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Microbes in the Papermachine Environment Linda Robertson TAPPI Monograph: Microorganisms in Papermaking Chapter 1 www.iMicrobial.com Independent consulting for industry PaperCon 2011 Page 2311
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Page 1: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Microbes c obesin the Papermachine Environment

Linda RobertsonTAPPI Monograph: Microorganisms in Papermakingg p g p g

Chapter 1

www.iMicrobial.comIndependent consulting for industry

PaperCon 2011 Page 2311

Page 2: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Mi b i P S tMicrobes in Paper System

Bacteria:filamentous* &filamentous &

single-cell Fungi Protozoa* Ameba* Rotifers * Worms* Algae* Algae

*primarily enter via inadequately treated water

PaperCon 2011 Page 2312

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Why do they grow?pH

Why do they grow?

TemperatureTemperature

Oxygen Levels

Nutrients

PaperCon 2011 Page 2313

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pH Preference of Microorganisms

Neutral/alkalinesizingsizing

Certainpigmentsystems

Kraftliquors

Whitewater

Rosinsizing

Acidbisulfiteprocess

Thio

baci

llus

Nitr

obac

ter

Most FungiT N

Orange

Most Bacteria

Most Fungi

pH

gJuice Pure Water Soap Ammonia

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

PaperCon 2011 Page 2314

Page 5: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Alkaline Vs. AcidAlkaline Vs. AcidAffect of pH on microbial growth

Acid Alkaline

Typical fungi filamentous bacteriaP d i t i l ll b t i i l llPredominant single cell bacteria single cell bacteriaOrganisms

Typical filamentous bacteria fungiMinor protozoa protozoaOrganisms algae algae

Biocide 1 X 2 - 4 XNeedsNeeds

PaperCon 2011 Page 2315

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Temperature Growth Ranges of Bacteriao Household Freezer-10oC Household Freezer

32oF 0oC

Psychrophiles 50oF 10oC Refrigerator

68oF 20oC

30oC

Mesophiles 98 6oF 37oC Human BodyMesophiles 98.6 F 37 C Human Body

40oC Paper Machines

122oF 50oC Starch Vats

140oF 60oCThermophiles 158oF 70oC Board machines

176oF 80oC

o o H t S iPaperCon 2011 Page 2316

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Oxygen Requirements ofOxygen Requirements ofMicroorganisms

PaperCon 2011 Page 2317

Page 8: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Why do we care aboutWhy do we care aboutWhy do we care about Why do we care about microbes?microbes?

PaperCon 2011 Page 2318

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Deposit scraped from machine & sheet defectmachine & sheet defect

Deposit from foilpan containing fungi & bacteria

Sheet defect and holePlastic bag

Paper

PaperCon 2011 Page 2319

Page 10: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Impact of microbes

• Reduced paper quality- Rejected paper- Rejected paper- Loss of customers

• Machine downtime• Machine downtime

• Decreased profitability- $14,000/hour loss due to downtime on high speed machine

based on $700/ton paper price

PaperCon 2011 Page 2320

Page 11: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Why do microbes grow?

• Machines contain: Fl id- Fluids

- Diverse microflora- Wood fibers, fines, sugars- Fillers- Various additives

PaperCon 2011 Page 2321

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Nutrients

• Sunlight • Sugars

• Contaminants• Cellulose

• Lignin• Lignin• Other microbes

• Minerals• Dilute biocides

PaperCon 2011 Page 2322

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i.e. machines contain:

Multiple & ideal i h fniches for growthgrowth

& &Food!

PaperCon 2011 Page 2323

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Industry changes resulting in y g gincreased microbial problems:Hi h d hi• High speed machines - Increased surface area at wet end/high misting

• Alk li H• Alkaline pH• Increased filler levels

I d l l• Increased recycle pulp• Water system closure• Lighter weight grades• Boilout interval changes

PaperCon 2011 Page 2324

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Detrimental microbial activity

• Deposits- Biofilm formation- Sheet defects

S il• Spoilage- Less visible often

overlookedoverlooked- Frequently occurs in:

• Chests• Additives

PaperCon 2011 Page 2325

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Microscopy of deposits

• Brightfield

• Stains

• Phase contrast

PaperCon 2011 Page 2326

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Unicellular bacteria

• Endospore stain of Bacillus colony

• Cells rod shaped• Endospores green

( l hit )(malachite)• Vegetative cells red

(safranin counter(safranin counter stain)

