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HP Boiler Water Treatment Training

APEC

Water & Steam Chemistry Control


Alan T. Sugod
Consultant
November 13, 2018

NALCOWater
An Ecolab Company
2

Introduction
3

Electricity = The Modern World


4

High Capital Cost To Produce

Must be protected!
5

Water Creates Problems

 Corrosion

 Deposition

 Steam Purity
Issues/Turbine
Deposits

Water in the Rankine Cycle


6

Purpose, Process, PayOff

 Purpose: The review the basics of power plant boiler water


treatment to control corrosion, deposition and steam purity
problems.
 Process: Discuss: [1] why pretreatment is key [2] basic
principles of feedwater and boiler water treatment, [3] what
is the consequence if key treatment parameters are not
met? [4] what can we do?
 Pay Off: Be able to understand the rationale behind boiler
water treatment and help in improving reliability, efficiency
and safety of the power plant boiler operations.
7

Importance of Pretreatment
8

The Hydrologic Cycle


9

Impurities in Water

Air Earth

Calcium Oxygen Carbon


Magnesium Dioxide Carbon
Sodium Clay
Monoxide Silt
Iron Hydrogen Sulfide Sand

Dissolved Solids Dissolved Gases Suspended Matter


10

Boiler Make Up Water Guidelines


Parameter EPRI Std VGB Std
Specific Cond, < 0.1
uS/cm
Cation Cond, uS/cm < 0.2
Na, Cl, SO4, ppb <3
Silica, ppb < 10 < 20
TOC, ppb < 300
11

Contaminants and Pretreatment


Contaminants Unit Operations Principle of Process

Suspended Solids Clarifier • Coagulation & Flocculation


(Turbidity) • Settlement/ Sedimentation
Suspended Solids, Collodial, MMF Filter Activated • Filtration
Organics, & Bacteria Carbon Filter • Adsorption
Membrane
Dissolved Solids Ion Exchanger Ion exchange

Dissolved Solids Reverse Osmosis Membrane filter separation

Dissolved Solids Thermal Desalination • Evaporation


• Heat transfer
Dissolved Solids EDI/CDI Electro Deionization
12

EPRI Study

“The purity of water and steam is central


to ensuring fossil plant component
availability and reliability.”
13

Problems with Impurities


14

Contaminants of Concern in Steam

 Sodium
Stress Corrosion Cracking and
 Chloride corrosion on turbine blades

 Sulfate
 Silica
Deposition on turbine blades resulting
 Iron
to efficiency losses.
 Copper
 TOC
May contribute to corrosion in the
steam turbine
 Organic Acids
Turbine Problems Related to Carry
Over and Steam Purity

Solid Particle Corrosion Deposition Stress Corrosion Cracking


16

Sources of Impurities in Steam


Priming Foaming
 Boiler Water
 Superheater/Reheater Piping
 Attemperation Water
17

Typical Locations of Impurity Ingress in a


Drum Cycle
18

Process Condensate if not polished is a


potential source of contamination
High Pressure Boiler Definition
Terminology:
“Boilers in which steam
produced at or above 70 bar
(1000 psi)”
 Sub-critical, below critical
pressure (225 kg/cm2), Drum
type boilers.
 Supercritical, mostly operate at
245 kg/cm2. Highest is 350
kg/cm2. Once-through boilers
20

Steam Drum Mechanical Separators


Steam

Rely on
density
difference to
separate
liquid and
vapor phase
Difficulty in Steam Separation at HP’s
 Smaller density difference of liquid and vapor

34 barg

129 barg

220 barg
Boiler Pressure vs Mechanical Carry
Over

0.15%

0.11%

0.085%
61 bar 100 bar 143 bar
23

Other Sources of Carryover

 Priming
 Misting
 Foaming
24

Priming
Lifting of gross amounts of water into the steam due to some
abnormal mechanical or operating condition

Disruption Sudden
Operating High water Sudden Sudden
in boiler severe
the boiler level in reductions increases
water contaminat
> capacity drum in pressure of load
circulation ion

https://www.youtube.com/watch?v=4yW2mKqi8Gc&index=6&list=PL924D2D7822AD04E8
https://www.youtube.com/watch?v=8Lmagejlc1s&index=7&list=PL924D2D7822AD04E8
25

Foaming
Production of a stable frothlike blanket of tiny bubbles on a
boiler water surface.

