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BASIC WATER CHEMISTRY BOILER DESCRIPTION OXYGEN PITTING & CONTROL CONDENSATE TREATMENT INTERNAL TREATMENT, COORDINATED pH/PO4 STEAM PURITY BOILER STORAGE DISCUSSION, Q&A
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The Basics
Hydrologic Cycle Properties of Water pH and Alkalinity Langelier Saturation Index Analytical Expressions Water Analysis/Deposit Analysis Corrosion and Deposition & Monitoring Chemical Feed
Properties of Water
Density - 1 kg/l @ 4 oC ; 0.998 kg/l @ ambient temperature and varies inversely with temperature Boiling point = 100 oC and freezing point @ 0 oC Viscosity ~ 1 cps at ambient temperature and varies inversely with temperature Specific heat - 1 BTU/lb-deg F or 1 kcal/kg-deg C or 4.2 kJ/kgdeg C Universal solvent - dissolves most substances to some extent
3 Categories
Cations - Ions that carry net positive charges e.g. Calcium (Ca2+), Magnesium (Mg2+), Sodium (Na+), Iron (Fe2+), Aluminium (Al3+) Anions - Ions that carry net negative charges e.g. Bicarbonates (HCO3-), Carbonates (CO32-), Sulfate (SO42-), Chlorides (Cl-), Oxides (O2-), Hydroxides (OH-)
Water Impurities
Impurity
Suspended Solids Silt, Iron, Microbiogical Dissolved Solids Minerals, Organics Dissolved Gases O2, CO2, NH3
Concern
Fouling Erosion Underdeposit corrosion Scaling Corrosion Pitting General Corrosion Corrosion products
Removal
Clarification Filtration Ion Exchange Reverse Osmosis Evaporation Deaeration Steam Stripping
Dissolved Solids
Cations
Temporary Hardness Permanent Hardness
Anions
HCO3possibly OH- & CO3-ClF-
Ca++
Mg++
Total Alkalinity
Na+ K+ NH4+
Mineral Acidity
Cation
Calcium
Anion
Bicarbonate Sulfate Bicarbonate Sulfate Bicarbonate Sulfate Chloride Oxide Bicarbonate Hydroxide Sulfate
Chemical Name
Ca(HCO3)2 CaSO4 Mg(HCO3)2 MgSO4 NaHCO3 Na2SO4 NaCl SiO2 Fe(HCO3)2 Fe(OH)3 FeSO4
Magnesium
Sodium
Silica Iron
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Temperature - Most salts increases except for Ca and Mg Salts with increasing temperature Alkalinity - Most salt solubility increases with decreasing alkalinity with the exception of Silica pH - most salts solubility increases as the pH drops Oxidation state - Fe and Mn salt solubility increases with decreasing oxidation state
Turbidity - suspended solids silt, organic matters, precipitated salts Color - suspended solids and dissolved solids Dissolved gases e.g. CO2, O2, NH3, H2S Organics - humus, vegetation, microorganisms
Parameter
Conductivity S/cm Alkalinity P as CaCO3, ppm Alkalinity M as CaCO3, ppm Sulfate as SO4, ppm Chloride as Cl, ppm Hardness, Total, as CaCO3, ppm Calcium Hardness, as CaCO3, ppm Magnesium Hardness, as CaCO3 ppm Copper, Total as Cu, ppm Iron, Total as Fe, ppm Sodium, as Na, ppm Phosphate, Total, as PO4, ppm Silica (reactive), as SiO2, ppm Turbidity, NTU TSS, ppm Color, Hazen RIL-Hazira/BWT-Technical Training TOC, as C, ppm
GEWPT- Confidential Material
pH
Special Ions
pH
pH
Hydrogen Ion Concentration Logarithmic Scale pH = -log [H+] Unit change in log scale
Alkalinity Relationships
M-Alkalinity = Total Titration to pH = 4.3 Sum of: HCO3- + CO3- + OHP-Alkalinity = OH- + 1/2 CO3 Titration to pH 8.3 OH-Alkalinity = 2P - M or titration Neutral barium chloride precipitates CO3-
Conductivity
Types of Solubility
Analytical Expressions
Concentration
units of solute per unit of solvent: PPM (parts per million)
parts of solute per million parts of solvent
Analytical Expressions
Mg as CaCO3
Analytical Expressions
