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    C. Boiler Internal Cycle Chemistry & Control

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    Rajendran Srn
    This document provides an overview of boiler internal cycle chemistry for a customer seminar in Indonesia. It discusses factors affecting cycle chemistry in high pressure boilers like smaller density differences and higher volatility at higher pressures. It then summarizes the phosphate continuum treatment program, which aims to prevent corrosion and deposition while producing pure steam. This involves maintaining tight pH control between 9.0-9.7 using sodium phosphate and sodium hydroxide. The document also outlines action levels for how long water chemistry can be outside normal specifications before requiring action.

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    C. Boiler Internal Cycle Chemistry & Control

    Uploaded by

    Rajendran Srn
    620 views46 pages
    This document provides an overview of boiler internal cycle chemistry for a customer seminar in Indonesia. It discusses factors affecting cycle chemistry in high pressure boilers like smaller density differences and higher volatility at higher pressures. It then summarizes the phosphate continuum treatment program, which aims to prevent corrosion and deposition while producing pure steam. This involves maintaining tight pH control between 9.0-9.7 using sodium phosphate and sodium hydroxide. The document also outlines action levels for how long water chemistry can be outside normal specifications before requiring action.

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    Boiler internal Cycle Chemistry & Control

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    This document provides an overview of boiler internal cycle chemistry for a customer seminar in Indonesia. It discusses factors affecting cycle chemistry in high pressure boilers like smaller density differences and higher volatility at higher pressures. It then summarizes the phosphate continuum treatment program, which aims to prevent corrosion and deposition while producing pure steam. This involves maintaining tight pH control between 9.0-9.7 using sodium phosphate and sodium hydroxide. The document also outlines action levels for how long water chemistry can be outside normal specifications before requiring action.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    620 views46 pages

    C. Boiler Internal Cycle Chemistry & Control

    Uploaded by

    Rajendran Srn
    This document provides an overview of boiler internal cycle chemistry for a customer seminar in Indonesia. It discusses factors affecting cycle chemistry in high pressure boilers like smaller density differences and higher volatility at higher pressures. It then summarizes the phosphate continuum treatment program, which aims to prevent corrosion and deposition while producing pure steam. This involves maintaining tight pH control between 9.0-9.7 using sodium phosphate and sodium hydroxide. The document also outlines action levels for how long water chemistry can be outside normal specifications before requiring action.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 46

    1

    Boiler Internal Cycle Chemistry

    Indonesia Customer Seminar


    June 13 & 14 2012
    Jakarta Indonesia

    Agenda

    Factors Affecting Cycle


    Chemistry

    HP Boiler Cycle Chemistry

    Continuum Treatment
    Program

    Action

    Boiler Lay Up

    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

    Factors Affecting Chemistry in HP Boiler


    Smaller

    density
    difference and greater
    volatility

    High

    Cycle of
    Concentration

    Concentrating

    Mechanisms

    #1 Boiler Pressure and Carry Over


    Higher pressure =
    greater volatility of
    dissolved solids

    CuO

    Fe3O4
    (NH4)2SO4

    SiO2

    Na3PO4

    NaOH
    NaCl

    NH4Cl

    Volatile

    Mechanical

    Higher pressure =
    smaller difference of
    liquid and vapor
    density

    #2 High Cycle of Concentration


    Make-up

    water cost for HP


    boiler is high

    Energy

    loss from blow down in


    HP boiler is also high

    HP

    boiler running with high


    cycle compare (50- >100 cycles
    or 2-1% BD)to save the cost
    from blow down and make-up

    #2 High Cycle of Concentration


    Higher

    solids accumulation in
    the boiler higher potential
    for deposition problem

    Longer

    holding time

    Limiting effectiveness of chemical


    dispersant that commonly use to
    minimize deposition

    Iron Transport and Boiler Deposition


    The majority of iron entering the boiler remains in
    the boiler (even when dispersants are used)
    Cycle

