Mill Supply

or
Water Distribution System
Protection
and
Once Through Cooling
A Division of Somebody
 Supply Water System
Mill Supply or Distribution
System-- used for
Domestic Water
Firewater makeup
CT Makeup
Boiler System
Process Water

2
Distribution System Problems
Corrosion of the steel piping
delivering high soluble iron into
downstream processes
Iron Bacteria contamination of
the Water

3
 What Affects Corrosion

pH
Alkalinity
Dissolved Solids
(conductivity)
Calcium Levels

4
 Once Through Cooling
or low cycle recirc water
Common in power industry
Commonly raw water - not
clarified
High suspended solids
loading

5
 Once-Through Cooling
Systems
Problems
Deposit Control
- CaCO3
- Iron
- Manganese
- Particulate Solids
Corrosion Control
Steel, Stainless Steel, Copper Alloys

6
 Once-Through Cooling
Utility Systems
CaCO3 Deposition Control
HEDP - most cost-effective inhibitor
ppb HEDP = 102.16 LSI x 0.014
Examples:
LSI = 1 2.0 ppb HEDP1
LSI = 1.2 5.6 ppb HEDP
LSI = 1.5 24 ppb HEDP
LSI = 1.8 109 ppb HEDP
Notes: 1. Minimum recommended HEDP dosage
is 5 ppb
2. Equation is not adjusted for Fe, Mn, or Solids

7
 Once-Through Cooling
Mill Supply
CaCO3 Deposit Control
HEDP most effective, but may be cost-
ineffective
0.5 ppm HEDP for LSIs < 2.2
Hexmeta - more cost-effective, but limited
applicability
0.5 - 1.5 ppm for LSIs < 1.5

Dosage is LSI dependent

Dosage usually dictated by $

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 Once-Through Cooling
Utility Systems
Manganese and Iron Deposition Control
Control by sequestering soluble metals
ppm HEDP = 2 (ppm Mn + ppm Fe)
Control by dispersing insoluble (precipitated)
metals
ppm HPS-1 = 4 x (ppm Mn + ppm Fe)
Generally, 2:1 blend of HPS -1:HEDP is used
Use higher ratio blends for suspended solids > 20
- 40 NTU

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 Once-Through Cooling
Mill Supply
Manganese and Iron Deposition Control
Control by sequestering soluble metals
ppm HEDP = 1/2 (ppm Mn + ppm Fe) for Ca < 50
ppm HEDP = ppm Mn + ppm Fe for Ca > 50
ppm pyro = 2 x (ppm Mn + ppm Fe) for Ca < 50
loss of effectiveness at Ca > 50
Control by dispersing insoluble (precipitated) metals
ppm HPS-1 = 2 x (ppm Mn + ppm Fe)

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 Mill Supply & Utility
Systems
Why the differences?
Utility Systems - not as prone to CaCO 3 Scaling
High Velocity
Copper And Stainless Steel - low fouling potential
Utility Systems - performance more sensitive to
fouling
must ensure adequate deposit control
metallurgy prone to scaling and localized corrosion
Mn induced corrosion
Under-deposit corrosion
makeup water not pretreated

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 Manganese & Iron
Monitoring
Millipore Filters
0.2 - 0.45 microns filtration
color intensity: brown-black
particulate
Polyester Bags
on-line monitor - timed exposure
staining - no staining
not sensitive to silt/clay fouling
Delta P monitor
sensitive to particulate and MB
fouling

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 Once -Through Cooling
Manganese
Manganese - causes corrosion and deposition
Control Techniques
Remove - Pretreatment
Precipitation & Clarification
Oxidize soluble Mn with halogen
O3 > ClO2= KMnO4 > > >> HOBr = HOCl >
O2 @pH<8.5
Sequester Soluble Species/Disperse
Insoluble
Minimize halogen - for corrosion control

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 Manganese Influenced
Corrosion
Mechanism Involves Mn + Oxidizing Biocides
Soluble Reduced Manganese Salts (Mn +2) In
Sediments or Well Water
Oxidized to Insoluble MnO2
MnO2 Deposits Autocatalytically Onto Copper Alloy
and Stainless Steel Surfaces
Further Oxidized to Soluble MnO 4- at Tube Surface
by Halogen
Permanganate Dissolves Metal

