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.

Boiler Water Processes

Steam Generation (Evaporation)

- where boiler water in the steam drum has sufficient
energy to convert from liquid to gas (steam).

Note that only the pure water is converted to steam, so the dissolved solids are left behind to accumulate in the remaining boiler water.

Boiler Water Processes

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

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

Boiler Water Problem

Corrosion (all type of boiler) Scale (LP Boiler with softener) Deposit (HP boiler, Fe & Cu) Carry Over (all type of 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

BOILER FEED WATER Source

Returned Condensate Pretreated Make-up Water

WATERSIDE PROBLEMS IN HIGH-PRESSURE BOILERS

CORROSION

DEPOSIT

CARRY OVER

WATERSIDE PROBLEMS IN HIGH-PRESSURE BOILERS

M ajorprob lem s C orrosio n O xygen A lk. / 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

N ote : A lk. : A lkalinity, F/W: Feedw ater, H P: H ighpressure

CORROSION
An electrochemical process where metals are reverted back to their natural (oxidised) state.

For example, steel is pure iron, Fe. In the presence of air and water, the iron corrodes to form iron oxide, Fe2 O3 (rust).

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

Rate of Corrosion
Corrosivity of Oxygen Influenced by :

pH
Corrosivity of oxygen decrease as pH increase pH optimum > 9.0

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

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

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

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

DEAERATOR
Evaluate ON-LINE performance:
1. Check Temperature and Pressure Gauges of the DEAERATOR DOME & STORAGE SECTION

Dome

2. Check to See That the DEAERATOR is Venting Steam 3. Check The Feed Water Temperature & Flow Rates against Design Specifications 4. Check The Steam Temperature & Flow Rate

Storage

5. 5. Check CheckOxygen OxygenLevels Levelsin inthe the Deaerated DeaeratedWater Water

Product Selection Considerations

Regulatory Issues Solid Contributions :
Cycles Attemperation

Pressure/temperature use Desired attributes :Scavenger vs passivator Handling Costs

Chemical Oxygen Scavenging Requirements

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

What is PASSIVATION ?
Formation of a very dense, protective film at the metal surface which inhibits further corrosion of the base metal. Under reducing conditions the preferred iron oxide - 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

ELIMINOXTM
Carbohydrazide = (N2H3)2CO Safe, 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, then to NH3 in boiler THE MOST SIMILAR CHEMISTRY as Hydrazine alternative

MECHANISM REACTION of ELIMIN-OX

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 0.029 ppm) CO2&

NO IMPACT to STEAM & CONDENSATE corrosivity

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

Passivation
N-1250 as Passivator
Continuously formation of insoluble, nonporous material on metal surface, i.e. magnetite Iron will self passivate in water, 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

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. (starting from LOW to HIGH temp. section). While HYDRAZINE has GOOD PASSIVATION Performance at HIGH temp. section only 50-85% reduction in Fe & Cu transport

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.)
0 13.3 65.5

Reaction and/or Breakdown Products

Nitrogen, water, ammonia Hydrazine, nitrogen, water, ammonia, carbon dioxide Benzoquinone, light alcohols, ketones, low molecular weight species, carbon dioxide Acetaldehyde, acetic acid, dialkylamines, ammonia, nitrate, nitrite Methylethylketone, hydroxylamine, nitrogen, nitrous oxide, ammonia, carbon dioxide Dihydroascorbic acid, salts of lactic and glycolic acid, carbon dioxide

53.9 55.2

40.9

Scale Problems
Loss of Boiler Efficiency
Scale reduces heat transfer

Boiler Tube Failure

Scale elevates tube temperature, causing tube overheating

Under-deposit Corrosion
Caused by high localized concentration of corrosive molecules

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)

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 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 -> 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 2.85 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

Types of Internal Treatment Coordinated Phosphate

CONGRUENT SODIUM PHOSPHATE PROGRAM ( Na : PO4 molar ratio = 2.6 : 1 ) TO RESPOND THE SOLUBILITY DIFFERENCES OF CONCENTRATED SODIUM PHOSPHATE & CAUSTIC EXPERIMENT RESULTS : At high temp. sodium phosphate soln. with a Na : PO4 molar ratio > 2.85 => Dangerous free caustic region ( > 3.0 ratio ) With a soln. Na : PO4 molar ratio : 2.85 => the Na : PO4 molar ratio is identical

Types of Internal Treatment Coordinated Phosphate

EXPERIMENT RESULTS : At higher temp., the congruent point at Na : PO4 = 2.6 CONGRUENT CONTROL PROGRAM : Operates between safe Na : PO4 molar ratio : 2.3 - 2.6 ADVANTAGES : 1. EASY / SIMPLE - Properly blended by Nalco 2. NO FREE CAUSTIC 3. PREVENT CAUSTIC CORROSION 4. PREVENT TURBINE DEPOSIT 5. ABILITY TO BUFFER HYDRATE ALK.