Different Conventions We use ppm as CaCO3 ppm as substance factors Ca 50 2.5 Mg 20 4.1
ppm as CaCO3
125 82
FIRETUBE BOILERS
ADVANTAGES
High load swing capacity Ease of repair Low space requirement Self contained package Relatively low cost Ease of installation
DISADVANTAGES
Low pressure Capacity limit Usually no superheater Usually no economizer Usually low efficiency One fuel at a time FOUR-PASS FIRETUBE BOILER
WATERTUBE BOILERS
Economizer Steam drum Mud Drum Headers Boiler Bank Downcomers - Risers Waterwalls Screen tubes Arches Floor tubes Roof tubes Superheater Air Heater
WATERTUBE BOILERS
RISERS DOWNCOMERS
STEAM DRUM
AIR HEATER
MUD DRUM
Coal
140-150 C
BOILER DESIGN
Fire Tube
CBD
Water
Risers
Flue Gases
Flue Gases
Mud Drum
Downcomers IBD
WATERTUBE BOILERS
Low to super critical pressure Virtually unlimited capacity Typically high efficiency Superheaters Economizers Multiple fuels Drum or once-through Package or field-erected
ADVANTAGES
DISADVANTAGES
High Cost Require Large Space Usually require higher quality feedwater Sensitive to low load operation
Risers
W BF
Downcomers
Burner
Steam Drum
Downcomers
Infrastructure Power Utility Boiler Simplified Flow Diagram Water & Process Technologies
Condenser IP Turbine B&W Boiler BD Cold Reheat LP Heaters Cond Polisher LP Turbine
MB MU
DOWNTIME CORROSION
POOR BOILER FEEDWATER QUALITY CONDENSATE CONTAMINATION POOR EXTERNAL TREATMENT INADEQUATE BLOWDOWN CONTROL DEPOSITION CONCENTRATING MECHANISM STRESSED AREA
BOILER CORROSION
Boiler Calculations
FeedWater (kg/hr) = Steam Generation (kg/hr) 1 (%blowdown) 100 FW= STM ( C ) C-1
Check via Chlorides, Silica Do not use compounds that routinely precipitate (phosphate, hardness) or that are part of treatment (sulfite/sulfate)
Feedwater = Steam + Blowdown BD = FW ST = (105.3 100) MM ppy = 5.3 MM ppy Feedwater = Make-up + Condensate
Oxygen Control
O2 Fe(OH)3 Fe2+
OHWATER
O2
ELECTRON FLOW
ANODE
ANODE REACTION Fe. = Fe++ 2eMECHANISM
CATHODE
CATHODE REACTION 1/2 O2 + H2O + 2e- = 20H-
Iron Is Oxidized on the Surface (Anode) - Metal Loss Oxygen Is Reduced (Cathode)
Oxygen Corrosion
Corrosion Rate Doubles With Every 10 C Increase in Water Temperature Metal Loss is low Localized attack Pit Formation Rapid Failure
Oxygen Guidelines
15 - 40
Sodium Bisulfite Sodium Sulfite Non-Solids Hydrazine Hydroquinone Diethylhydroxlamine (DEHA) CARBOHYDRAZIDE ASCORBIC ACID
ATTEMPERATION / DESUPERHEATING: NO
Hydrazine
Reaction: N2H4 + O2 N2 + 2H2O Decomposition Reaction: 2N2H4 + HEAT + 2H2O 4NH3 + O2 Feedrates: 3 x (ppm O2 + Residual) Control Limits: 0.1 ppm Residual N2H4 at Economizer Inlet Attemperation / Desuperheating: Yes
Hydrazine
Advantages: Doesnt contribute to TDS True residual test Disadvantages: Poor reactivity with low temperature Expensive compared to Sulfite Suspect carcinogen Requires special handling / feed equipment Decomposes to NH3, which can lead to copper corrosion
Organic O2 Scavengers
Pressure > 900 psig (60 bar) BFW used for superheat attemperation Condensing turbine present High-Purity Makeup (Demin./RO) Coordinated PO4 / pH control
OH
H2O + C6H4O2
CONTROL LIMITS:
DISSOLVED OXYGEN TEST IRON REDUCTION TEST
OH
HYDROQUINONE
ADVANTAGES
DOES NOT CONTRIBUTE TO TDS FASTEST ORGANIC OXYGEN SCAVENGER REQUIRES NO SPECIAL HANDLING EXCELLENT FOR WET LAY-UP AVOIDS SULFUR CATALYST POISON NOT A LISTED CARCINOGENIC
OH
+ O2 =
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OH
Carbohydrazide
REACTION:
N4H6CO + O2
-N
H3 2
2 N2
+ 3H2O + CO2
DECOMPOSITION REACTION:
N4H6CO + H2O + HEAT 2N2H4 + HEAT + 2H2O 2N2H4 + CO2 4NH3 + O2