4Feo + 2MnO4- + 4H2O 2MnO2 + 4Fe(OH)2 +

2e-

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 Effect of Metal on
Oxidation of Mn
8
7
6
5
Soluble Mn
(ppm) 4
3
2
1
0
No Metal Zinc Copper

Conditions: 8 ppm Mn(II), 200 ppm CaH, pH 8.5

50C, 5.5 Hours, 0.2 Micron Filter
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 Effect of Manganese on
SS

Manufacturers Ratings
Tverberg and Leuchak, Carpenter Tech., 1979
Certain waters have periodic incursions of
manganese ions that have caused serious
pitting problems of Type 304 stainless steel
When sum of Fe and Mn >1, given a 3 rating
3 - Definite adverse effect unless special
precautions are taken
Special Cases:
1. Waters with more than 0.3 ppm
manganese

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 Once -Through Cooling
Relative Performance

HEDP PBTC AEC HPS-1 PAA Citric Acid Pyro Hexameta

CaCO3 5 3 2 2 3 1 1 3
Fe-Sol.(<1ppm) 5 2 2 3 3 2 5 2
Fe-Particulate 2 1 1 5 4 1 2 1
Mn-Sol. (<0.5 ppm) 5 2 3 2 3 3 4 2
Mn-Particulate. 1 1 1 5 5 1 1 1
Clays 1 1 1 4 5 1 1 2

17 5 - most effective
 Once-Through Cooling
Corrosion Control
Utility Systems
Copper Alloy Corrosion Inhibition
Intermittent feed of HRA
Frequency of feed depends on:
water chemistry, halogen
concentration, frequency of halogen
feed. Must be determine on-site.
Generally, not treated unless halogen
used or copper discharge a concern.
Steel Corrosion
Generally, not an issue.
Follow mill supply guidelines.

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 Once-Through Cooling
Corrosion Control
Mill Supply
Steel Corrosion - generally, most significant
issue
Most significant factors in choosing program:
Water Hardness
< 20 ppm Ca - difficult to treat without
zinc
Conductivity
Water Temperature
< 16-18 oC transition temperature
pH
< 7.2 - difficult to treat without Zinc

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 Once-Through Cooling
Mill Supply Systems
Steel Corrosion Inhibitors
Premier Program
3 ppm ortho-PO4/1 ppm Zinc
3 ppm pyro -PO4/1 ppm Zn
cost-prohibitive
Typical Program
Dictated mostly by COST $$$$$$$

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 Once-Through Cooling
Mill Supply Systems
Steel Corrosion Inhibitor Programs
Calcium < 15 - 20 ppm
Ortho-PO4 more effective than pyro-PO 4
> 1.5 ppm required
addjust pH if possible to 8.0 > pH > 7.5
pyro-PO4 alone will increase copper corrosion rate
ortho-PO4/Zn and pyro-PO4 are preferred
ortho-PO4/Zn most effective
Zn eliminates pyro-PO4s effect on copper
T < 25 - 30 C
1-1.5 ppm PO4 and 0.3 to 0.5 ppm Zn effective
as temp decreases - inhibitor level decreases
hot water systems may require supplemental
inhibitor

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 Once-Through Cooling
Mill Supply Systems
Mississippi Paper Mill
Water Chem: 15-17 ppm TH, pH7.2-7.4,
0.2-0.5 ppm Cl2, 120 ppm M alk.
Treatment:
1 ppm pyro / 0.5 ppm HPS-1 / 0.25-0.45
ppm Zn
Steel Corrosion Rates < 1 mpy @ 25 oC
0.5 ppm pyro/1 ppm HPS-1
supplemental feed to hot steel bundles
(>56oC) to suppress localized corrosion

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 Once-Through Cooling
Mill Supply Systems
Louisiana Paper Mill
Water Chem: 20-30 ppm Ca, pH6.2-
6.8, 0.5 ppm Cl2, 8-14 M alk., 200-
300 micromhos, 0.1-0.3 ppm Fe,
0.06-0.07 ppm Mn.
Treatment:
1.5 ppm ortho / 0.4-0.5 ppm
pyro / 0.35 ppm Zn
Steel Corrosion Rates < 1 mpy @ <
32oC