Chemical condition Stabilization of


or contamination Foaming & carry
water films around
over
(TDS & SS) the bubbles

Normal Bubbles Stabilized Bubbles

https://www.youtube.com/watch?v=gBNeIBgVfvk&index=8&list=PL924D2D7822AD04E8
26

Misting (Spray Carry Over)

 Wet fog-like condition above a boiler water surface


when the individual bubbles on the water surface
burst and throwing off tiny water particles into the
steam space
 Have 3 process stages:
▪ a bubble of steam vapor reaches the water surface
▪ the bubble bursts, leaving a dent in the water
▪ the water rises to fill the center of the dent fills at a faster
rate than the edges ➔ a small droplet of boiler water that is
thrown off as a fine mist

 Misting and foaming seldom occur together


Higher Boiler Pressure and
Vaporous Carry-Over
SiO2
• Higher pressure =
greater volatility of Na
dissolved solids Volatile

SiO2 starts to have


significant volatilization
at 600 psiG (41 barG)

2
7
28

Total Carryover
Total Carryover =
Mechanical
Carryover +
Vaporous Carryover

100 bar = 700


ppb SiO2

145 bar = 300 ppb


SiO2
29

Handling Carry Over


 Priming
▪ Reduce or minimize and eliminate potential causes of priming
by mechanical and operational approaches
▪ Optimize performance of mechanical steam purification
equipment in the boiler drum

 Foaming
▪ Minimize boiler water contamination from upstream side
▪ Control TDS level in BW by means of boiler blowdown
▪ Optimize performance of mechanical steam purification
equipment in the boiler drum
30

Handling Carry Over


 Misting
▪ Optimize performance of mechanical steam purification
equipment in the boiler drum

 Selective Carry Over


▪ Minimize boiler water contamination from upstream side
▪ Control TDS level in BW by means of boiler blowdown
▪ Optimize performance of mechanical steam purification
equipment in the boiler drum
Other Source of Carryover -
Direct Contact Attemperator
Effects of contaminated Attemperation water
▪ Fouling of both superheater and turbine if sprayed at
midspan
▪ Attemperation after the steam passed the superheater
affects only the turbine
32

Water Quality Limit for Direct Contact


Attemperator

 Have same purity as


steam as well!
33

BW Contaminants of Concern

 Iron  TOC

 Sodium  Organic Acids


 Chloride  Impurities
from
condenser leaks
 Sulfate
▪ Deposition
 Silica
▪ Chemistry control
problems
 Copper
 Regenerants
Key Issue of Impurities in HP Boilers:
High Cycles of Concentration
 Make-up water cost for HP
boiler is high
 Energy loss from blow
down is high
 Blowdown has to be
minimized
Expensive to run at low cycles

Feedwater Rate
Cycles = ---------------------------
Blowdown Rate
35

Negative impact of Low Blowdown –


High Cycles
 Multiplies the concentration of trace impurities coming in
from the feedwater –> cycles X concentration in feedwater
▪ Leads to deposition due to saturation
▪ Higher tendency to contaminate steam

 Transport of impurities, i.e. insoluble particles like SS and


iron oxide is greatly reduced
▪ Higher potential for deposition

 High residence time


▪ Renders organic polymer dispersants unusable
▪ Difficult to purge out contaminants
Iron oxide Deposit Accumulation
 Particulate iron removal is not very effective
through the continuous blowdown at high cycles
▪ Blowdown orientation and flow velocities do not
favor high removal efficiency of iron oxides
(corrosion products)
- Low cycles and low heat flux ~ 35% iron removal
- High cycles and low heat flux ~ 10% iron removal
- High cycles and high heat flux < 5% iron removal
Ineffective Removal of Iron at the CBD

Key to Iron Deposition Control is Reduction in Entering Iron


38

Iron Deposit Concentrating Mechanisms:


Wick Boiling

• Super concentration of
dissolved solids beneath a
porous deposit through
capillary action
• Capillary channels draw liquid
to the base of the deposit.
• Steam escapes through a
“chimney” through the
successive formation and
release of steam bubble
Key Issue of Impurities in HP Boilers:
No Tolerance for Deposits
 HP boiler tubes already
operate at higher temps
 Deposit will retard the
heat transfer and further
increase the tube metal
temperature

HP Boiler Tubes have


practically no tolerance
for mineral deposits
Key Issue of Impurities in HP Boilers:
Concentrating Film Mechanisms
• The concentration of TDS in
the film is higher – due to
concentrating mechanisms

