CoolingWaterFundamentals

SteelIndustryWaterConference
ClearwaterBeach,FL
Clearwater Beach FL
September1214,2012
RaymondM.Post,P.E.
DirectorCoolingTechnology
RayP@chemtreat.com
 Outline
TypesofCoolingSystems
Oncethrough
ClosedLoop
Openrecirculating
CoolingTowers
Cooling Towers
PhysicalDesign
HeatTransfer
CyclingorConcentrationRatio
C li C t ti R ti
IssuesandTreatment
Deposition
p
Corrosion
MicrobiologicalFouling

WhatCoolingtopicswouldYOUliketodiscusstoday?
2
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 CoolingWaterSystems

R
RemoveHeat
H t (BTUs)
(BTU )
Two Mechanisms:
1.TemperatureChangeSensibleHeat
Heatcapacity
p y Cp =1BTU/lboF (1cal/g g oC)
Heattransferred Q=mxCp x(Th Tc)
2.Evaporation
p
LatentHeat LH=1,000BTU/lb (556cal/g)
Heattransferred Q=mxLH

Howdoindustrialcoolingsystemsusetheseproperties?
3
Property of ChemTreat, Inc. Do not copy without permission.
 Once ThroughSystem
g y
Cooling Water
Supply

Process
Heat Load
Cooling Water Discharge
or to Mill Water

Q(Btu/hr.)=mCp
Q(Btu/hr.)=mCp(Tout
(Tout Tin)=gpmx500(Tout
Tin)=gpmx500(Tout Tin)
4
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 ClosedRecirculatingSystem

To Heat
Sink
Heat Process
E h
Exchanger
Heat
Makeup
Load
From
Heat
Surge
Sink Tank

Whatplantheatexchangersuseclosedcooling?
5
Property of ChemTreat, Inc. Do not copy without permission.
 OpenRecirculatingSystem
Hot
Humid Drift
Air Bl d
Blowdown

Cooling
Tower Cool
Dry Heat
Evaporation
Air Load

Makeup Recirculating Pump(s)

Q=mLH
Q= mLH =mx1,000Btu/lb=mCp
=mx1,000Btu/lb=mCp(Tout
(Tout Tin)
6
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 Cooling System Comparison
CoolingSystemComparison

OnceThrough ClosedLoop CoolingTower

Pro Con Pro Con Pro Con
Lowestcapitalcost
p Poorchemistry
y Excellentchemistry
y Highest
g sinktemp
p Smaller water Consumeswater
control control source(~100x) (evaporation)
Lowestoperating Large sourceand Corrosionproduct Fairlylowtemp Higheroperating
cost water accumulation sink(wetbulb) cost(fan&pump)
requirements
L
Lowesttempsink
i k Th
Thermal
l discharge
di h LLessthermal
h l C
Concentratessalts
l
dischargetowater
Supplieshotwater Fishandplankton Goodchemistry Saltdrift
entrainment control
Aquatic Weeds&
Weeds & Potential toreduce
to reduce Airborne
Airborne
Debris wastewatervolume pathogens

7
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EvaporationOverACoolingTower
OnlyThePureWaterIsLost

Mineralsareconcentrated
8
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 CyclesofConcentration
Cycles of Concentration
ConcentrationRatio
Cycles,COC,CR,C
MU IBD
C= =
BD IMU
MU Make p flo
MU=Makeupflow IBD =AnyioninBlowdown
Any ion in Blowdown
BD=Blowdownflow IMU =SameioninMakeup

9
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 Cooling Tower Balances
CoolingTowerBalances
Solving the Cooling Tower Equation

Mass(WaterandSaltConcentration)
Mass (Water and Salt Concentration)
Makeup=Evaporation+Blowdown
Blowdown = BD intentional + Drift + Windage
g + Leaks

Energy(Heat)
Qin =Q
= Qout

Howdowecalculatetheenergybalance?
10
Property of ChemTreat, Inc. Do not copy without permission.
 Energy(Heat)Balances
Qin =RR*Cp*(TR TS)
Cp~1.00Btu/lbF
p /
Qout =E*LH/f
LH~1,000Btu/lb
E=[RR*1.00*(TR TS)*f]/1,000 BD
E
RH TR T1 T2
Tdb Vs. Twb

TS RR

Whatisf?
11
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 actor EvaporationFactor(f)
1.1
10
1.0 20% RH
aporattion Fa

