BOILER WATER TREATMENT TECHNOLOGY

DSS HEAD OFFICE - SERPONG 26 – 27 May 2008

PURPOSE

Discuss the BOILER WATER TREATMENT TECHNOLOGY in general Provide an understanding of the problems inherent with the BOILER SYSTEM operation. Provide an understanding of how these problems can be SOLVED

PROCESS

• PRESENTATION • DISCUSSION • QUESTION AND ANSWER

PAY OFF • More understanding about BOILER Treatment Program • Better BOILER Treatment control program implementation in the field to optimize the treatment results and deliver more benefits .

OVERVIEW • Pre-treatment • Boiler System • Feed Water System & Boiler Feed Water Treatment • Internal Boiler Treatment .

HIGH PRESSURE BOILER • A boiler which operates at a pressure above 700 psig (USA standard) .

OBJECTIVES HPB WATER TREATMENT • Increase Unit Reliability • Minimize contaminant • Decrease downtime • Increase safety • Decrease operational costs .

Type Of Boiler
1. Fire Tube Boiler

low pressure steam, small capacity

Type Of Boiler
2. Water Tube Boiler (Package)

Low & High Pressure Steam, Big Capacity

Type Of Boiler
3. Water Tube Boiler (Field Erected) High Pressure Steam (turbine Drive) Capacity: Big.

so the dissolved solids are left behind to accumulate in the remaining boiler water.Boiler Water Processes Steam Generation (Evaporation) . Note that only the pure water is converted to steam.where boiler water in the steam drum has sufficient energy to convert from liquid to gas (steam). .

Feedwater has TDS of 2.0 ppm Boiler water has TDS of 70 ppm Cycles of concentration = 70/2 = 35 .g.the ratio of TDS in the boiler water to TDS in feed water E..Boiler Water Processes Cycles of Concentration .

This is how we control cycles This lost water is replaced with an equal volume of fresh. Remember. high TDS  higher potential for scale and corrosion to occur. less concentrated feed water. .Deliberate ‘dumping’ of water in the steam drum to limit the total dissolved solids in the boiler water.Boiler Water Processes Blow Down .

Fe & Cu) Carry Over (all type of boiler) .Boiler Water Problem • • • • Corrosion (all type of boiler) Scale (LP Boiler with softener) Deposit (HP boiler.

Boiler Water Treatment Objective • Prevent Corrosion – BFW : Oxygen Corrosion – Boiler Corrosion : Caustic Corrosion – Steam and Condensate Corrosion : CO2 Corrosion • Prevent Deposit • Promote Production of Pure Steam .

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BOILER FEED WATER Source  Returned Condensate  Pretreated Make-up Water .

WATERSIDE PROBLEMS IN HIGH-PRESSURE BOILERS  CORROSION  DEPOSIT  CARRY OVER .

: A lkalinity. H P: H ighpressure . / CO 2 Am m onia D ep osits M etal oxides C arryover ‘D issolved’ so lids D eaerator F/W H P System b oiler X X X X X X S up erheater T urbine Steam -usin g eq uipm ents X X X C o nd en sate system X X X X X X X X X N ote : A lk. F/W: Feedw ater.WATERSIDE PROBLEMS IN HIGH-PRESSURE BOILERS M ajorprob lem s C orrosio n O xygen A lk.

steel is pure iron.CORROSION An electrochemical process where metals are reverted back to their natural (oxidised) state. Fe2 O3 (rust). the iron corrodes to form iron oxide. In the presence of air and water. Fe. For example. .

CORROSION Boiler corrosion usually classified as:     Oxygen corrosion Acid attack Caustic corrosion / embrittlement Erosion corrosion (flow accelerated corrosion) Can be either general or localised (pitting) attack .

Corrosion Mechanism .

Oxygen Corrosion Stopping Corrosion • Metallurgy Selection Oxygen Resistant Materials are expensive and poor heat conductor • Scavenge Oxygen Take away the active ingredient (both mechanical and chemical) • Passivate Metal This what the “Second generation” oxygen scavengers tend to do .

Oxygen Corrosion Source of Oxygen • Dissolved Oxygen  Feed Water  Return Condensate • Air in Leakage  Feed Water Pump  Condensate Pump .

Oxygen Corrosion Why Scavenge Oxygen • Remove remaining oxygen after mechanical deaeration • Prevent oxygen pitting in the preboiler system • O2 Attack results in pitting type corrosion • Rapid localized metal loss .

0 • Temperature – Higher temperatures reduce O2 solubility. but significantly increase corrosivity • • Dissolved oxygen concentration – Higher O2 concentrations increase corrosivity Fluid velocity – Enhances effect of other corrodents .Rate of Corrosion Corrosivity of Oxygen Influenced by : • pH – Corrosivity of oxygen decrease as pH increase – pH optimum > 9.

Prevent Corrosion • Metallurgy Selection – Oxygen resistant material are expensive and poor heat conductor • Corrosion Control by Remove All Oxygen : – Mechanically – Dearation – Chemically – Scavenge Oxgygen • Passivate Metal – This is what the “second generation” oxygen scavengers tend to do .