• The higher the temperature


difference between the film
and bulk water, the greater
TDS concentration in film

• High concentration of
agressive ions on the tubes
surface could lead to
localized corrosion
BW Impurities = Boiler Tube Failures
42

HP Boiler Water Treatment


43

Power Plant Boiler Cycle Chemistry


The Background – Problems and Issues

Turbine Corrosion & Deposition


• Corrosion in Phase Transition Zone
• Carry Over & Volatility

Boiler Tube Failure


• Hydrogen Damage
• Acid PO4 & NaOH Corrosion

Flow Accelerated Corrosion


• pH & ORP Impact

Copper Corrosion & Transport


• pH & ORP Impact
• Copper solubility
44

HP Boiler Water Treatment

1. Feedwater Treatment 2. Boiler Water Treatment


 Focus on FW chemistry  Boiler water chemistry
and treatment to reduce and treatment to minimize
corrosion products corrosion damage and to
transport to the boiler, help ensure steam purity
prolong the life of the FW compliance to steam
system and to minimize turbine requirements.
Flow Accelerated
Corrosion (FAC) potential.
45

Feedwater Treatment
47

Bigger Surface Area in BFW System

Bigger Area to Corrode !


48

LP, HP Feed Water Heaters, Condenser

Attention if CS and Cu Metallurgy


Flow Accelerated Corrosion (FAC)
 FAC : dissolution of protective magnetite layer (Fe3O4)
 Influenced by several factors:
▪ Velocity
▪ Flow geometry,
▪ Two phase flow
▪ Temperature
▪ pH
▪ Oxidizing-Reducing Potential
(ORP)
▪ Metallurgy
Flow Accelerated Corrosion (FAC)
Fe3O4 Solubility vs pH

FAC Potential vs Temperature


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
Boiler Feed Water Cycle Chemistry
There are only 2 (two) boiler feed water chemistry
treatment recommended for Power Plant Boilers:
1. All Volatile Treatment
- AVT (O)
- AVT (R)

2. Oxygenated Treatment (OT)


HP BFW Treatment Options

Feed Water
Treatment

All Volatile Oxygenated


Treatment Treatment
(AVT) (OT)

All Volatile
Reducing
(AVT-R)

All Volatile
Oxidizing
(AVT-O)
All Volatile Treatment (AVT) Concept

The AVT attempts to reduce corrosion product generation


via pH increase through application of
volatile alkalizing chemicals

Source: EPRI, Cguidelines for Controlling Flow-Accelerated Corrosion in Fossil and Combined Cycle
Plants ,2005
54

AVT vs OT - Comparison
AVT Reducing (R) Control Parameter
Parameter AVT(R)

pH (all steel) 9.2–9.6


(Cu alloys) 9.0-9.3
Cat Cond, uS/cm < 0.2
Na, Cl, SO4 ppb <2
Silica, ppb < 10
Fe, ppb @EI <2
Cu, ppb @EI <2
Oxygen, ppb @CPD < 10
Oxygen, ppb @EI <5
Reducing Agent Yes
ORP, mV @DA In -250 to -350
Source: Nalco, Steam Cycle Chemistry Guide Line Rev I, 2007
AVT Chemicals Injection Points

 Volatile pH Adjuster
N1800
▪ 1st : Down stream of CPD
▪ 2nd: Down stream of DA

 ReducingAgent
Passivator Eliminox
▪ 1st: Down stream of CPD
▪ 2nd: Down stream of DA

Source: EPRI, Cycle Chemistry Guidelines for Fossil Plants, All


Volatile Treatment, 2002
AVT Chemical Feed Control

 Nalco 1800
▪ Feedback control loop based on FW conductivity/ pH at Economizer
Inlet
▪ Feed forward control loop based on FW flow

 Oxygen Scavenger/ Reducing Agent


▪ Feedback control based on ORP at Deaerator inlet or Economizer
inlet
▪ Feed at a constant rate based on material balance for normal load
operation.
Oxygenated Treatment
 Recommended for all steel systems with condensate
polishers.
- Less corrosion of steels
- Lower metals transport to boilers
- Little need to chemically clean
 The most recommended program for supercritical boilers
 2 indispensable prerequisites:
▪ Requires high water quality and very tight control.
- <0.15 cation conductivity (at 25 oC) in condensate, feedwater, and steam.
▪ All ferrous metallurgy (copper alloys may be used only in condenser
tubing).
59