40% RH
60% RH
0.9 80% RH
100% RH
0.8
0.7
Eva

0.6
0.5
20 30 40 50 60 70 80
Wet Bulb Temperature (F)
Howdoweputthisinfotogetherintoanequation?
12
Property of ChemTreat, Inc. Do not copy without permission.
 CombinedEnergyandMassBalance
gy
E=(RR*(TR TS)*f)/1,000
MU=BD+E
MU = BD + E
C=MU/BD(also,C=ConcBD/ConcMU )
C=(BD+E)/BD
BD*C=BD+E BD
BD*C BD=E
BD*(C1)=E E
TR
BD=E/(C 1)

TS RR
MU

Ifweincrease(decrease)cycles,whatstheimpactonMU&BD?
13
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 EffectofCyclesonMU&BD

Tower Parameters
TowerParameters
RecirculationRate 58,824gpm
DeltaT 20 F
EvaporationFactor 0.85

WhatCyclesdoyouoperateyourtowerat?WhatlimitstheCOC?

14
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 Definitions Approach&Range
107FHotReturnH2O

90FAir DryBulb
73 FWetBulbAir
73F Wet Bulb Air
45%Rel.Humidity 84.5FColdSumpH2O

Approach Temperature = 11 5FF

ApproachTemperature=11.5 Cooling Range (T) = 22 5FF
CoolingRange(T)=22.5

The wetbulbtemperature isthelowesttemperaturetowhichwatercan

becooledbyevaporation
Thedifferencebetweenthecoldsumptemperatureandthewetbulb
temperatureiscalledtheapproach
Thetemperaturedifferencebetweenthehotreturnwaterandthecold
sumpwaterisreferredtoasthecoolingrange
t i f dt th li (D lt T)
(DeltaT)
Whatwouldhappento
Whatwouldhappentoefficiencyifwehadto
efficiencyifwehadtouseDryCooling?
useDryCooling?
15
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 CoolingTowerDesigns
CrossFlow Induced Draft
CrossFlowInducedDraft CounterFlow Induced Draft
Counter FlowInducedDraft

Drift
Eliminators
li i
Drift
Eliminators
Air

Air Louvers

AirflowdirectionAcrosstheWaterflow AirflowdirectionisCountertoWaterflow
16
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 CoolingTowerFill
WATER
S l h Fill
SplashFill Fil Fill
FilmFill

WETTED
SURFACE

AIR

OpenDesign
OpenDesign LessPronetoFouling TightPassages MoreEfficient
TightPassages
17
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 Cooling System Review
CoolingSystemReview
Whatarethe3generaltypesofcoolingsystems?
What are the 3 general types of cooling systems?
Howdocoolingtowersremoveheat?
WhatismeantbyCyclesofConcentration?
What is meant by Cycles of Concentration?
WhatcanhappenifCyclesgettoohigh?
TooLow?
WhyisEvaporativecoolingmoreefficientthanDry?
Whatis
What is Approach
ApproachtotheWetBulbtemperature
to the Wet Bulb temperature
Whatishighefficiencyfilmfill?
Whatconcernshouldwehave?

18
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Section2

COOLING WATER CHEMISTRY

COOLINGWATERCHEMISTRY

19
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FundamentalCoolingTriangle
g g
Corrosion

Control

Deposition BioFouling

Howiseachelementaddressedatyourplant?
How is each element addressed at your plant?
Howwellisitworking?
20
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 Deposition
p

Whatisit?
What is it?
Whyshouldwecare?
How is it measured?
Howisitmeasured?
Whatfactorseffectit?
How is it controlled at
Howisitcontrolledat
yourmill?
Howwellisitworking?
How well is it working?
21
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 TypesofDeposition
yp p
Scaling
Mineralscale
Mi l l
Fouling
Suspendedmatter
S d d tt
Transientcorrosion
products
ProcessContamination
Lubricants,millscale,glycol,
otherprocesssolids&fluids
th lid & fl id

Howdoesscaleform?
22
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Scaling EvaporationOverACoolingTower
C Th Mi l
ConcentratesTheMinerals

Only the pure water (H2O)islostbyevaporation

Onlythepurewater(H O) is lost by evaporation
Whatfactorsaffectscaleformation?
23
Property of ChemTreat, Inc. Do not copy without permission.
 ScaleFormation
CoolingTowerpHChemistrySimplified
Functionof: H2OH+ +OH
H+ =Acid=LowpH
= Acid = Low pH
ConcentrationofIons OH =Caustic=HighpH

pH Evaporationconcentratesminerals:
HCO3 (bicarbonate)OH +CO2
Temperature pHincreases
HCO3 +OH H2O+CO3=(carbonate)
Velocity Ca++ +CO
+ CO3= =CaCO
= CaCO3
PresenceofSolid Calciumcarbonatescale

