PAPER MILL DEPOSIT CONTROL

INORGANIC DEPOSITS

OmniKlir, Inc.

INORGANIC DEPOSITSScope of ProblemSources Problem Areas in MillAnalytical MethodsWater ChemistryScale FormationTreatment Options

OmniKlir, Inc.

SCOPE OF PROBLEM

Loss in Productivity

OmniKlir, Inc.

PRODUCTIVITY LOSSES DowntimeMachine BreaksReduced Machine SpeedFormation ProblemsReduced Efficiency

OmniKlir, Inc.

COST OF DOWNTIMELoss of Profits on tons not produced

Example:

$300/ton x 20 ton/hr = $6,000/hr

OmniKlir, Inc.

SECONDARY EFFECTSDecreased Equipment LifeCorrosionLower Quality ProductIncreased Cost

OmniKlir, Inc.

INORGANIC DEPOSITS

Sources of Components

OmniKlir, Inc.

SOURCES OF INORGANIC DEPOSITS

WoodWaterSystem AdditivesSecondary FiberByproducts of Pulping & Bleaching

OmniKlir, Inc.

WOOD COMPONENTSCalciumMagnesiumManganeseIronBariumSilica

OmniKlir, Inc.

VARIABILITY OF WOODBark

Wood SpeciesLignin & TanninComplexes with FiberLocationSand & Dirt

10 x minerals in woodHW > SWBleaching"Ion Exchange"

Local MineralsWashing

OmniKlir, Inc.

WATERCalciumMagnesiumBicarbonate/CarbonateIronManganeseSilicate

OmniKlir, Inc.

SYSTEM ADDITIVESFillers

CaCO3KaolinTiO2Structured Pigments

OmniKlir, Inc.

SYSTEM ADDITIVESAluminum compounds

AlumSodium AluminatePolyaluminum Chloride

OmniKlir, Inc.

SYSTEM ADDITIVESCalcium

DeinkingMake-up LimeWhite Liquor CarryoverCaCO3 FillerWater

OmniKlir, Inc.

SYSTEM ADDITIVESSilicate, Silica

BleachingDefoamerDirtSandFillers

OmniKlir, Inc.

BYPRODUCTS OF PROCESS

OxalateBreakdown of celluloseMost likely in bleaching

Lignin ModificationsVary ability to bind metalsOxidation releases metalsSoft scale

OmniKlir, Inc.

INORGANIC DEPOSITS

Problem Areas in Mills

OmniKlir, Inc.

KRAFT PULP MILL PROBLEM AREAS

Scale DigestersEvaporators

Hard ScaleSoft Scale

Liquor LinesWashers (w or w/o pitch)Sewer LinesPumps

OmniKlir, Inc.

KRAFT MILL DEPOSIT TYPES

Calcium CarbonatePitch/Calcium CarbonateSilica Silicates (calcium or magnesium)Calcium SulfateBarium Sulfate

OmniKlir, Inc.

MECHANICAL PULPING PROBLEM AREAS

Trouble SpotsRefinersGrindersChestsScreensLinesPumps

Combined with Fiber or Pitch

OmniKlir, Inc.

MECHANICAL PULP MILL DEPOSITS TYPES

AluminaBarium SulfateSilicatesManganese DioxideCalcium Oxalate

OmniKlir, Inc.

BLEACH PLANT PROBLEM AREAS

ScaleWashersLiquor LinesTowerChestsPumps

OmniKlir, Inc.

BLEACH PLANT DEPOSIT TYPES

Calcium CarbonateCalcium OxalateSilicatesBarium SulfateManganese DioxideIron Oxide

OmniKlir, Inc.

DEINK PLANT DEPOSITSCalcium CarbonateCalcium soapsSilicatesFillers

OmniKlir, Inc.

PAPER MILL PROBLEMSScale

ChestsLinesCleanersHeadboxMachine FramePumps

OmniKlir, Inc.

PAPER MACHINE PROBLEMS

Fillers DepositsHeadboxMachine FrameChestsSavealls

OmniKlir, Inc.

PAPER MILL DEPOSIT TYPES

FillersAluminaIron OxideBarium SulfateCalcium CarbonateCalcium Oxalate

OmniKlir, Inc.

FELT FILLINGAlumina

PitchSize

FillersCaCO3

OmniKlir, Inc.