BFW Chemistry Control Parameter


Parameter All Volatile All Volatile Oxygenated
Reducing Oxidizing Treatment
pH (all steel) 9.2–9.6 D 9.0–9.6
9.2–9.6
(Cu alloys) 9.0-9.3 O 8.0-8.5
Cat Cond, uS/cm < 0.2 < 0.2
< 0.15
W/ organic amine < 0.4 < 0.4
Na, Cl, SO4 ppb <2 <2 <2
Silica, ppb < 10 < 10 < 10
Fe, ppb @EI <2 <2 <2
Cu, ppb @EI <2 <2 <2
Oxygen, ppb @CPD < 10 < 10 < 10
Oxygen, ppb @EI D 30-50
<5 < 10
O 30 - 150
Reducing Agent yes Yes, if cycling no
ORP, mV @DA In -250 to -350 +/- 50 100 to 150
60

Feed Water Treatment


The Benefits and Limitations

All Volatile All Volatile Oxygenated


Reducing Oxidizing

• CC < 0.2 mS/cm • CC < 0.15 mS/cm


• CC < 0.2 mS/cm
• Very good air in- • Excellent air in-leakage
• Good air in-leakage
leakage control control
control
• ORP neutral • ORP Positive
• ORP Negative
• FAC control very good • FAC control excellent
• FAC control moderate
• Fe < 2 (1) ppb • Fe < 2 (0.5) ppb
• Fe < 2 ppb
61

Boiler Internal Cycle Chemistry


62

Boiler Internal Treatment Chemistry

• To achieve non-corrosive
boiler water pH levels

• Provide adequate “buffer”


to deal with BFW
contamination

• Provide minimum solids


contribution to the boiler
water
Why pH Control is Important ?
Chemical Cleaning Guide Line
65

Caustic Corrosion

 Causes:
▪ Deposition
▪ Free NaOH > 1 ppm
- Na contamination
- Caustic overfeed

 Solution
▪ Minimize NaOH
concentration
▪ Na:PO4 = 2.3-2.6
(Congruent PO4)
66

Acid Phosphate Corrosion


Hideout Hideout Return
 Causes Load
▪ Deposition
▪ Phosphate Hide Out PO4
▪ Control Na:PO4 < 3:1
pH
 Solution
▪ Control PO4 residual at
lower range
▪ Control Na:PO4 > 3:1
▪ Equilibrium PO4 (EPT)
67

Hydrogen Damage
 Causes:
▪ Deposition
▪ Acidic condition
- Condenser in-leakage
- Pretreatment upsets
- Improper cleaning
▪ Inadequate buffer

 Solution
▪ Better BFW quality
▪ Control Na:PO4 3:1 to 1 ppm NaOH
▪ Continuum PO4
Phosphate Treatment Evolution
 1940’s: Coordinated Phosphate
▪ 3:1 Na:PO4, limited NaOH
Caustic
 1960’s: Congruent Phosphate Corrosion

▪ < 2.6:1 Na:PO4, zero OH


Phosphate
Hideout
 1986: EPRI Interim Consensus Guideline APC
▪ Congruent Phosphate Treatment (CPT) H2
Damage
 1994: EPRI Cycle Chemistry Guidelines
Failure to
▪ Equilibrium Phosphate Treatment (EPT) & PO4 Treatment (PT) adjust pH
for NH3
▪ Congruent Phosphate Treatment dropped Too low PO4
for Contam.
▪ EPT / PT both 3:1 Na:PO4, with 1.0 ppm NaOH APC
H2 Damage
 2004: EPRI Phosphate Continuum and Caustic Treatment
▪ Introduces “Continuum of Treatments”
▪ Replaces EPT / PT with Phosphate Continuum (PC)
▪ Includes Caustic Treatment (CT) as option
69

Phosphate Continuum (PC)


 Control at Na:PO4 = 3: 0 to 1 ppm NaOH
 TSP and NaOH only – no Phosphate with ratio < 3: 1
 Tight boiler water pH control required
 Transition from PC (Low) to PC (High) at approximately 3
ppm PO4
 Advantages:
▪ Better pH control and buffering
▪ Greater tolerance of FW contamination
▪ Reduced potential for acid phosphate corrosion if hideout occurs
▪ Easier to stay in specification
70
Phosphate Continuum
Control Chart