SeedingMaterial Addsulfuricacid:
H2SO4 +2OH= H2O+SO4=
Ca++ +SO4= CaSO4?
Calciumsulfatescale(gypsum)
More soluble than CaCO3, but
MoresolublethanCaCO3,but

Whatdowemeanbyinversesolubility?
24
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 CommonScaleFormingMinerals
InverseSolubilitywithTemperatureandpH
ncreasing g

ncreasingg
Solubility
Solubility
In

In
S
S

Temp pH

Whyisinversesolubilityaproblem?
25
Property of ChemTreat, Inc. Do not copy without permission.
 CalciumCarbonateIsInverselySoluble
With Temperature (and pH)
WithTemperature(andpH)
(Process)

HEAT
Ca+ CO3 Ca+ CO3 Ca+ CO3
Ca+ CO3 Ca+ CO3 Ca+
CO3
Ca+
CO3
Ca+
C
Ca+
CO3
Ca+ CO3 Ca+ CO3 Ca+
Ca+ CO3 Ca+ CO3 Ca+ CO3

METALSURFACE HEAT
(Process)

26
Property of ChemTreat, Inc. Do not copy without permission.
 Co
CommonMineralScales
o e a Sca es
CaCO3 CalciumCarbonate
CaSO4 CalciumSulfate
Ca3(PO4)2 CalciumPhosphate
CaF2 CalciumFluoride
ZnPO4 ZincPhosphate
Zn(OH)2 ZincHydroxide
Fe2(PO4)3 IronPhosphate
Fe2O3 Iron Oxide
IronOxide
MnO2 ManganeseDioxide
SiO2 Silica
Mg3Si4O10(OH)2 Magnesium Silicate
MagnesiumSilicate
(AlO)2SiO3 AluminumSilicate
CaMgSi2O6 CalciumMagnesiumSilicate

Whatisthemostcommonscale?
27
Property of ChemTreat, Inc. Do not copy without permission.
 CaCO3Indices
LSI LangelierSaturationIndex
LSI=pH pHs
pH=ActualpH
pHs =SaturationpH
pHs =functionofCalcium,MAlkalinity,TDS,&Temp.
MAlkalinityortotalalkalinityisanapproximationofthe
bicarbonate concentration
bicarbonateconcentration
USFederalRegisterAug27,1980,p.57338Vol 45(No.168)
InterpretingLSI
Negative
g calciumcarbonateScaleisNotPossible
Positive calciumcarbonateScaleisPossible
>0.5 ScaleisLikelywithouttreatment
>1.0 ScaleisProbablewithouttreatment
Typically,operate<2.5withscaleinhibitor
3.0isthemax.recommendedwithheroictreatment

Whatisthechemistrybasisforthisindex?
h h h b f h d ?

28
Property of ChemTreat, Inc. Do not copy without permission.
 PredictingMineralScaling
g g
Safe, Needs OKwith DoYou
NoTreatment Treatment Treatment FeelLucky?
Proprietarysoftware
Proprietary software pH
H
Writeyourown
Workwithcooperatingchemical 6 7 8 9
orconsultingcompany
LSI
Commerciallyavailablesoftware
ConsiderFrenchCreekSoftware 0.50.00.5 1.0 2.0 2.5 3.0
WaterCycle (Cooling)
HydRODose
H d RO D SiO2
DownHole SAT
100 150 200 300
PHREEQE
WATEQ4F
Q CaH x SO4
CaHxSO
Manufacturerspecs.
Firstresource 1x106 5x106 10x106 40x106
Whenallelsefails,readtheinstructions
Tendtobeconservative
T d b i MgH x SiO2
MgHxSiO
pH7 400,000 pH8 100,000pH9 20,000

29
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ControllingDepositFormation
 ChemicallyControllingMineralScales

With
Without
Without
Inhibitor
Inhibitor

ThresholdInhibition
Adsorbontogrowingcrystalembryo
Distort orderly growth pattern
Distortorderlygrowthpattern
Encouragedissolutionoftheembryosintoions
ContrasttoChelation
Phosphonates(OrganicPhosphates)
PBTC,HEDP,AMP,DETPMPA,andothers
Generally most effective but are affected by iron and can be degraded by oxidizers and UV light
Generallymosteffective,butareaffectedbyironandcanbedegradedbyoxidizersandUVlight
Polyphosphates(InorganicPhosphates)
Hexametaphosphateprimarily
HydrolyzefairlyrapidlytosimpleorthoPO4
Polymers
Polymaleate,polyacrylate,polymers,copolymers,oligomers
Lesseffective,butmorestableandnonP
Alsousedincombinationwithphosphonatestodisperseanddistortcrystalnuclei 31

Property of ChemTreat, Inc. Do not copy without permission.