    % Fe Transport
    (with dispersant)

    25-50

    20-30

    75-100

    Pressure, Temperature and Deposits


    Deposit

    will retard the heat


    transfer and increase the tube
    metal temperature

    High

    tube metal temperature in


    HP boiler makes its tolerance
    for water deposit is reduce

    #3 Concentrating Mechanisms
    The concentration of TDS
    in the film is higher than
    the bulk
    The higher the
    temperature difference, the
    greater TDS concentration
    in film (tube surfaces)
    High concentration of
    agressive ions could lead
    to localized corrosion

    #3 Concentrating Mechanisms
    Concentrating mechanisms
    lead to localized corrosions
    type that only found in HP
    Boiler
    Critical Factors: DNB,
    Deposition & Evaporation in
    water line
    Deposit will enhance
    concentrating mechanisms and
    increase potential for under
    deposit corrosion

    Boiler Tube Failures !


    300 MW Unit, Rp 656 / kWH

    Chemical Cleaning Guide Line

    Objectives
    HP Boiler Internal Cycle Chemistry
    Prevent

    Internal

    Corrosion
    Prevent

    Deposition

    Promote

    Production of

    Pure Steam

    15

    Boiler Internal Treatment Chemistry


    Achieinge non-corrosive
    boiler water pH levels

    Providing adequate
    buffer to deal with BFW
    contamination
    Providing minimum
    solids contribution to the
    boiler water

    Why pH Control is Important ?

    17

    Caustic Corrosion
    Causes:

    Deposition
    Free NaOH > 1 ppm
    - Na contamination
    - Caustic overfeed

    Solution

    Minimize NaOH
    concentration
    Na:PO4 = 2.3-2.6
    (Congruent PO4)

    18

    Acid Phosphate Corrosion


    Hideout

    Causes

    Deposition
    Phosphate Hide Out
    Control Na:PO4 < 3:1
    Solution

    Control PO4 residual at


    lower range
    Control Na:PO4 > 3:1
    Equilibrium PO4 (EPT)

    Load
    PO4
    pH

    Hideout Return

    19

    Hydrogen Damage
    Causes:

    Deposition
    Acidic condition
    - Condenser in-leakage
    - Pretreatment upsets
    - Un-proper cleaning

    Inadequate buffer
    Solution

    Better BFW quality


    Control Na:PO4 3:1 to 1 ppm NaOH
    Continuum PO4

    20

    Continuum
    EPRI New Cycle Chemistry Guide Line 2004

    Solid
    Treatment

    All Volatile
    Treatment

    Phosphate Continuum
    (PC)

    All Volatile (AVT)


    - Oxidizing
    - Reducing

    Caustic Treatment (CT)

    Oxygenated Treatment
    (OT)

    Phosphate Continuum (PC)


    Control
    TSP
    Tight

    at Na:PO4 = 3: 0 to 1 ppm NaOH

    and NaOH only no Phosphate with ratio < 3: 1


    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

    Phosphate Continuum Control Chart


    Phosphate Continuum Control Chart
    10.2

    TSP + 2 PPM NaOH


    Na/PO4 = 3.4

    Na/PO4 = 4.0

    TSP + 1 PPM NaOH


    Na/PO4 = 3.0

    10.0

    Na/PO4 = 2.8

    pH at 25 deg C

    9.8

    Na/PO4 = 2.6

    9.6

    PC

    9.4

    Note:
    Minimum PO4
    > 0.2 mg/L

    NaOH
    TSP

    9.2
    9.0
    PC (L)

    PC (H)

    8.8

    BD
    8.6
    0

    mg/L PO4

    10

    23

    Phosphate Continuum Control Chart

    PC(L)

    PC(H)

