Kraft Recovery Course

Recovery Boiler January

Water Treatment 2008

Presented By

Sheppard T. Powell
Associates, LLC

Baltimore Maryland
www.stpa.com

Presentation Format
6 Objectives Of Treatment Program
6 Steam/Water Cycle: Basic Components
6 Top Routine Chemistry Parameters
6 Summary

1
 Objectives Of Treatment Program

Component Deposit Corrosion

Condensate System -- Minor
Feedwater System -- Minor
Boiler Minor 0 or Minor
Superheaters 0 0
Turbines 0 0

Boiler Deposit Example

6 Thick Nose Tube Deposits of Copper and Copper

Oxides Over Mixed Iron Oxide, Hardness Phosphate
and Carbon

2
Boiler Blistering Example

Boiler Corrosion Example

6 Deposits After
Brushing

6 Under-Deposit
Corrosion

3
 Turbine Deposits Example

Superheater Corrosion Example

4
 Steam/Water Cycle Diagram
Sweetwater
Condenser
FW Out
FW In CCNa Mill Condensate(s) Condensate
Desup. CCNa S
Water Steam S Storage
S
TU SC
pH
S Boiler Steam (For Each)
SC S S Condensate
Vent SC S Filter/Polisher
S Na System
CC Blowdown/Makeup
Desuper- Deaerator Heat Exchanger
pH
heating And Storage
SC Water
Na S S
DO S
SiO2 Treated Makeup
Feedwater S Makeup S Storage
Heater(s) SC
Na SiO
Usually Operated As A Grab Sample Point
2

Questions

5
 Specific Conductivity
6 Total Conductive Solids (Salts, Acids, Alkalis)
6 High Levels Can Cause Foaming and/or Corrosion
6 Units: Usually S/cm
6 Micromho (mho/cm) = Microsiemen (S/cm)
6 Millimho (mmho/cm) = Millisiemen (mS/cm)
6 1 mS/cm = 1000 S/cm (Beware of auto-switching ranges
on meter!)

Specific Conductivity
Normal Values,
Sample Main Source
S/cm

Demineralized Water 0.05 5.0 NaOH Leakage

Condensate &
2.0 6.0 Amine Feed
Feedwater

Boiler Water 20 150 (a) 3 to 5 PO4

(a) Much Higher For Low Pressure Boilers On Softened Makeup

6

Specific Conductivit y, S/ cm
Example of Amine Blend Effect on Conductivity
12
Trial A - Change in SC
10 (33.9 - 35.7C)
Trial B - Change in SC
8 (34.0 - 36.3C)

0
0 1 2 3 4 5 6 7 8 9 10
Volume of Amine Blend, ppm

pH (Relative Acidity and Alkalinity)

6 5 4 3 2 2 3 4 5 6
10 10 10 10 10 10 1 1 10 10 10 10 10 10
Acid Units Base Units

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH Neutral pH

Demineralized
Water
Condensate/Feedwater
Vinegar Boiler Water
Lemon Juice Household Ammonia
5% Sulfuric Acid 4% Caustic Soda

7
 Example of Amine Blend Effect on pH
9.4

9.2

9.0
pH

8.8
Trial A - pH (33.9 - 35.7C)
8.6
Trial B - pH (34.0 - 36.3C)
8.4

8.2
1 2 3 4 5 6 7 8 9 10
Volume of Amine Blend, ppm

Effect of pH on Copper Transport

50.0
Product Release, g/ m Year

10.0
Copper Corrosion
2

70Cu/30Ni
90Cu
/ 10 N
1.0 i

0.2
7.0 8.0 9.0 10.0
pH

8
 Dissolved Oxygen

6 Oxygen as O2 (from air)

dissolved in water.
Corrodes copper and
steel (economizer
shown).
6 1 ppm O2 =
1 mg/L =
1000 ppb =
1000 g/L

Dissolved Oxygen Effect on Copper Corrosion

16

14 70Cu/30Ni (Alloy 715) 3 ppb O2 100-200 ppb H

70Cu/30Ni (Alloy 715) 200 ppb O2 25 ppb H
Corrosion Rate, mpy

12
90Cu/10Ni (Alloy 706) 3 ppb O2 100-200 ppb H
10 90Cu/10Ni (Alloy 706) 200 ppb O2 25 ppb H
8