Corrosion of O2 Influenced by pH .

Corrosion Control System .

pH.1700C (power plants) – Deaerator Maintenance .10 ppb D. • Vacuum deaerators . spray nozzles and cracks inspection .spray. – Temperature in mechanical deaerators .Corrosion Control • Mechanical Dearation : – Purpose ? – Primary Means of O2 Removal – Types • Mechanical . Can remove up to 7 ppb oxygen. tray and spray / tray type.7 ppb D.104 .O. • Deaerating Condensers .O.

Corrosion Control • Chemical Oxygen Scavenger : – Purpose – Remove of trace amounts O2 remaining after dearation – Kind Of Oxygen Scavenger • First Generation : – SULPHITE. . – HIDRAZINE • Second Generation : – Eliminox. – Sugards.

DEAERATOR Remove Oxygen and Other Dissolved Gases from FeedFeed-water Why is Deaeration Necessary? • Oxygen Corrosive to Mild Steel • Cheaper to Remove Most of the Oxygen with Steam than to Remove Chemically .

Check The Steam Temperature & Flow Rate Storage 5. Check Temperature and Pressure Gauges of the DEAERATOR DOME & STORAGE SECTION Dome 2.DEAERATOR Evaluate ON-LINE performance: 1. Check The Feed Water Temperature & Flow Rates against Design Specifications 4. Check to See That the DEAERATOR is Venting Steam 3. Check CheckOxygen OxygenLevels Levelsin inthe the Deaerated DeaeratedWater Water . 5.

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Product Selection Considerations • • Regulatory Issues Solid Contributions : – Cycles – Attemperation • • • • Pressure/temperature use Desired attributes :Scavenger vs passivator Handling Costs .

Effective passivation of all system metals – Carbon steel – Stainless steel – Copper alloys (all) .Chemical Oxygen Scavenging Requirements  Oxygen Scavenging .Chemical reaction with trace quantities of dissolved oxygen  Passivation .

What is PASSIVATION ? • Formation of a very dense. • Under reducing conditions the preferred iron oxide . protective film at the metal surface which inhibits further corrosion of the base metal.Magnetite (Fe3O4) in carbon steel colour changes from red to grey/black • Cuprous oxide Cu2O in copper surfaces. Colour changes from black to red • Lower rate of metal loss after passivation • Lower corrosion rate during short upset conditions .

Oxygen Scavengers Commonly Used • • • • • • Sulfite Hydrazine Hydroquinone DEHA (Diethyhydroxylamine) MEKO (Methylethylketoxime) Carbohydrazide • Erythorbic acid .

Hydrazine Hydrazine Reaction N2H4 + O2 2 H2 O + N2 3N2H4 + heat ------> 4NH3 + N2 (At temperature > 200oC) Advantages • • • • All volatile No effect on cation conductivity No CO2 contribution Does not add solids Disadvantages • • • • Suspected carcinogen Requirement reportable spill quantity = 2.2 lb (1 kg) Flammable liquid Exposure to hydrazines may cause harmful health effects .

then to NH3 in boiler • THE MOST SIMILAR CHEMISTRY as Hydrazine alternative . non-carcinogenic – No reportable spill quantity – Not a hazardous waste • >20 years of use in high pressure boilers • Industry acceptance • Outperforms Hydrazine – Better passivation at lower temps – Faster O2 scavenger at lower temps • Performance – better passivator – 50-85% reduction in Fe & Cu transport • All volatile and Non solid contributions • Excess breaks down to Hydrazine.ELIMINOXTM • Carbohydrazide = (N2H3)2CO • Safe.

MECHANISM REACTION of ELIMIN-OX .

029 ppm) CO2& NO IMPACT to STEAM & CONDENSATE corrosivity .Reaction N-1250 (Eliminox Reaction) O NH2NH2 -NH NH-C-NH NH-NH2 Direct < 150oC + 2O2 2N2 + 3H2 O + CO2 ** Indirect + 2O2 + H2 O < 150oC 2N2 + 4H2 O 2N2 H4 + CO2 ** >205o C 2NH3 + N2 + H2 ** 1 ppm Elimin-Ox contribute 29 ppb (or 0.

Comparison With Hydrazine N-1250 REACTION RATE vs HYDRAZINE • ELIMIN-OX reaction rate 500 FASTER than HYDRAZINE ELIMIN-OX reacts STOICHIOMETRICALLY with O2 at all temperature • .

e.Passivation N-1250 as Passivator • Continuously formation of insoluble. if no contaminants are present • Reaction is very slow below 212oF • Reaction becomes fast only above 400oF • Natural passivation process can be accelerated by N-1250 – – – IronIII hydroxide/oxide hydrate formation by oxygen followed by reduction to magnetite by scavenger Metal oxidation by scavenger Activation of oxygen as passivating agent by scavenger . i. magnetite • Iron will self passivate in water. nonporous material on metal surface.

Passivation Reaction 12 Fe2 O3 + (N2 H3)2 CO 8CuO + (N2 H3)2CO 8Fe3 O4 + 3H2 O + 2N2 + CO2 4Cu2 O + 3H2 O + 2N2 + CO2 .

