Chemical Treatment and Control

Treatment Programs

Corrosion Historical Review

Neutral pH Programs
Alkaline pH Programs
Deposition
What’s New
Evolution of Cooling Treatment
Chromate (50's to early 60's)

Zinc Phosphate (late 60's)

Polynodic (early 70's)

Dianodic BAT / Zinc

(late 70’s to present) (early 80’s to present)
Polynodic Treatment Program
Orthophosphate
Pyrophosphate
Polymer
Historical Break-Through
Polymeric Dispersant
Effective Treatment Must:
Inhibit Corrosion
Minimize Deposition
Operate Under Broad Conditions
Be Economical
Have a Low Environmental Impact
Cooling Water Programs Components
Corrosion Inhibitors &
Deposit Control Agents
(Dispersants)
Cooling Water Program
Components:
Steel Corrosion Inhibitor
Cu/Alloy Corrosion Inhibitor
Polymeric Dispersant(s)
• Maintain corrosion inhibitor soluble
• Disperse Particulate
Calcium Carbonate Inhibition
• Allow operation at positive saturation
Program Classification

6.5 7.0 7.5 8.0 8.5 9.0

Neutral pH Programs (6.8 to 7.8)
• Corrosion Inhibitor Intensive
• Primarily Anodic Inhibitors

Alkaline pH Programs (> 7.8)

• Dispersant Intensive
• Primarily Cathodic Inhibitors Used
Conventional Cooling Programs
Components
Neutral pH Alkaline pH
Steel Inh. o-PO4, poly-PO4,Zinc o-PO4, Zinc
(phosphonate)

Copper Inh. TTA, BZT TTA, BZT

Dispersant Co & Terpolymer Co & Terpolymers

CaCO3 Inh. HEDP,PBTC HEDP, PBTC

Neutral pH Programs
Steel Corrosion Protection
• Orthophosphate: 10 - 18 ppm
• Polyphosphate: 0 - 6 ppm
• Zinc: 0 - 3 ppm
Copper Alloy Protection
• Azole (TTA): 1.5 - 5+ ppm
Deposition Control
• Copolymer/Terpolymer
Neutral pH Programs
“Stabilized” Phosphate Mechanism
Passive Iron Oxide Layer Formed at Anode
Polymer Allows Sufficient o-PO4 Dosage
Neutral pH Programs
Function of Polymer
Maintain Corrosion Inhibitors Soluble
Inorganic Phosphate / Zinc
Prevent Scaling of Hot Surfaces
Ca3(PO4)2, Zn(OH)2, Zn3(PO4)2, CaSiO2, ZnSiO2
Prevent Particulate Fouling
Silt, iron oxide/hydroxide, Alum (Aluminum
hydroxide), Manganese oxides
Neutral pH Programs
Challenges:
High Temp. and/or Low Flow
Calcium Phosphate Scaling
Low Flow Steel Exchangers
Excessive Corrosion
Iron Phosphate Fouling
High Calcium Water
Calcium Phosphate Scaling
Iron and Alum (aluminum) Contamination
Precipitation/Deposition of Phosphate
Neutral pH Programs
Advantages
• Passive Film at Anode
• Easy to Recover from Upsets
• Scaling Potential Minimized
Disadvantages
• High Levels Phosphate Required (Scaling)
• Copper Corrosion Inhibition is Difficult
• Susceptible to pH Excursions
Alkaline pH Programs

“Well” Buffered
pH vs. Alkalinity

400
350
115
M-Alkalinity

300
250
200
150 28
100
50
0
6.5 7 7.5 8 8.5 9

pH
Alkaline pH Programs
Corrosion Potential Minimized
Higher Buffering Capacity
• pH Control Simplified
• Capitalize on Calcium Carbonate Film