 ChemicallyControllingMineralScales
AdvancedQuadrasperse PhosphonateBlend
p
CalciteSupersaturation
CombinationofQuadrasperse
andPhosphonateallowsthe 300
highest calcium carbonate
highestcalciumcarbonate
supersaturation 200
USPatent6,645,384
Al
Alsopatentedformagnesium
t t df i 100
silicatecontrol
0

32
Property of ChemTreat, Inc. Do not copy without permission.
 Controlling Fouling By Suspended Solids
ControllingFoulingBySuspendedSolids

Solidparticlesenterthecoolingsystem
p g y
Makeupwater
Air airbornedust
Processcontamination
Process contamination oils,iron,glycol
oils iron glycol
Mechanicalcontrol
Removesuspendedsolidsfrommakeupwaterusingappropriate
pretreatment(clarifiers,softeners,andfilters)
Installsidestream orfullflowfilters
Redesignforhigherwatervelocity
g g y
Feedchemicaldispersantsand/orsurfactantstokeep
theminsuspensionandpreventthemfromdepositing

33
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 ChemicalControlofSuspendedSolids
Dispersion
Dispersion
Clay particles naturally have a negative surface charge
Anionic polymeric Dispersants adsorb onto suspended solids
solids...
...Reinforcing negative charges

Causing them to repel

Whataresomecommondispersants?
34
Property of ChemTreat, Inc. Do not copy without permission.
 Typical Dispersants
TypicalDispersants
Polyacrylicacid
Homopolymers
PAA,PMA,
Copolymers CH2 CH
SSMA AA/AMPS HPS1 APES t .
SSMA,AA/AMPS,HPS1,APES,etc n
Terpolymers C
HSP,STP

Quadrasperse O O
USPatent6,645,384
Charged carboxylic acid group
Chargedcarboxylicacidgroup

35
Property of ChemTreat, Inc. Do not copy without permission.
Copolymer Vs.Quadrasperse
Cooler #3 High Temp Heat Exchanger
Cooler#3,HighTemp.HeatExchanger
Gulf Coast Chemical Plant - HX Flow with
AA/AMPS Vs.
Vs ChemTreat Quadrasperse

6000 Copolymer (10 ppm) Quad Polymer (8 ppm)

ooling Water Flow
w

5800
5600
5400
m)
(gpm

5200
5000
4800
Co

4600
0
4
8
12

16
20
24
28
32
36
40

44
48
52
56
Week
Cooling water flow top Cooling water flow bottom

36
Property of ChemTreat, Inc. Do not copy without permission.
OilDispersionandBiofilmPenetration
- SURFACTANTS -
Polar Non-Polar

Water OIL

Canbeanionic,nonionic,cationic,amphoteric
37
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Corrosion
 Corrosion
Whatisit?
Whyshouldwecare?
Howisitmeasured?
Whatfactorseffectit?
Howisitcontrolled?
Howiscorrosion
controlledatyourplant?
Howwellisitworking?

39
Property of ChemTreat, Inc. Do not copy without permission.
QuantityofCorrosionProductsGenerated
in 2 000 Yards Piping
in2,000YardsPiping

Rambie,D.
PaperTradeJournal,1984

Decreasesflow Foreignmaterialinpipe
Decreasesflow
Increasespressuredrop
Increasespressuredrop Increasespumpingcost
Blockscriticalspraynozzles
40
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CorrosionIsAnElectrochemicalProcess

Necessary
NecessaryElements
Elements

Anode
A d

nFlow
Anode
(Zinccase)
Cathode
Electron
Cathode
Cathode
Electrolyte (Carbonrod)
Electrolyte
ElectronFlow (Conductivepaste)
E

41
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Corrosion is an Electrochemical Reaction
CorrosionisanElectrochemicalReaction
WATER (ELECTROLYTE)
CircuitCompleted