Spores brightfield stained 1000x

PaperCon 2011 Page 2327

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Bacterial Growth

Vegetative CellsCell Growth

PaperCon 2011 Page 2328

Page 19: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

MYTH

• If counts go up from 2 illi t 1 illi

• Unlike Enron or your b k t th imillion to 1 million

• YOU ARE IN terrible SHAPE!!!

bank account there is no statistical significance between 1SHAPE!!! significance between 1 million and 2 million

PaperCon 2011 Page 2329

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PLATE COUNTPLATE COUNT

1.0 mL 1.0 mL 1.0 mL

9.0 mL 9.0 mL 9.0 mLfurnish

100 101 102 103

1 mL

3210 103102101100

Petrifilm

PaperCon 2011 Page 2330

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Myth

• Not likely- many will not grow on

th di

• With a “total” count you can identify and count all of the the media you use

- many will not grow in the standard

count all of the microbes in the system

incubation time period- many have probably

never been identified!

y

never been identified!

PaperCon 2011 Page 2331

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Model of Biofilm Growth

M d

BULK LIQUIDMontana State University

Mondan

Planktonic

Sessile

SUBSTRATUM

PaperCon 2011 Page 2332

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Filaments

• Many speciesMany species

• Form long gstringers

• Alkaline to neutral machines

Phase-contrast 400x

PaperCon 2011 Page 2333

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Filamentous bacteria

Although “normal” bacteria they form long filaments that mat & trap materialsmat & trap materials.Many types have sheath structures that make them difficult to kill

PaperCon 2011 Page 2334

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Fungi

PaperCon 2011 Page 2335

Page 26: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Fungi AKA mold, yeast

• Form tough rubbery mats• Different from bacteria

genetically, respond to different biocideswet lap

• Seen in wet lap, recycle pulp, additives, acid

machines or alkaline

wet lap

machines, or alkaline using biocides with no

anti-fungal activity• End se prod ct iss e• End use product issue

- Mold-proofingconidia

PaperCon 2011 Page 2336

Page 27: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

• Algae enter the mill via inadequately treatedinadequately treated water- Fresh- Run off- Out door clarifier

• They need light to growThey need light to grow- Produce chlorophyll

• Found around light sources

• Green spots on paper• Safety hazardsSafety hazards

PaperCon 2011 Page 2337

Page 28: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

“higher” life forms

Microbes indicative of inadequate freshwater qtreatment. Excellent in wastewater treatment not on machine Highlynot on machine. Highly motileVideos on request……

PaperCon 2011 Page 2338

Page 29: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Non-microbial deposits

• In addition to wood fibers, fibrils, fines and fillers otherand fillers other materials deposit

• Mimic microbes:- Strength additivesStrength additives - Uncooked starch

granules

PaperCon 2011 Page 2339

Page 30: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Starch

Generic machine diagram

DIP Chest150 M3

Mixing Chest150 M3, 4%

M/C150 M3

3%, 70~80%Level Box

DIP Tower700 M3 H/B

1.2 %

Couch Pit

0 7% B k

Silo65 M3

screen

Decbculator

1 st

2 ndfan pump

Thickener water Cleaner

Water from cloudy

0.7%1556 L/m

BrokeTower700 M3

Calendar

Reel pit50 M3

3 hr

254 L/m

Thickener

4 0 % 484 L/

Seal Pit5 M3

Wire Pit100 M3

1 stfan pump

VacuumFresh waterHeat exchanger

Thickener waterShower water Vacuum

Cleaner Rewinder 1 hr residence

M

Super ClearRelay

RecoveryFiber80 M34.0 %

3432 L/m

4.0 % 484 L/m

Clear Relay

Broke Chest

150 M3

Pulp dilution0.005%, 3585 L/m

Or opportunities

Shower Pit 20 M3

Clear10 M3

Cloudy55 M3

yTank1 M3

yTank1 M3

Fresh water is treated with Cl2.

500 M3

M hi40 M3

ppfor microbial growth!