Carbohydrazide
Advantages
Low/no cation conductivity contribution Does not form LMW organic acids CO2 contribute to non degassed cationic conductivity Well-accepted in Industry Much safer than hydrazine
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MINIMUM TEMP* 80 OF (27 C) 190 OF (88 C) 80 OF (27 C) >200 OF (> 93 C) 180 OF (82 C) >200 oF(> 93 C)
Monitoring
1 ECONOMIZER 2
Ideal Point
1) 2)
Primary sample point for oxygen testing Sample point necessary for deaerator studies and for troubleshooting oxygen intrusion through the pump
MONITORING
Condensate Treatment
In The Condensate: Carbon Dioxide
CO2 + H2O H2CO3 H2CO3 H+ + HCO3-
pH DECREASES
2HCO3CO3=
FEEDWATER HCO3CO3=
OH-
BLOWDOWN
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7
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8 pH
10
NEUTRALIZING AMINES
10
CONDENSATE, pH
BASICITY
Neutralizing Basicity Constant Morpholine Ammonia Ethanolamine DEAE MOPA Cyclohexylamine 2 18 32 66 126 440
DISTRIBUTION RATIOS
DISTRIBUTION RATIOS
AMINE AMMONIA CYCLOHEXYLAMINE DEAE MOPA MORPHOLINE ETHANOLAMINE DIAMINE CONTAMINANTS CO2
DR 200 PSIG 1000 PSIG 7.1 3.6 16.0 9.3 4.5 3.4 2.4 2.5 1.6 1.0 0.15 0.29 1.9 2.7 500 100
Deposit Formation
Deposition rate increases with heat flux (Btu/Ft2) Reduces Heat Transfer Increases tube wall temperature Induces corrosion Ultimately - Tube failure
Insulating Scale
Monitoring Tools 1. Boiler Feedwater/ Condensate Iron Monitoring 2. Turbidity Monitoring 3. Equipment Inspections
Hardness Salts Intermittent Contamination Condensate Hardness Contamination Poor NaZ Performance Chemical Underfeed Poor Blowdown Control Intermittent Contamination Condensate Corrosion
Iron
Poor Chemical Feed Control Condensate Hydrocarbon Contamination High Boiler Silica Poor Separation Equipment Performance Rapid Load Swings Hydrocarbon Contamination Poor Blowdown Control Hydrocarbon
Monitoring Tools 1. On-Line Total Analyzer 2. Boiler Feedwater Inspection 3. Equipment Inspections
Superheater/Turbine Fouling
Monitoring Tools 1. Steam Purity Monitoring 2. Routine Boiler Testing 3. On-Line Sodium Analyzer 4. Equipment Inspections 5. Data Tracking
Used Primarily in high pressure boilers to protect against caustic gouging Applicable for lower pressure boiler systems on demin quality makeup Sodium (caustic) is primary feedwater contaminant Iron may also be a problem polymers used for iron control
Under-Deposit Corrosion
8.5 pH
10 11 12 13 14
pH
RIL-Hazira/BWT-Technical Training GEWPT- Confidential Material
NaOH + Na2HPO4
Caustic Disodium Phosphate
Na3PO4 + H2O
Trisodium Phosphate Water
2Na2 HPO4 + 2NaOH Exact DSP Fed 6Na + 2PO4 Na:PO4 = 3:1
2Na3PO4 + 2H2O
Under-Deposit Neutralization
M A X IM U M B O U N D A R Y 3 .0 :1 M O L A R R A T IO
``F re e '' C a u s tic R e g io n 2 .8 :1 N a /P O 4
<900 psi
C o n tr o l A r e a
9 0 1 -1 5 0 0 p s i
`` C a p tiv e ''
A lk a lin ity R e g io n
pH AT 25C
9 .6 9 .4 9 .2 9 .0 8 .8 8 .6 8 .4 8 .2 1 .0 2 .6 :1 N a /P O 4
1 5 0 1 -2 0 0 0 p s i
C o n tr o l A r e a
C A U S T IC
C o n tr o l A r e a V e c to r 2 0 0 1 -2 5 0 0 p s i C O N T R O L B O U N D A R Y C o n tro l
C o n tr o l A r e a >2600 psi
2 .2 :1 N a /P O 4 M O L A R R A T IO
D ia g ra m
BLOW DOW N
CO NTRO L AR EA 2 5 0 1 -2 6 0 0 p s i 2 3 4 5 6 7 8 10 15 20 30
40
50
60
p p m O rth o p h o s p h a te , a s P O 4
Caustic-Phosphate Equilibrium
Caustic
Tri-sodium PO4
Reality Check
Your 90 bar boiler has a pH 9.5 and PO4 of 30 ppm. Boiler PO4 control range is 10 - 20 ppm How should we respond?