Fe(OH)2
O2 2OH- O2
Fe++
Fe2O3(Rust)
ELECTRON 2eCATHODE
2
ANODE
FLOW
(MetalLoss)
Metal(Conductor)
ANODICREACTION CATHODICREACTIONS
CHEMICAL OXIDATION
CHEMICALOXIDATION CHEMICAL REDUCTION
CHEMICALREDUCTION
Fe0 Fe++ +2e O2 +H2O+2e 2OH
Whatfactorsaffectcorrosion? LowpHonly:2H+ +2e H2 42
Property of ChemTreat, Inc. Do not copy without permission.
 on Rate
Factors Affecting Corrosion
FactorsAffectingCorrosion

n Rate
Conductivity
pH
Corrosio

Corrosion
C
4 pH 10
Dissolved Solids
(Conductivity)
sion Rate

120 F
Temp & Oxygen
90 F
Corros

48 F
Temp or ppm Oxygen

Aretheredifferentformsofcorrosion?
43
Property of ChemTreat, Inc. Do not copy without permission.
 TypesofCorrosion
yp
Uniform
Localized(
Localized (pitting)
pitting )
Crevicecorrosion
Concentrationcell
U d d
Underdepositcorrosion
it i
Stresscorrosioncracking
MicrobiologicallyInfluenced(MIC)
Erosion
Dealloying
Thermal cell
Thermalcell
Straycurrent
Galvanic(dissimilarmetals)

44
Property of ChemTreat, Inc. Do not copy without permission.
 Uniform Corrosion
UniformCorrosion
LeastDamaging
L tD i
CathodicandAnodicSites
ContinuouslyChanging
EvenMetalLoss
Even Metal Loss
LongTimeBeforeFailure

11mpy
36dayexposuretime

Whathappensiftheanodedoesnotshiftrandomly?
45
Property of ChemTreat, Inc. Do not copy without permission.
 LocalizedCorrosion
VeryDetrimental
SmallAmountofMetalLoss
ShortTimeBeforeFailure
Classicpittingcorrosion

Pitting,strictlydefined,occursonafullyexposedsurface
46
Property of ChemTreat, Inc. Do not copy without permission.
 AnatomyOfAPit PitHappens
WATER (ELECTROLYTE)
2e
OH Cl OH Cl
Cl OH
OH Cl

Cl OH

H+ H+ H+ H+ H+
Fe(OH)
Fe+22 +2HOH ( )2 +2H+

Metal(Conductor)

Rusttuberclebehaveslikeasemipermeablemembrane
Chlorideionsaresmalleranddiffusefasterthanhydroxideions
Chloride ions are smaller and diffuse faster than hydroxide ions
Pitbecomesacidicandconcentratedinchlorides
Onceapitforms,themetalisverydifficulttorepassivate 47
Property of ChemTreat, Inc. Do not copy without permission.
 GalvanicCorrosion
Galvanic Series
GalvanicSeries

Corroded End
(Active)
Magnesium Copper
Zinc Bronzes
Aluminum Copper-Nickel
Steel Titanium
Iron Monel
304 SS (Active) 304 SS (Passive)
316 SS (Active) 316 SS (Passive)
Lead Silver
Tin Graphite
Brasses Protected End
(Most Noble)

48
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 StainlessSteelCorrosionBehavior
ActivePassiveAlloy
Chromiuminthealloypromotestheformationofa
protectivehydrousironoxidefilmonthesurface
Pitsrapidlyifaportionofthesurfacebecomesactive
Pits rapidly if a portion of the surface becomes active
Requirementformaintainingpassivity
Oxygenmustbecontinuallyreplenishedatthesurface
Oxygen must be continually replenished at the surface
Avoid:
Deposits,especiallymanganese
Stagnantconditions(extendedwetlayup)
Highchlorides

Forstainlesssteel,thedepositcontrolprogramisyourcorrosioncontrolprogram!

49
Property of ChemTreat, Inc. Do not copy without permission.
 Stainless Steel Corrosion
StainlessSteelCorrosion
GeneralCorrosion
Acids
d
Reducingenvironment
StressCorrosionCracking
Stress Corrosion Cracking
Chlorides
Hightemperature(>
High temperature (> ~140
140FFor60
or 60 C)
C)
TensileStress(ResidualorApplied)
PittingCorrosion
Pitting Corrosion
Chlorides
Crevices
WhatsaSafeChlorideLevel?
50
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