    CC BFW
    Phosphate
    pH

    : < 0.15 mS/cm


    : 0.3 3 ppm
    : 9.0 9.7

    CC BFW
    Phosphate
    pH

    : < 0.20 mS/cm


    : 3 10 ppm
    : 9.5 10.1

    Phosphate Continuum Product Options


    Phosphate Continuum Control Chart
    10.2

    TSP + 2 PPM NaOH


    Na/PO4 = 4.0

    10.0

    Na/PO4 = 3.4

    TSP + 1 PPM NaOH

    Na:PO4 = 3 :1

    Na/PO4 = 3.0
    Na/PO4 = 2.8

    Na:PO4 = 3.4 :1

    pH at 25 deg C

    9.8
    9.6

    Na/PO4 = 2.6

    PC

    Na:PO4 = 4:1

    9.4

    Note:
    Minimum PO4
    > 0.2 mg/L

    9.2
    9.0
    PC (L)

    PC (H)

    8.8
    8.6
    0

    mg/L PO4

    10

    Chemical Product Options

    Dry TSP (Nalco 444) plus Caustic

    Liquid TSP (BT 3000) plus dilute


    Caustic

    Blended Na:PO4 ratio products


    Nalco BT-3400 (3.4:1)
    Nalco BT-4000 (4.0:1)

    Caustic Treatment

    Candidates are boilers with severe phosphate hideout, condenser


    leaks, and saline cooling water.
    Would not be able to use AVT under these conditions.

    Maintain to EPRI specifications


    Cl- allowed varies by pressure (0.3 ppm @ 2500 psi)
    NaOH = 2.5 x Cl-

    SO4 < 2 x Cl

    Provides more buffering capacity for SO4 or Cl contaminant ingress


    than PC(L), less than PC(H).

    Boiler Chemistry Guidelines


    EPRI Guideline
    Parameter

    Units
    psi
    MPa

    Na
    PO4
    pH
    Cl
    SO4
    SiO2
    Conductivity
    Cation Cond

    mg/L
    mg/L

    Na
    PO4
    pH
    Cl
    SO4
    SiO2
    Conductivity
    Cation Cond

    mg/L
    mg/L

    Na
    NaOH
    pH
    Cl
    SO4
    SiO2
    Conductivity
    Cation Cond

    mg/L
    mg/L

    mg/L
    mg/L
    mg/L
    uS/cm
    uS/cm

    mg/L
    mg/L
    mg/L
    uS/cm
    uS/cm

    mg/L
    mg/L
    mg/L
    uS/cm
    uS/cm

    900
    6.2

    1500
    10.3

    VGB Std

    Drum Pressure
    1900
    2300
    2700
    13.1
    15.8
    18.6

    3.50
    5.00
    9.68
    1.70
    3.40
    2.80
    40
    75

    Phosphate Continuum - High


    2.70
    2.10
    1.60
    1.30
    3.50
    2.90
    2.30
    1.70
    9.53
    9.45
    9.35
    9.23
    1.20
    0.90
    0.70
    0.52
    2.40
    1.80
    1.40
    1.10
    0.90
    0.45
    0.25
    0.12
    28
    21
    17
    14
    48
    37
    28
    22

    2.30
    3.00
    9.52
    0.90
    1.80
    2.80
    24
    38

    Phosphate Continuum - Low


    1.80
    1.50
    1.20
    0.95
    2.40
    2.00
    1.60
    1.20
    9.38
    9.30
    9.20
    9.09
    0.45
    0.30
    0.19
    0.12
    0.90
    0.60
    0.37
    0.24
    0.90
    0.45
    0.25
    0.12
    15
    12
    9
    7
    25
    17
    12
    8

    2.20
    2.60
    9.80
    0.90
    1.80
    2.80
    27
    27

    Caustic Treatment
    1.60
    1.20
    0.90
    1.80
    1.40
    1.10
    9.65
    9.55
    9.45
    0.58
    0.44
    0.34
    1.20
    0.90
    0.68
    0.90
    0.45
    0.25
    18
    13
    10
    18
    13
    10

    0.70
    0.90
    9.35
    0.27
    0.55
    0.12
    8
    8

    < 136 bar> 136 bar


    < 13.6 > 13.6

    <6
    9.8 - 10.2
    pressure
    < 50

    <3
    9.3 - 9.7
    pressure
    < 50

    9.3 - 9.7
    pressure
    < 50

    All Volatile Treatment


    Only

    use volatile chemicals. No solid chemicals.