4000 tons/day

MachineShower water 2000 M3/day

40 M3

Broke system

PaperCon 2011 Page 2340

Page 31: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Fresh water

• All types of microbes enter mill via this route• Filamentous bacteria, algae, protozoa, worms

are so called “fresh water contaminates”• C iti l t t l f hi• Critical to control of machine

PaperCon 2011 Page 2341

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White water system

• Water is recovered and reused on machineW t filt d• Water filtered through saveall

• Issue covered in• Issue covered in Chapter 5

PaperCon 2011 Page 2342

Page 33: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Fiber-Virgin

Can be sterile if bleached with harsh chemistrieswith harsh chemistries

Then the microbes present come from dilution water

“Gentler” bleaching chemistries allow organisms to survive gand/or thrive

Recycle water used for dilution can be heavilydilution can be heavily contaminated

PaperCon 2011 Page 2343

Page 34: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Fiber-Broke Towers

Frequently heavily contaminated

Coated broke is loaded with nutrients to i i bi lincrease microbial activity

Anaerobic spoilageAnaerobic spoilage serious problem with pH depression, ORP reduction, fiber strength loss during storage

PaperCon 2011 Page 2344

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Fiber-Recycle

Often heavily contaminatedPeroxide bleaching may select

for bacteria that produce catalase and consume the bleaching chemical

Reductive bleaching chemicals can inactivate commoncan inactivate common biocides

Long storage times lead to anaerobic bacterial activity

PaperCon 2011 Page 2345

Page 36: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Fiber

• Dry lap• Wet lap

- Moisture allows growth

PaperCon 2011 Page 2346

Page 37: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Machine surfaces

• Headbox• Approach pipingpp p p g• Frame

Microbes prefer to attach to surfaces

Prevention of adhesion critical to d it t ldeposit control and reduction of sheet defects

Microbes and stickies from a closed machine

PaperCon 2011 Page 2347

Page 38: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Additives

• N t i t f i bi l th• Nutrients for microbial growth• Microbes destroy properties critical for functional

propertiesp p• Directly added/Indirectly in system via broke

PaperCon 2011 Page 2348

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Additives

• Dyes• Polymers• Fillers

- Clay- TiO2

- Carbonate• Protein• Latex

PaperCon 2011 Page 2349

Page 40: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Summary Chapter 1

• Microbial colonization of machines increases downtime and decreases profitability.

• Understanding the papermaking process and basicUnderstanding the papermaking process and basic microbial physiology is essential in diagnosing and solving problems.

• Biofilms form deposits that lead to sheet defects.

• Microbial spoilage of additives and fibers can alter pH, cause odors, and reduce sheet strength and quality. q y

PaperCon 2011 Page 2350

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Ch t 3Chapter 3:Control of Microorganisms in

P ki S tPapermaking Systems:Development of Treatment

St t iStrategiesAuthors: Lynda Kiefer & Tod StonerAuthors: Lynda Kiefer & Tod Stoner

Presented by: Janet H WoodwardPresented by: Janet H. Woodward

Commitment makes the best chemistry.

PaperCon 2011 Page 2351

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Introduction

• Microbial contamination can cause numerous issues- Holes- Defects- Off-spec paper (e.g. liquid packaging)

• Typical deposits seen in a paper machineTypical deposits seen in a paper machine are a combination of organics, inorganics, and microorganismsg g g

PaperCon 2011 Page 2352

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Key Elements of a Successful Microbial Control ProgramMicrobial Control Program• Engineering survey

• Microbiological survey

• Product selection

• Implementation / Follow-upImplementation / Follow up

• Housekeeping

PaperCon 2011 Page 2353

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Engineering Surveys• Three major systems of concern• Three major systems of concern

- WaterSt k- Stock

- Additives• Tank/Chests• Tank/Chests

- Volumes / capacity / flowsAgitation- Agitation

- Sampling points

PaperCon 2011 Page 2354

Page 45: Microbes in the Papermachine Environment - TAPPI pptA.pdfImpact of microbes • Reduced paper ... “higher”life forms Microbes indicative of inadequate freshwater ... Microbes in

Engineering Surveys, Con’t• Recycle lines / Dead legs• Recycle lines / Dead legs• Freshwater / Dilution water sources• Temperature and pH• Process additives• Current biocide program• Grades producedp

PaperCon 2011 Page 2355

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Pulp Processing Paper Machine Flow Diagram