[A]
Reality Check
Your readings for this 100 bar boiler are pH 10.2 and PO4 of 6. PO4 control range is 4 - 8 ppm. What actions will put you back into control?
[A]
Acid PO4 corrosion potential exists when boiler water Na/PO4 ratio is less than 2.3
Sodium PO4 (Di or Mono) can react with Magnetite or Iron to form Maricite (NaFePO4) under high temperature (>300 C)
Steam Purity
Importance of Steam Purity
Protect Capital Investments, such as: Superheaters Turbines Steam lines and valves Maintain Production Prevent Process Contamination
Definitions
Steam Purity Solid, liquid or vaporous contamination in the steam Steam Quality A measure of the moisture in the steam
Turbine manufacturer (ppb levels) Boiler manufacturer (ppm levels) Industry professional organizations Operations
PARAMETER Cation Cond. uS/cm Sodium, ppb Chloride, ppb Silica, ppb Iron, ppb Copper, ppb Oxygen, ppb
24 HR. 1 10 A A A A A
10-30
30-100
Air In-Leakage
Water and Steam
Demineralizers
Condenser Leaks
Corrosion Products
Process Chemicals
Parameter
Na, SiO2, ppb ppb
GE <20 < 20
Westinghouse Mitsubishi < 10 < 20 < 20 <2 < 15 <2 < 0.2 < 10 < 15 <5
<0.2
< 0.2
< 0.3
Parameter Cation Cond. us/cm Na, ppb SiO 2, ppb Cl, ppb SO 4, ppb
2-week *
24-Hour *
0.5 - 1.0 20 - 35 40 - 80 30 - 50 30 - 50
ATTEMPERATION WATER
FEEDWATER
SODIUM
On Line Analyzer Isokinetic Sampling Bottle Study (Na free
bottles)
Saturated Steam
Boiler Storage
Most oxygen corrosion occurs or is initiated when boiler is off-line (wet storage) Key to Success - Alkaline & oxygen-free during wet storage
Boiler Storage
Dry Storage with a desiccant is recommended for long-term storage What constitutes long-term? Off-season storage Rule-of-thumb: Normally recommend dry storage if lay-up will be >1 month and boiler will not be needed on short notice
Boiler Storage
Wet storage is recommended when: Boiler is required for emergency stand-by or on short notice Capacity required to meet peak demand Unit will be out-of-service for < 1 month
Add chemicals to fill water as it is pumped into boiler Fire boiler moderately after chemical addition to circulate & distribute or utilize external circulation pump Always follow boiler manufacturers recommendations for firing the boiler Adjust pH/alkalinity with amine or caustic consistent with the lay-up chemical being used.
Weekly testing during wet storage Measure pH/Alkalinity Test dissolved oxygen and/or scavenger residual Maintain dissolved oxygen level below 10 ppb Supplement scavenger/amine as required Preventing oxygen ingress during storage: Connect surge tank (drum) filled with lay-up solution to upper vent Alternative - 5 psig (0.34 bar) nitrogen cap
Volatile Chemicals
Required when: Above 900 psig (60 bar) Non-drainable superheaters Turbines High-purity make-up Sulfite is NOT suitable
Volatile Chemicals
Acceptable water for preparation of highpressure boiler lay-up solutions: Good-quality demineralized H2O Good quality condensate (no solids) No softened-quality, RO or raw water with appreciable TDS Add chemicals to fill water as it is pumped into boiler
Hydroquinone Fastest reaction with oxygen at ambient temp Must use neutralizing amine with HQ Important - Amine MUST be compatible with HQ (or will develop sludge): Hydroxylamines Most volatile & compatible with amines
Hydrazine - 200 ppm as N2H4 Excellent passivator at > 200 ppm as N2H4, BUT: Not recommended - Safety hazard! Amine is not typically required Ascorbic acid - Not recommended: Poor thermal stability Acidic decomposition products Non-volatile
Volatile Chemicals
Special lay-up product - CorTrol OS7700 HQ plus special low-volatility amine package Avoids low pH excursions on re-start Feedrate: 2000 ppm product 4000 ppm in new systems (nonpassivated) Maintain pH above 10.5 throughout
Hot air/heat to remove all moisture Use desiccant (with color indicator) Silica gel Quick lime Activated alumina
CORTROL-5613-OXYGEN SCAVENGER FEED RATE 0.5-1.0 PPM RESIDUAL MONITORING. STEAMATE-NA8590 CONDENSATE TREATMENT LOW DR AMINE TRI SODIUM PHOSPHATE FOR pH/PO4 coordination AMMONIA FEED WATER & STEAM pH CONTROL
Thank You