Phosphate Continuum Control Chart


10.2 TSP + 2 PPM NaOH

Na/PO4 = 4.0 Na/PO4 = 3.4


TSP + 1 PPM NaOH

10.0
PC Na/PO4 = 2.8
Na/PO4 = 3.0
pH : 9.0 – 9.7
9.8 Low PC PO4 : 0.3 – 3 ppm Na/PO4 = 2.6
pH at 25 deg C

9.6

PC
9.4
Note:
Minimum PO4
> 0.2 mg/L
9.2
pH : 9.5 – 10.1
9.0 HighPC (L) P
PO4 : 3 - 10ppm
C (H)
8.8

8.6
0 1 2 3 4 5 6 7 8 9 10
m
g
/
L

P
O
4
Phosphate Continuum Control Chart
Phosphate Continuum Control Chart
10.2 TSP + 2 PPM NaOH

Na/PO4 = 4.0 Na/PO4 = 3.4


TSP + 1 PPM NaOH
10.0 Caustic Na/PO4 = 3.0
Corrosion Na/PO4 = 2.8

9.8 Na/PO4 = 2.6


pH at 25 deg C

9.6
PC
9.4 Note:
NaOH Minimum PO4
> 0.2 mg/L
9.2 Acid Phosphate TSP
Corrosion
9.0
PC (L) PC (H)
8.8
BD
8.6
0 1 2 3 4 5 6 7 8 9 10

mg/L PO4
72

Continuum
EPRI New Cycle Chemistry Guide Line 2004

Solid All Volatile


Treatment Treatment
All Volatile (AVT)
Phosphate Continuum
- Oxidizing
(PC)
- Reducing

Oxygenated Treatment
Caustic Treatment (CT)
(OT)
Boiler Internal Treatment
The Benefits and Limitations

Caustic
PC- High AVT- R AV
T- O OT
& C-
P Low

Increase of
• High purity
• Ease of operation
• Better
performance

integrity • CC < 0.2 mS/cm • CC < 0.2 mS/cm


• CC < 0.2 mS/cm • Tight Condenser • Tight Condenser
• Tight Condenser • Full flow • Full flow
condensate condensate
• CC < 0.3 mS/cm polisher is highly polisher is highly
• Good Condenser recommended recommended
• CC < 0.15 mS/cm
• Tight Condenser
• Full flow
condensate
polisher is a must
74
Boiler Internal Treatment
Options and Control Parameter
Caustic
Parameter PC(L) PC(H) AVT(O) AVT(R) OT
Treat
pH (all steel) 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) 9.0-9.3 9.0-9.3 9.0-9.3 9.0-9.3 O 8.0-8.5
Cat Cond, uS/cm < 0.2 < 0.3 < 0.2 < 0.2 < 0.2 < 0.15
Na, Cl, SO4 ppb <2 <3 <2 <2 <2 <2
Silica, ppb < 10 < 10 < 10 < 10 < 10 < 10
Fe, ppb @EI <2 <2 <2 < 2 (1) <2 < 2 (0.5)
Cu, ppb @EI <2 <2 <2 <2 <2 <2
Oxygen, ppb @CPD < 10 < 10 < 10

Oxygen, ppb @EI D 30-50


< 10 < 5 (< 2)
O 30 - 150
Reducing Agent no yes no
ORP, mV @DA In +/- 50 -300 to -350 100 to 150
Boiler Internal Treatment
FW and Steam Limits
Feedwater and Steam Quality Limits

4 0.4

3.5 0.35

3 0.3

2.5 0.25

uS/cm
ppb

2 0.2

1.5 0.15

1 0.1

0.5 0.05

0 0
OT AVT PC(L) PC(H) CT

Na, Cl, SO4 Cat Cond


Boiler Internal Treatment
Boiler Water Quality Limits
Boiler Water Quality Limits @ 2500 psi

1400 28

1200 24

1000 20

800 16

uS/cm
ppb

600 12

400 8

200 4

0 0
OT AVT PC(L) PC(H) CT

Cl ppb SO4 ppb Cat Cond uS/cm


78

Takeaways
 Pretreatment is key. The purity of water and steam is
central to ensuring fossil plant component availability and
reliability. You can download and study the EPRI Guideline.
 Feedwater treatment centers on the minimization of iron
corrosion products that enters the boiler.
 Boiler water internal treatment controls corrosion and helps
ensure steam purity.
 Various treatment programs can be adapted depending on
the systems capability.
 Control of important parameters is important to ensuring the
expected water treatment results are achieved.