Acid Reduction or Elimination

CaCO3...The “Free” Inhibitor

+2
Ca CO -2
- 3
OH
HCO3-

CaCO3 CaCO3 CaCO3

Anode
Cathode
-
HCO3 + OH
-
CO3-2 + H2O
Ca+2 + CO3-2 CaCO3
Alkaline pH Programs
Deposition Control
• Phosphonate(s) for CaCO3
• Polymer for Inhibition & Dispersion
Alkaline pH Programs
Deposition Control
• Phosphonate(s) for CaCO3
• Polymer for Inhibition & Dispersion
Steel Corrosion Control
• CaCO3 - Maintain “+ LSI”
• Orthophosphate: 3 to 8 ppm
• Phosphonate: 4 - 8 ppm
• Zinc: 0.5 - 2 ppm
• Azole (TTA): 1 to 3 ppm
Alkaline Phosphate
Deposition/Precipitation Control
• Phosphonate (HEDP) - CaCO3
• Copolymer /Terpolymer - Ca3(PO4)2 , Ca-
Phosphonate, & Particulate Matter
Alkaline Phosphate
Deposition/Precipitation Control
• Phosphonate (HEDP) - CaCO3
• Copolymer /Terpolymer - Ca3(PO4)2 , Ca-
Phosphonate, & Particulate Matter
Corrosion Inhibition:
• Orthophosphate - Primarily Cathodic
• Phosphonate - Anodic and Cathodic
• TTA - Copper & Alloys
Alkaline Zinc
Deposition/Precipitation Control
• Phosphonate (HEDP) - CaCO3
• Copolymer/Terpolymer - Ca-Phosphonate,
Ca3(PO4)2, Zn(OH)2 & Zn2(PO4)3 & TSS
Alkaline Zinc
Deposition/Precipitation Control
• Phosphonate (HEDP) - CaCO3
• Copolymer/Terpolymer - Ca-Phosphonate,
Ca3(PO4)2, Zn(OH)2 & Zn2(PO4)3 & TSS
Corrosion Inhibition
• Phosphonate - Anodic and Cathodic
• Zinc - Cathodic Inhibitor
• TTA - Copper & Alloys
Common Phosphonates
CaCO3 Scale Control
PO3H2
HEDP
CH3 - C - OH HydroxyEthylidine
DiPhosphonic acid
PO3H2

CH2 COOH
PBTC
H2O3P C COOH
2-PhosphonoButane
CH2
1,2,4 TriCarboxylic acid
CH2 COOH
Common Phosphonates
CaCO3 Scale Control
PO3H2
HEDP
CH3 - C - OH HydroxyEthylidine
DiPhosphonic acid
PO3H2

CH2 COOH
PBTC
H2O3P C COOH
2-PhosphonoButane
CH2
1,2,4 TriCarboxylic acid
CH2 COOH
Problem with Phosphonates & Halogen

Phosphonate + Halogen ---->

ortho-PO4
+
Ineffective
Chlorinated Organics
Alkaline pH Programs
Advantages
• Buffering Reduces pH Swings
• Corrosion Potential Minimized
• Acid Feed Reduced / Eliminated
Disadvantages
• Phosphonate Instability with Halogen
• Phosphonate Precipitated by Calcium
• Upset Recovery Difficult
Conventional Neutral and Alkaline pH
Technology
Limits Cycles of Concentration
• Calcium Hardness & Retention Time
Halogen Instability
• Limits use of Halogen for disinfection
• Loss of copper corrosion protection
• Pitting of Steel due to copper plating
Approaches to Limitations of
Conventional Programs
Develop Friendly Halogen
Stabilized Bromine

Develop Halogen and Calcium Stable Programs

Neutral pH
Stabilized Phosphate

#1 Concern:
Calcium Phosphate Scaling
Polymer Dispersant Package

Improved Deposit Control:

Up to Three Dispersants

Custom Blended Based on System

All Are Halogen Stable

All Are Calcium Stable

HPS-I
Sulfonated Co-Polymer
Excellent Calcium Phosphate Control
• Inhibitor
• Dispersant
Excellent Dispersant for TSS
TMPS
Sulfonated Ter-Polymer
Improves Calcium Phosphate Control
• High Temperature
• Iron
• Aluminum
CAPS
Sulfonated Co-Polymer
Good CaCO3 Inhibitor
Aids HPS-I
• Control Of Calcium Phosphate
• Iron Dispersion
Alkaline Programs Components
Conventional Continuum AEC
Steel Inh. o-PO4, Zinc o-PO4, Zinc
(HEDP, PBTC) (AEC)

Copper Inh. TTA, BZT HRA

Dispersant Co & Terpolymer Copolymer (HPS-1)

CaCO3 Inh. HEDP,PBTC AEC

(phosphonate)