Thick StockFW Makeup

WWChest

Thin StockWhite Water

Recovered Stock Gwd Broke

To Showers

Biocide

Biocide Blend Mach.Chest

Flow Box

Fan Pump

SaveallChest

Screens

Refiners

pSilo Fan Pump

KroftaAbsorption

TankHydro-Sieve

Makeup from WW Chest

Felt Pit Headbo

Felt WaterTank

KroftaTank

Felt & Wire

Pulp

HeadboxClarified

Water Tank

Felt & WireShowers

Wire Pit TrayPulp Processing

PaperCon 2011 Page 2356

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Microbiological SurveyG l i bi l i l f hi• General microbiological survey of machines- Visual observations, odors, collecting

d it th i d ti d tdeposits, gathering production data• Deposit analysis

- Microbiological analysis of deposits• Can include wet mounts, simple stains, differential stains• Looking for type of organism(s) and quantity

- Chemical analysis (inorganic salts, organics)

PaperCon 2011 Page 2357

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Microbiological Survey, Con’tMi dit f• Micro audit of process waters, additives, stock chests

H d h ld b d- pH and temperature should be noted- Plating for aerobic/anaerobic

bacteria fungi other problem causingbacteria, fungi, other problem-causing organisms

PaperCon 2011 Page 2358

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Paper Machine Deposit Analysis

Inorganics Organics Biological

Calcium

Aluminum

Fatty acids

Rosin acids

Bacteria

FungiAluminum

Silica

Iron

Rosin acids

Machine oils

Cellulose

Fungi

Algae

ProtozoaIron

Barium

Clay

Cellulose

Lignin

Dyes

Protozoa

Nematodes

Clay Dyes

Polymers (size)

PaperCon 2011 Page 2359

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Product Selection• Microbiocides• Microbiocides

- Biocide (slimicide; quick killer)Kill i i• Kills microorganisms

• Used for wet-end applicationsBiostat (preservative)- Biostat (preservative)• Inhibits reproduction; doesn’t necessarily kill• Used for stock broke and additive preservationUsed for stock, broke, and additive preservation

- For an effective biocide program, have to consider:• Product• Contact time• Concentration

PaperCon 2011 Page 2360

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Product Selection• Regulatory requirements• Regulatory requirements

- Environmental Protection Agency: All microbiocides must be registeredmicrobiocides must be registered

- Food and Drug Administration: Four allowances that affect microbiocides used in the production ofthat affect microbiocides used in the production of paper/board that may contact food• 21 CFR § 176.300: Wet-end applications• 21 CFR § 176.170: Dry-end applications where

paper/board may contact aqueous or fatty food (strictest regulation)regulation)

• 21 CFR § 176.180: Dry-end where paper/board may contact dry food (e.g. cereal boxes)

• 21 CFR § 170.105: Adhesive applications

PaperCon 2011 Page 2361

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Product Selection• Regulatory requirements• Regulatory requirements

- Parallel regulations in Canada and EuropeS f /• Safety / Environmental- MSDS- Discharge permits

PaperCon 2011 Page 2362

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Product Selection• Oxidizing biocides• Oxidizing biocides

- Hypochlorous acid, hypobromous acid, chlorine dioxide chloramine chemistriesdioxide, chloramine chemistries

- May be “stabilized”; e.g. hydantoins Typically applied on a continuous basis- Typically applied on a continuous basis

• Organic biocides- Organosulfurs, organobromines, cationics, isothi

azolones, and aldehydes T i ll li d i t itt t d i- Typically applied on an intermittent dosing

• Non-biocidal technology- Enzymes, biodispersants, and adjuvants

PaperCon 2011 Page 2363

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Lab-Based Bioassay Screening(Biocide Dose Response Study)(Biocide Dose Response Study)

Control Biocide Biocide BiocideConc #1 Conc #2 Conc #3Conc. #1 Conc. #2 Conc. #3

Incubate with Aeration

Count Bacteria at Time = 0 and Appropriate Intervals

% Kill = 1 – Treated Count x 100% Kill 1 Treated Count x 100Control Count

PaperCon 2011 Page 2364

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Biocide Dose Response Curve

8090

100K

ill 607080

%

304050

01020

Biocide Dose (ppm)

0

0 2 4 6 8 10

(pp )

PaperCon 2011 Page 2365

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Field Evaluation of Biocides(Biocide Pulse Test)(Biocide Pulse Test)1. Biocide is pulse-

fed (slug dosed) to 140,000

Pulse addition of biocide( g )a tank to achieve target dose immediately

100,000

120,000

immediately2. Bacterial counts

taken over time60,000

80,000

cfu/

ml

taken over time with no further biocide added 20,000

40,000

3. See effect of dilution

00 5 10 15 20

Time, min.