Passivation Passivation Better than Blank at High Temperatures Increasing Passivation 200 Blank 250 300 Temperature ( o F) Carbohydrazide 350 Erythorbate Hydrazine .

Passivation PASSIVATION PERFORMANCE • ELIMIN-OX (CHZ) has EXCELLENT PASSIVATION performance at all Temp. section). (starting from LOW to HIGH temp. While HYDRAZINE has GOOD PASSIVATION Performance at HIGH temp. section only 50-85% reduction in Fe & Cu transport • • .

9 .3 65. nitrogen. hydroxylamine.5 Reaction and/or Breakdown Products Nitrogen. ammonia. light alcohols. ammonia.2 40. ketones. carbon dioxide 53. water.) 0 13.Reaction and/or Breakdown Products Chemical/Formula Hydrazine N2H4 Carbohydrazide (N2H3)2CO Hydroquinone C6H4(OH)2 Diethylhydroxylamine (CH3CH2)2 NOH Methylethylketoxime (CH3)(CH3CH2)C=NOH Erythorbic Acid C6H8O6 % C (wt. carbon dioxide Acetaldehyde. nitrous oxide.9 55. nitrogen. nitrate. dialkylamines. carbon dioxide Dihydroascorbic acid. carbon dioxide Benzoquinone. nitrite Methylethylketone. ammonia Hydrazine. acetic acid. ammonia. water. salts of lactic and glycolic acid. low molecular weight species.

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causing tube overheating • Under-deposit Corrosion – Caused by high localized concentration of corrosive molecules .Scale Problems • Loss of Boiler Efficiency – Scale reduces heat transfer • Boiler Tube Failure – Scale elevates tube temperature.

Effect of Scale on Tube Temperature .

Under-Deposit Corrosion Magnetite NaOH Steam Out NaOH NaOH NaOH Water In Fe3O4 porous deposit NaOH .

Types of Caustic Damage in Boilers There are two forms of damage caused by caustic soda to high pressure boilers. namely:   Caustic corrosion Caustic embrittlement .

Caustic Corrosion      Usually found only in high pressure boilers Problem usually due to deposits Localized in boiler Also called crater attack or caustic gouging No embrittlement of metal .

Requirements for Caustic Corrosion Two conditions are necessary for caustic corrosion to occur:  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        Porous metal oxide deposits Metal oxide deposits Operation above rated capacity Excessive rate of load increase Excessive localized heat input Localized pressure differentials Restrictions in generating tube(s) .

     Coordinated phosphate Congruent sodium phosphate Phosphate-low hydroxide (tri-ad) Equilibrium phosphate control All-volatile treatment .Prevention of Caustic Corrosion Prevention of caustic corrosion is achieved by minimizing or eliminating the presence of ‘free’ caustic soda in the boiler water.

Coordinated Phosphate  Control of pH comes from hydrolysis of trisodium phosphate in water Na3PO4 + H2O -> Na2 HPO4 + NaOH   Molar ratio of sodium : phosphate is 3 : 1 in water Feedwater contamination usually dictates causticconsuming chemicals. such as disodium and trisodium phosphate Does not ensure absence of caustic under concentrating conditions  .

Coordinated Phosphate Advantages • Can be used in boilers up to 2400 psig • FDA/CFIA Approved .

Coordinated Phosphate Disadvantages • Does Not Prevent Mineral Scale • Does Not Prevent Iron Deposition • Requires Auxiliary Polymer • Hardness upsets can cause acidic conditions (corrosion) • Requires Frequent Testing and Careful Control .

Congruent Phosphate  This program was developed to prevent free caustic in boiler water during concentrating conditions At sodium:phosphate ratio of 2.3 .85 in boiler water. precipitated solids have same concentration Safe range is between ratio 2.2.6 Control is based on pH and PO4 values    .

Na : PO4 molar ratio : 2.85 => the Na : PO4 molar ratio is identical .Types of Internal Treatment Coordinated Phosphate •CONGRUENT SODIUM PHOSPHATE PROGRAM ( Na : PO4 molar ratio = 2.0 ratio ) •With a soln. with a Na : PO4 molar ratio > 2.85 => Dangerous free caustic region ( > 3. sodium phosphate soln.6 : 1 ) •TO RESPOND THE SOLUBILITY DIFFERENCES OF CONCENTRATED SODIUM PHOSPHATE & CAUSTIC •EXPERIMENT RESULTS : At high temp.

6 CONGRUENT CONTROL PROGRAM : Operates between ‘safe’ Na : PO4 molar ratio : 2.3 .Properly blended by Nalco 2. PREVENT CAUSTIC CORROSION 4. EASY / SIMPLE .. ABILITY TO BUFFER HYDRATE ALK.6 ADVANTAGES : 1. PREVENT TURBINE DEPOSIT 5.2.Types of Internal Treatment Coordinated Phosphate EXPERIMENT RESULTS : At higher temp. . NO FREE CAUSTIC 3. the congruent point at Na : PO4 = 2.

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