ANALYTICAL METHODS

Inorganic Deposits

OmniKlir, Inc.

ANALYTICAL METHODSAtomic AbsorptionX-ray FluorescenceMicroscopic ExaminationWet ChemistrySpeck & Spot Analyses

OmniKlir, Inc.

ATOMIC ABSORPTIONBest Suited for Soluble Water ComponentsDeposits must be DigestedExtremely AccurateLaboratory Procedure Only

OmniKlir, Inc.

X-RAY FLUORESCENCESample must be DriedSmall Sample SizeMapping CapabilitiesLaboratory Technique Only

OmniKlir, Inc.

MICROSCOPIC EXAMINATION

Morphology of ParticlesOther Gross ContaminantsExtent of Fiber & FinesDone at the Mill

OmniKlir, Inc.

WET CHEMISTRYBest Suited for Water ComponentsDeposit Samples must be DigestedTraditionalHigh AccuracyLaboratory Method

OmniKlir, Inc.

SPECK & SPOT ANALYSISRapid TestsSemi-quantitativeIdentify Organic ComponentsMill DeterminationGood Problem Solving Tool

OmniKlir, Inc.

WATER CHEMISTRY IN PAPER MAKING

Solubility, Precipitation, and Scale Formation

OmniKlir, Inc.

SOLUBILITY OF SALTS IN WATER

Cl- HCO3- OH- NO3- CO3--- SO4-- PO4---Na, K, NH4 S S S S S S S

H+ S CO2 H2O S CO2 S SCa++ S SS VSS S I VSS IMg++ S S I S VSS S IBa++ S VSS S S VSS I ISr++ S VSS SS S I VSS IFe++ S SS VSS S VSS S I

Fe+++ S I I S I S IAl+++ S NP I S NP S ICu++ S I I S I S I

S > 5000 ppmSS 2000 - 5000 ppmVSS 20 - 2000 ppmI < 20 ppm

OmniKlir, Inc.

SOLUBILITY PRODUCT CONSTANT

CA C + A+ -

Ksp = [ C ] [ A ]+ -

[ CA ]

Ksp = [ C ][ A ]+ -

(Slightly Soluble)

(Very Low Solubility)

* Concentration Expressed in Moles/Liter

OmniKlir, Inc.

SOLUBILITY PRODUCT CONSTANTSCOMMON SCALE TYPES

BaSO4 1.1 x10 -10BaCO3 2.6 x10 -9CaCO3 5.0 x10 -9Ca(OH)2 7.9 x10 -6CaOxalate 2.0 x10 -8Ca3(PO4)2 2.0 x10 -33CaSO4 3.7 x10 -5Fe(OH)2 1 x10 -14Fe(OH)3 2 x10 -39Al(OH)3 1 x10 -9Mg(OH)2 5.7 x10 -12

OmniKlir, Inc.

CARBON DIOXIDE CHEMISTRY

CO2 + H2O H2CO3

H2CO3 + NaOH NaHCO3 + H2O

NaHCO3 + NaOH NaCO3 + H2O

OmniKlir, Inc.

CALCIUM CARBONATE CHEMISTRY

CaCO3 + H2CO3 Ca + 2HCO3

Ca + CO3 CaCO3

Ca + HCO3 + OH CaCO3 + H2O

Ca + 2HCO3 CaCO3 + CO2++

++

++

++

-

-

-

-

- -

OmniKlir, Inc.

CARBON DIOXIDE SPECIES vs. pH

01

23

45

67

89

1011

1213

14

pH

00.10.20.30.40.50.60.70.80.9

1Fraction of Total Carbon Dioxide

CO3 or bound CO2

HCO3 of half bound CO2

H2CO3 or CO2 gas

OmniKlir, Inc.

CALCIUM CARBONATE SCALEHeating 2 HCO3- CO3-- + CO2

OH - + HCO3 - CO3-- + H2O

CaCO3 has Inverse Solubility with Temperature

OmniKlir, Inc.

ALKALINITY TITRATION

0 10 20 30 40 50 60

12111098765432

pH Value

ppm H2SO4 added

NaOH

Na 2CO3P Endpoint

M Endpoint

OmniKlir, Inc.

SCALE FORMATION

Precipitation of insoluble compounds from water, which adheres to a surface.

