FAC)
Temperature
pH
Dissolved oxygen
Conductivity
Stability of oxide layer /
passivation

Corrosion product transport

varies with:
Load / flow velocity
Expansion / contraction
Vibration

Monitor corrosion stress with

At Temperature ORP
(AT ORP)

Cycling
Base
Load
Monitor corrosion product
transport with
Chemtrac Particle Monitor

Nalco, the logo, 3D TRASAR, and AT ORP are trademarks of Nalco Company.
Chemtrac is a trademark of Chemtrac Systems, Inc.

Two
Shifting

43

ORP1 and At Temperature ORP (AT ORP)

ORP correlates to the corrosion

stress of the aqueous environment

+
0

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.

More oxidizing - can be more

corrosive

Greatly improves sensitivity and

response. Allows AT ORP to be used
for feedback control.

Potential difference between

measuring and reference
electrodes
More reducing can be more
passive

ORP is influenced by temperature,

pH, O2, dissolved solids, etc.

Development of AT ORP has been an

industry goal.
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 allferrous 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.
- Reducing or oxidizing agent
- Feed on demand and eliminate over or under feed.

Nalco Europe AT ORP

Control Equipment

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 theres 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
Dearator Performance
Pump Leaks

Operational

Load changes
Startup and shutdown
Condensate flow
Makeup flow
Process leaks
Temperature

Chemical
Dissolved oxygen
(All) Oxygen scavenger/
passivator dosage
pH
Condensate treatment
recycle

NCSM

What Types of Corrosion

NCSM can Minimize ?

Oxygen Pitting Corrosion

Flow Accelerated Corrosion

(FAC)

NCMS is superior to conventional

measurements
Feature
Response
Time
Sensitivity
Accuracy
Precision
Dosage
Control
Corrosion
Control

NCSM

Scavenger
Residual

Corrosion
DO Monitor Monitor

DO Test

V. Fast
V. High
High
High

Slow
Med
Med
Med

Slow
Med
Med
Med

Med
Med
High
High

Slow
Poor
Poor
Poor

Slow
Low
Low
Low

High

Poor

Poor

Poor

Poor

Poor

High

Poor

Poor

Med

Poor

Poor

RT ORP

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

Detects

Control Your Boiler

Response
24/7
from Anywhere .

Communicate

Thank You