0
0 50 100 150 200 250 300 350 400 450
Temperature F

9
 Dissolved Oxygen
6 Normal Values
Mill Water or Demineralized Water
Saturated (8,000 - 14,000 ppb)

Condensate: 10 - 100 ppb O2

Feedwater: <5 - 10 ppb O2
6 Sources
Air Leaks
Where Water Leaks Out, Air Leaks In

Mill Water In-leakage

0.1% Raw Water = 8 - 14 ppb O2

Dissolved Oxygen Control: Deaerator

Water Inlet
Vent Distributor Nozzles

Trays

Steam
Inlet

10
 Deaerator Spray Nozzles And Trays

Oxygen Scavengers Carbohydrazide Example

6 Oxygen Scavenging (Reduces Oxygen)
Oxygen + Carbohydrazide Inerts + Carbonic Acid
6 Passivation
Red Rust + Scavenger Black Rust + Carbonic Acid

11
 Oxygen Scavenger Feed
6 Underfeed
Copper Corrosion in Steam/Condensate System
Pitting of Economizer
6 Overfeed
FAC: Flow Accelerated Corrosion and Rupture of Steel Pipe
Lines (e.g., Feedwater Line)
Decomposition Products

Questions

12
 Hardness In Generation Bank Tube
6 Hardness Scale In
Generation Bank
Tube, Dispersant
Treatment
6 Without Dispersants,
Gray Mayonnaise
Deposits Are In
Drums

Hardness Definition
6 Mainly the Calcium (Ca) and Magnesium (Mg)
6 Precipitates and Forms Hardness Scale In Boiler
6 Precipitation Can Result in Decreased Boiler pH

Hardness + Phosphate Sludge + Salt + Acid

Calcium Sodium Calcium Sodium Sulfuric

+ + +
Sulfate Phosphate Phosphate Sulfate Acid

3CaSO4 + 2Na2HPO4 Ca3(PO4)2 + 2Na2SO4 + H2SO4

13
 Hardness - Limits
6 Expected Values (ppm CaCO3)
Feedwater and Turbine Condensate: 0.0
Process Condensate 0.0 Trace
6 Sources
Mill Water In Condensate/Feedwater
Problem In Makeup Demineralization System

Control of Hardness: Prevent Intrusion

Condensate/Feedwater
Condensate/ Pump Discharge
Feedwater
Two Isolation Valves
For HP Service
Pump Seals

Cooling
Water Drain
Drain
Seal Water
Throttling
Valve

14
 Phosphate (PO4)
6 Amount of Sodium Phosphate Dissolved in Boiler Water
6 Units: ppm PO4 = mg/L PO4
6 Purpose:
Stabilizes pH
Precipitates Hardness as Softer Deposits
Backup Indication of Hardness Contamination

Phosphate/pH Control Curves

10.5 3.0
aOH) 2.7
(1 ppm N 800 psig
um Line
Equilibri sig (5.5 MPa) 2.4
10.0 1 200 p )
a
psig ( 8.3 MP
1500 MPa)
( 10.3
Molar Rat io
Na:PO4

9.5
pH

9.0

8.5

8.0
6 10 14 18 22 26 30
Phosphate, mg/L

15
 Phosphate Effect on Boiler Water pH

Sodium-To-Phosphate
Molar Ratio
3 .0

NaOH 2. 6
2 .4
TSP
2. 2
DSP
pH

2. 1
(MSP)
Blowdown
2.0

Phosphate, mg/L

Summary: What Should You Know?

6 Top Chemistry Parameters in Steam/Water Cycle
Conductivity S/cm
pH
Dissolved Oxygen, ppb O2 (and Oxygen Scavengers)
Hardness, ppm CaCO3
Phosphate, ppm PO4
6 Steam/Water Cycle, Basic Components
6 Other (See Appendices)

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 Appendices
6 A: Makeup Water Treatment
6 B: Condensate Collection and Treatment
6 C: Feedwater Treatment System
6 D: Boiler Water Treatment
6 E: Steam Purity Considerations
6 F: Additional Chemistry Testing
6 G: Preventive Maintenance
6 H: Personnel Training
6 I: Chemical Cleaning

For More Information

6 TAPPI Technical Information Papers
TIP 0416-03 Water Quality and Monitoring Requirements
for Paper Mill Boilers Operating on High Purity Water, 1999
TIP 0416-04 Design Engineer Decision Tree: Paper Mill
Boiler Feedwater, 1999
TIP 0416-05 Response to Contamination of High Purity
Boiler Feedwater, 2000
TIP 0416-06 Keys to Successful Chemical Cleaning of
Boilers, 2000

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