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Pre-Treatment
Boiler
Process
Process
Process Low pressure steam Blowdown flash tank Flash tank Condensate Receiver
Major Problems
Corrosion
Scale
Solubilities
Compound Calcium Bicarbonate Carbonate Sulfate Magnesium Bicarbonate Carbonate Sulfate Sodium Bicarbonate Carbonate Chloride Hydroxide Sulfate ppm as CaCO3 o o o o 32 F (0 C) 212 F (100 C) 1620 15 1290 decomposes 13 1250
decomposes 75 356,000
Silica
Selective silica carryover Cannot be controlled mechanically by steam separators Not usually a problem with boilers with less than 600 psig pressure
Silica is selectively dissolved into the steam Controlled by limiting the silica concentration in the boiler water Controlled by limiting boiler pressure Controlled by maintaining high pH
Hematite
Magnetite
Fe2O3
Fe3O4
Temp Drop Across Water Film = 76o F. Temp Drop Across Internal Scale = 362oF. Temp Drop Across Tube Wall = 66o F.
Max. Tube Temp (1004o F.) is above allowable Oxidation Temp limit of SA-210 Carbon Steel
Scale Problems
Boiler tube failure Caused by reduced heat transfer and tube overheating
Scale Prevention
Coagulation Treatments
Principles
Coagulation Treatments
Advantage
Disadvantages
Low cycles
Phosphate Residual
Chemistry
Phosphate Technology
Types of Phosphates
Ortho phosphates
Poly Phosphates
Phosphate Technology
Feedpoints
Poly phosphate
Feed to feedwater line
Phosphate Technology
Detailed Chemistry
(poly)
(ortho)
Phosphate Technology
Advantages
Well understood
Can be FDA and/or USDA approved Can handle feedwater hardness fluctuations
Phosphate Technology
Disadvantages
Produces precipitates in boiler water Excess alkalinity can produce corrosion May require more blowdown
Sludge Conditioning
Insoluble Calcium Phosphate and Magnesium Hydroxide solids formed (Sludge) Particulate Iron Oxide returned in condensate Solids settle on hot boiler surfaces Heat transfer impaired, tube failure risk
Phosphate-Polymer Programs
Affects Calcium & Magnesium precipitation Same precipitation chemistry as other phosphate programs but different dosage requirements for sludge conditioner & phosphate Provides cleaner boilers
Phosphate-Polymer Programs
Advantage
Can provide much cleaner boilers than other conventional Phosphate programs
Disadvantage
Chelants
Common Chelants
EDTA (Ethylene diamine tetracetic acid)
Has 6 metal complexing sites which include nitrogen and oxygen atoms NTA (Nitrilo triacetic acid)
Comparison of Chelants
NTA is more thermally stable 900 psig max. for NTA, 600 psig max. for EDTA
Application of Chelants
Must be fed continuously to feedwater using a stainless steel injection quill & piping Oxygen must be absent
Residual concentration must be kept below 10 ppm as CaCO3 in boiler water to minimize corrosion Accurate feed control is required
Chelant Advantages
No precipitates formed Heat transfer surfaces cleaner Less frequent acid cleaning Can sometimes reduce blowdown
Chelant Disadvantages
Cost more than phosphates Require stricter control of feedwater quality More difficult control test Excessive residuals are corrosive Competing ions can form deposits
All-polymer program, polymeric blend Contains no chelants or phosphates, does not require supplemental dispersants
Functions by solubilization for Calcium and Magnesium and by dispersancy for iron and other particulates
Non-aggressive to boiler metals
Feed to deaerator storage for boilers at < 600 psig and using softened water Use other feed points for high pressure boilers using high purity (e.g. demineralized) makeup
Feed program based on statistical upper control limit for hardness and iron, not average values
Under dosing (<20% of requirement) can produce Calcium Acrylate deposits in boiler
Non corrosive to boiler internals Offers clean boilers - enhanced heat transfer Transports 100% of hardness Non-volatile - safe for turbines Can test for boiler hardness Simple product test - easy to test for product Good passivating program
Limited to boiler pressures <1000 psig Requires low hardness feedwater Some formulations contribute ammonia to steam Cannot be used as a clean-up program
Boiler Corrosion
Types of Corrosion
Oxygen corrosion Alkalinity concentration Caustic corrosion Acid corrosion Chelant corrosion Erosion/Corrosion
Oxygen Corrosion
Can be found throughout the system Mechanism same as other oxygen corrosion cells
Oxygen concentration
Temperature
pH
Reduces general corrosion Forms protective barrier on metal Black magnetite film - Fe3O4 Difficult to quantify results
Caustic Corrosion
Localized in boiler
Also called crater attack or caustic gouging
No embrittlement of metal
The presence of a corrosive material in the boiler water (caustic soda) A mechanism for concentrating this material
Concentrating Mechanisms
The following conditions can result in dangerously high localized caustic soda concentrations
Coordinated phosphate Congruent sodium phosphate Phosphate-low hydroxide (tri-ad) Equilibrium phosphate control
All-volatile treatment
Coordinated Phosphate
Control of pH comes from hydrolysis of trisodium phosphate in water Na3PO4 + H2O -> Na2HPO4 + NaOH
Molar ratio of sodium : phosphate is 3 : 1 in water Feedwater contamination usually dictates caustic-consuming chemicals, such as disodium and trisodium phosphate Does not ensure absence of caustic under concentrating conditions
Congruent Control
This program was developed to prevent free caustic in boiler water during concentrating conditions At sodium:phosphate ratio of 2.85 in boiler water, precipitated solids have same concentration Safe range is between ratio 2.3 - 2.6 Control is based on pH and PO4 values
Tri-Ad Programs
Equilibrium Treatment
Coordinated and congruent treatments can be difficult to control Phosphate hideout interferes PO4 levels kept between 1 - 5 ppm Controlled by pH, OH and PO4 in boiler water
Phosphate Hideout
All-Volatile Treatment
Caustic Embrittlement
Three conditions must be present Concentrating mechanism present Metal under high stress Must contain silica
Inhibited by improved fabrication techniques and by organic and nitrate-based inhibitors
Feedwater acid contamination Surface condenser leaks Acid leaks from demineralizer Organic materials Chelant corrosion