OmniKlir, Inc.

SCALE FORMATION PROCESS

Transportation

Deposition

Dissolution

Problems?

OmniKlir, Inc.

REQUIREMENTS FOR SCALE FORMATION

SupersaturationNucleationContact Time

11223

4567

8910

11

OmniKlir, Inc.

SCALE DEPOSITION SCHEMATIC

Water

Supersaturation

Nucleation

Crystal Growth

SCALE

Dissolved Minerals

SuspendedSolids

OmniKlir, Inc.

NEGATIVE EFFECTS OF SCALE

Heat Transfer LossFlow RestrictionWashing ProblemsInaccurate Flow MeasurementsFormation ProblemsStock LumpsPicking

OmniKlir, Inc.

MINERAL SCALE

.001 .005 .010 .050 .100

Scale Thickness (in.)

0

20

40

60

80

100

% Reduction in Heat Transfer Coefficient

Al2O3CaCO3CaSO4ClaySiO2

Uniform Layer of Scale

OmniKlir, Inc.

HANDLING DEPOSIT PROBLEMS

Treatment Options

OmniKlir, Inc.

TREATMENT OPTIONSPretreatment to remove dissolved & suspended solids

SofteningIon exchangeFiltrationCoagulationReverse osmosis

OmniKlir, Inc.

WATER PRETREATMENT

Sedimentation

Clarification Chlorination

Raw Water Lime Softening Filtration Adsorption

Screens Aeration Ultrafiltration

Reverse Ion Electro-

Osmosis Exchange dialysis

Pure Water

OmniKlir, Inc.

TREATMENT OPTIONSLeave solids in and treat to prevent deposition

Scale InhibitorsAntifoulantsSludge conditionersFlocculantsCoagulantsDispersants

OmniKlir, Inc.

TREATMENT OPTIONSLeave solids in and allow deposits to form - then remove periodically

Chemical removal - boiloutsMechanical removal - hydroblastingCombination programs

OmniKlir, Inc.

DEPOSIT CONTROL ALTERNATIVES

Inorganic Materials

OmniKlir, Inc.

CALCIUM CARBONATEPULP MILL

Liquor ClarificationpH ControlCondensate for Pulp WashingHigher Flow RatesAcid cleaningWater Softening"Dispersants"

OmniKlir, Inc.

CALCIUM CARBONATEPAPER MILL

pH ControlWater SofteningImprove RetentionDispersantsBoilouts

OmniKlir, Inc.

BARIUM SULFATEPULP MILL

Reduce H2SO4Reduce AlumReduce soda lossBoiloutsDispersants

PAPER MACHINEReduce AlumReduce soda lossDispersantsBoilouts

OmniKlir, Inc.

MANGANESE DIOXIDEWater SofteningChlorination of Mill WaterChelating AgentsBoilouts

OmniKlir, Inc.

IRON OXIDESWater SofteningChlorination of Mill WaterCorrosion Inhibitors in Mill WaterLow Iron AlumChelating AgentsBoilouts

OmniKlir, Inc.

SILICA & SILICATESSilicate Reduction (Bleaching)Water SofteningImproved Chip WashingSwitch DefoamersImproved Retention

OmniKlir, Inc.

FILLER DEPOSITSWet End Chemistry

Improve Retention Aluminum ChemistrypH Control

DispersantsBoilouts

OmniKlir, Inc.

WET END CHEMISTRYFiber source & propertiesMachine designFillerspHWater chemistryCoagulantsFlocculantsSystem charge

OmniKlir, Inc.

ALUMINUM SPECIES vs. pH

34

4.254.5

4.755

5.255.5

5.756

78

910

11

pH

0

0.2

0.4

0.6

0.8

1Fraction of Aluminum

Al+3

Al+2

Al8(OH)20+4

Al(OH)3

Al(OH)4-

OmniKlir, Inc.

ALUMINA DEPOSITSAvoid pH shockCheck for overuseClarified White Water vs. Fresh WaterChange feed points

OmniKlir, Inc.

SCALE INHIBITION

Mechanisms for Control

OmniKlir, Inc.

HISTORICAL PERSPECTIVEPotato starch reported effective for boiler scale - 1821First scale control patent - 1869

OmniKlir, Inc.