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 Once-Through Cooling
Mill Supply Systems
Steel Corrosion Inhibitor Programs
Ca > 20 ppm
If Zinc is allowed - always use it, no matter
how low the concentration!!
Ortho or pyro can be used
Dosage: 0.75 - 1.5 ppm ortho or 1 - 2
ppm pyro.
HPS-1 required for CaPO4 control if
T>32oC or Ca > 40 ppm

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 Once-Through Cooling
In General
Diagnose the problem! Dont treat the
symptom!
Symptom = Steel Corrosion
Water Chemistry? Poor Inhibitor Program? MIC?
Conduct On-Site Corrosion Studies
Optimize Inhibitor Program
Adjust Inhibitor to system parameters
Satellite feed of dispersant/corrosion inhibitor.
Dont mistake MIC for traditional corrosion

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 Once-Through Cooling

Cleaning -
High pyro dosages periodically
-Too costly
Low pyro levels (0.5 to2) with/without
polymer - continuously
- not very effective
- some removal of soft iron deposits
- largest effect - reduced corrosion

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 Open Recirculating
Systems

Low Hardness Programs

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 Low Hardness Programs
Recirculating Systems
Corrosion!
Copper Alloy Corrosion
not problematic - azole chemistry
does not depend on Calcium

Steel Corrosion Inhibition

Both ortho and pyro-PO4 require Ca
to act as cathodic inhibitors.

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 Low Hardness Programs
Recirculating Systems
Steel Corrosion Inhibitor
Programs
Low Hardness = < 50 ppm Ca

Ortho-PO4 and ortho-PO4/Zn most effective

Pypro-PO4 - limited utility alone - requires

higher calcium for complex formation.

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 Low Hardness
Dianodic III Guidelines
Low Temperature Systems (<38oC)
ppm Ca pH Cond ppm o-PO4 ppm Zn
mmhos
<20 7-7.5 <1250 15 2
<20 7 - 7.5 > 1250 15 4
<20 7 -7.5 < 1250 25-30 0
<20 7-7.5 >1250 30-35 0
<20 7.5-9 <1250 7.0-9.0 2
<20 7.5-9 >1250 7.0-9.0 4
<20 7.5-9 <1250 20-30 0
<20 7.5-9.0 >1250 25-30 0
20-50 7-7.5 <1250 17-21 2.5
20-50 7-7.5 >1250 25-27 3.5
20-50 7-7.5 >1250 28-30 0
20-50 7.5-9 all 15-16 2
20-50 7.5-9 all 17-20 0
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 Low Hardness
Dianodic III Guidelines
High Temperature Systems (38 - 50oC)
ppm Ca pH Cond ppm o-PO4 ppm Zn
mmhos
<20 7-7.5 <1250 15 3.5
<20 7 - 7.5 <1250 40-45 0
20-50 7 -7.5 < 1250 12 3
20-50 7-7.5 <1250 30-35 0
<20 7.5-8.5 <1250 12 3
<20 7.5-8.5 <1250 35-40 0
20-50 7.5-8.5 <1250 10 2.5
20-50 7.5-8.5 <1250 25-30 0
20-50 7-7.5 <1250 25-30 0
<20 >8.5 <1250 10 2.5
<20 >8.5 <1250 30-35 0
20-50 >8.5 <1250 8 2
20-50 >8.5 <1250 20-25 0
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 Low Hardness
Continuum AEC
Corrosion Treatments
15 ppm AEC, 3-4 ppm Zn, 3 ppm o-PO 4 ,
HRA or TTA + 7.5 - 10 ppm HPS-1.
pH > 8.6
Cond. < 1250 mmhos
Ca = 5 -50 ppm
15 ppm AEC, 3-4 Zn, HRA or TTA + 5-7.5
ppm HPS-1.
pH > 8.9 when Ca<20
pH > 8.6 when Ca = 20 to 75 ppm

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 Programs
Recirculating Systems
50 - 100 ppm Ca
Follow Dianodic II and Continuum
AEC Guidelines
Dianodic II - control at 20 ppm o-PO 4
pH ~ 7.5
Continuum AEC -
control at 8-10 ppm o-PO4 or

5-6 o-PO4 + 2-3 ppm Zn

maintain pH as high as possible

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