    Excellent

    program:

    For systems with condensate polishers and/or tight condensers


    For once through boilers
    Default

    program during steam blows and commissioning

    Requires

    very high purity feedwater at all times!

    < 0.2 uS/cm Cation Conductivity


    Dissolved O2 at CPD < 10 ppb

    AVT Feed Water Purity is Essential


    Boiler Water pH @Temperature with Contaminants

    Source: Albert Busik, Drum Boiler on All Volatile Treatment - The pH Pitfall, Power Plant Chemistry, 2004

    AVT Feed Water Purity is Essential


    Boiler Water pH (9.5) @Temperature with Chloride 10-50 ppb

    Source: Albert Busik, Drum Boiler on All Volatile Treatment - The pH Pitfall, Power Plant Chemistry, 2004

    31

    All Volatile Treatment


    All Volatile Reducing
    (AVT-R)

    All Volatile Oxidizing


    (AVT-O)

    Mixed metallurgy system


    Reducing agent (O2
    scavenger) + alkalizing
    agent
    ORP should be in the
    range: - 300 to -350 mV
    Can be used in all steel
    system with high O2 or
    cycling operation

    All-steel systems
    Once Through Boiler
    Cant be used in mixed
    metallurgy system
    No O2 scavenger feed
    Promotes formation of
    mixed of iron oxide layer
    ORP will be around 0 mV
    and could be positive

    Oxygenated Treatment (OT)


    Most

    preferred program
    for Once Through Boiler

    All

    steel metallurgy

    Very

    high purity boiler

    BFW
    CC < 0.15 mS/cm
    DO @CPD < 10 ppb
    Full flow polisher is a must
    No

    oxygen scavengers

    Disadvantages of OT
    Very

    high purity of
    BFW is required

    Upset

    of cation
    conductivity will lead
    to serious corrosion
    problem

    Source:, EPRI, Cycle Chemistry Guidelines for


    Fossil Plants: Oxygenated Treatment, 1994

    Continuum Program Selection

    Continuum: Feed Water Quality


    Feedwater and Steam Quality Limits
    4

    0.4

    3.5

    0.35

    0.3
    0.25

    0.2

    1.5

    0.15

    0.1

    0.5

    0.05

    0
    OT

    AVT

    PC(L)
    Na, Cl, SO4

    PC(H)
    Cat Cond

    CT

    uS/cm

    ppb

    2.5

    Continuum: Boiler Water Quality


    28

    1200

    24

    1000

    20

    800

    16

    600

    12

    400

    200

    ppb

    1400

    OT

    AVT

    PC(L)
    Cl ppb

    SO4 ppb

    PC(H)
    Cat Cond uS/cm

    CT

    uS/cm

    Boiler Water Quality Limits @ 2500 psi

    Action Levels
    EPRI

    developed Action Levels to specify how long and how


    far chemistry could be safely out of the normal control
    specification.
    Action Level 1:

    <1 week < 2x Normal

    Action Level 2:

    <24 Hr

    < 4x Normal

    Action Level 3:

    <4 Hr

    > 4x Normal

    Immediate Shut Down:


    - > 4 Hr at Action Level 3
    - < 8.0 Boiler Water pH

    Action Levels: PC Program <100 Bar


    Drum
    Normal
    Level 1
    Level 2
    Level 3
    Parameter
    Min
    Max
    Min
    Max
    Min
    Max
    Min
    Max
    pH
    Consistent with selected PC program
    S. Cond (uS/cm)
    28
    > 28 < 56 > 56 < 112 > 112
    Cat. Cond (uS/cm)
    48
    > 48 < 96 > 96 < 192 > 192
    Silica (mg/L)
    0.9
    > 0.9 < 1.8 > 1.8 < 3.6 > 3.6
    PO4 (mg/L)
    Consistent with selected PC program
    Na:PO4 Ratio
    Consistent with selected PC program
    Sodium (mg/L)
    2.7
    > 2.7 < 5.4 > 5.4 < 10.8 > 10.8
    Chloride (mg/L)
    1.2
    > 1.2 < 2.4 > 2.4 < 4.8 > 4.8
    Sulfate (mg/L)
    2.4
    > 2.4 < 4.8 > 4.8 < 9.6 > 9.6
    NaOH (mg/L)
    1.0
    > 1.0 < 2.0 > 2.0
    Note: Recommend immediate shutdown if pH < 8.0 or > 10.5

    Why Boiler Lay Up?


    Oxygen corrosion found in a boiler
    is generally occurred during the
    boiler in the idle condition and
    result of improper lay up procedure

    Factors that need to be


    considered:

    What is the duration of downtime


    Need to provide backup steam capacity ?
    Superheater? Drainable ?
    Can the boiler drained and left dry
    without affecting plant operation ?
    Can the boiler be sealed ? Do the valves
    hold ?
    39

    40

    Boiler Lay Up
    Wet Lay Up

    Dry Lay Up

    Idle < 3 weeks

    Best lay up method

    pH & O2 Scavenger at
    optimum level

    Idle > 3 weeks

    Pressurized blanket of inert


    gas to prevent air ingress
    Method:
    Short Term (Bottle Up) <72 hrs
    Long Term Wet Lay Up > 72 hrs

    Method
    Nitrogen Blanketing
    Dessicant
    Vapor Corrosion Inhibitor

    Boiler Lay-up Decision Tree

    41

    Short Term Wet Lay Up


    Water Chemistry Control Range
    Lay-up Method
    Time Period (After Shutdown)
    pH Target Range (All-steel)
    pH Target Range (Cu Alloys)
    Dissolved Oxygen (ug/L)
    Elimin-Ox Residual Target
    Range (All-Steel Systems, if
    Dissolved Oxygen can be
    controlled less than 100 ug/L)*
    Elimin-Ox Residual Target
    Range (All-Steel Systems if
    Dissolved Oxygen cannot be
    controlled)*

    Short-term Wet Lay-up


    < 72 Hours (as long as
    retains heat and pressure)
    9.5-9.6 (High in normal
    range)
    9.2-9.3 (High in normal
    range)
    <100
    75-150 ug/L (or high in
    normal range)
    Find and fix air leaks do
    not overfeed passivator for
    short term wet lay-up

    *Passivator target ranges approximately three times higher for copper alloys

    42

    Wet Lay Up with N2 Blanketing

    Wet Lay Up with Steam Sparging

    Long Term Wet Lay Up


    Water Chemistry Control Range
    Lay-up Method
    Time Period (After Shutdown)
    pH Target Range (All-steel)
    pH Target Range (Cu Alloys)
    Dissolved Oxygen (ug/L)
    Elimin-Ox Residual Target
    Range (All-Steel Systems, if
    Dissolved Oxygen can be
    controlled less than 100 ug/L)*
    Elimin-Ox Residual Target
    Range (All-Steel Systems if
    Dissolved Oxygen cannot be
    controlled)*

    Long-term Wet Lay-up


    > 72 Hours or when unit cools to
    ambient pressure and temperature
    10.0-10.5
    10.0-10.5
    <100
    75.0-100.0 mg/L

    1500-3000 ug/L

    *Passivator target ranges approximately three times higher for copper alloys

    45

    Thank You !

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