LANGUAGE OFSCALE CONTROL

ChelationSequestrationComplexationAntiprecipitationThreshold treatmentDispersant

DeflocculantAntinucleation agentModificationSurface ModificationCrystal modificationPeptization

OmniKlir, Inc.

CHELATIONCo-ordinate bonds with cationsInterfere with the thermodynamics of crystal formation

OmniKlir, Inc.

CHELANTS & SEQUESTERANTS

EDTADTPANTACitrateGluconateTartrate

HexametaphosphatePolyphosphatePhosphonatesPhosphate estersLignosulfonateTannin

OmniKlir, Inc.

CRYSTAL MODIFIERSAdsorb at surface of crystalsDistort scale crystals as they growInterfere with kinetics of crystal formation

OmniKlir, Inc.

THRESHOLD INHIBITORSHexametaphosphatePolyphosphatePhosphonatesPhosphate estersLignosulfonateTannin

PolyacrylatesPolymethacrylatesPolymaleatesPolyphosphonateCMCAlginates

OmniKlir, Inc.

DISPERSANTSAnionic Charge (increase repulsion)

LignosulfonateTanninPolyphosphatesAcrylic polymersSulfonate polymersCopolymers & terpolymers

OmniKlir, Inc.

INORGANIC DEPOSITS CONTROL

Know the entire processUnderstand your optionsEvaluate the economics of treatmentACTION Plan

OmniKlir, Inc.

INORGANIC DEPOSIT CONTROL

The key to improved runnability.

OmniKlir, Inc.

PAPER MILL DEPOSIT CONTROLSCOPE OF PROBLEMPRODUCTIVITY LOSSES COST OF DOWNTIMESECONDARY EFFECTSINORGANIC DEPOSITSSOURCES OF INORGANIC DEPOSITSWOOD COMPONENTSVARIABILITY OF WOODWATERSYSTEM ADDITIVESSYSTEM ADDITIVESSYSTEM ADDITIVESSYSTEM ADDITIVESBYPRODUCTS OF PROCESSINORGANIC DEPOSITSKRAFT PULP MILL PROBLEM AREASKRAFT MILL DEPOSIT TYPES MECHANICAL PULPING PROBLEM AREASMECHANICAL PULP MILL DEPOSITS TYPESBLEACH PLANT PROBLEM AREASBLEACH PLANT DEPOSIT TYPESDEINK PLANT DEPOSITSPAPER MILL PROBLEMSPAPER MACHINE PROBLEMSPAPER MILL DEPOSIT TYPESFELT FILLINGANALYTICAL METHODSANALYTICAL METHODSATOMIC ABSORPTIONX-RAY FLUORESCENCEMICROSCOPIC EXAMINATIONWET CHEMISTRYSPECK & SPOT ANALYSISWATER CHEMISTRY IN PAPER MAKINGSOLUBILITY OF SALTS IN WATERSOLUBILITY PRODUCT CONSTANTSOLUBILITY PRODUCT CONSTANTS� COMMON SCALE TYPESCARBON DIOXIDE CHEMISTRYCALCIUM CARBONATE CHEMISTRYCARBON DIOXIDE SPECIES vs. pHCALCIUM CARBONATE SCALEALKALINITY TITRATIONSCALE FORMATIONSCALE FORMATION PROCESSREQUIREMENTS FOR SCALE FORMATIONSCALE DEPOSITION SCHEMATICNEGATIVE EFFECTS OF SCALEMINERAL SCALE HANDLING DEPOSIT PROBLEMSTREATMENT OPTIONSTREATMENT OPTIONSTREATMENT OPTIONSDEPOSIT CONTROL ALTERNATIVESCALCIUM CARBONATECALCIUM CARBONATEBARIUM SULFATEMANGANESE DIOXIDEIRON OXIDESSILICA & SILICATESFILLER DEPOSITSWET END CHEMISTRYALUMINUM SPECIES vs. pHALUMINA DEPOSITSSCALE INHIBITIONHISTORICAL PERSPECTIVELANGUAGE OF�SCALE CONTROLCHELATIONCHELANTS & SEQUESTERANTSCRYSTAL MODIFIERSTHRESHOLD INHIBITORSDISPERSANTSINORGANIC DEPOSITS CONTROLINORGANIC DEPOSIT CONTROL