PaperCon 2011 Page 2366

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Monitoring and Follow Up• P f ti it i• Perform routine monitoring

- Machine runnability, quality, defects, deposits, etc• Compare new program to old one• Compare new program to old one

Machine Downtime Due to Wash-ups

T itiTransition

PaperCon 2011 Page 2367

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Summary• Monitor microbiological contaminants throughout• Monitor microbiological contaminants throughout

the process- Utilize chemical analyses as neededUtilize chemical analyses as needed

• Define biocide treatment with lab studies and confirm with field testing- Evaluate best options

• Follow biocide manufacturers recommended d i d f t i f tidosing and safety information

• Follow up with routine monitoring- Do not allow microbiological problems to get

established; they are easier to prevent than to remove

PaperCon 2011 Page 2368

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Effect of Water Recovery & Reuse on Microbial Activityon Microbial Activity

Linda RobertsonTAPPI Monograph: Microorganisms in Papermaking

Chapter 5p

www.iMicrobial.comIndependent consulting for industry

PaperCon 2011 Page 2369

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Water

• 21st Century severe competition for planet’s21st Century severe competition for planet s resources

• Historically mills sited near abundant watery• Water critical:

- Pulping, p g,- Chemical dilution- Process makeup, etc.

• Treatment of incoming and exiting water expensive

PaperCon 2011 Page 2370

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Costs of an Open System

• water treatment• chemicals loss• fines loss• fines loss• energy

PaperCon 2011 Page 2371

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Optimizing Water

• Conservation- Example: minimize water loss by shutting off continuously

running hoses• Water Reuse• Water Reuse

- Reclaim water from one source and use it in another without making changes to water qualityg g q y

• Water recycling- Improve the water quality before reuse- Becomes more expensive

PaperCon 2011 Page 2372

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Degree of closure

• Difficult to define- zero effluent- tons or gallons of fresh

water/ton of paper

• Water use- 1993 Panchapakesan

water/ton of paper• Grade specific

- fine vs board mill

• <19 m3/t good• 19-30 m3/t average• >30 poorfine vs. board mill

- many board mills zero effluent

30 poor- 2005 fine papermachines

• 12-15 m3/t common• 9-11 m3/t frequent• China reports 5-6 m3/t

PaperCon 2011 Page 2373

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Changes in operational practices increase microbial problems:

- Water system closureWater system closure• Noxious chemical cycle up• Nutrients cycle up• Stagnant chests

- Neutral to alkaline conditions allow anaerobes to thrive

- Increased use of recycle fiber• Coatings on paper• “Extra” nutrients and contaminants• “Poorer’ quality recycle fiber

- Large chests constructed with long dwell timesLarge chests constructed with long dwell times- Reduced biocide programs due to cost constraints

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Freeze dried/cycled up water

Water Analys is In ppm: Inductively Coupled Plasma Argon Analysis: Sodium 81 900Sodium 81 900 Calcium 46 440 Magnesium 5.4 58 Aluminum 1.5 15 Iron < 0.1 0.3 Potassium 2.5 28 Manganese < 0.1 0.5 Phosphorus < 0.1 0.5 osp o us 0. 0.5Sulfur 43 470 Ion Chromatography: Chloride 53 550 Nitrite (NO ) < 2 9 < 2 9Nitrite (NO2) < 2.9 < 2.9 Nitrate (NO3) < 2.9 < 2.9 Sulfate (SO4) 120 1200 COD (Filtered) 430 4100

As received Concentrated

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anaerobic problemsanaerobic problems!!!

OdOd

H2S

PropionicOdorOdorButyric

Acetic

Toxic GasesToxic Gases

AcidsAcidsAcidsAcids

E l iE l i

H2SH2

ExplosionsExplosions

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Mill Safety Issues• H S & H h d d th f k i• H2S & H2 have caused deaths of workers in

industry- Known problemKnown problem- More serious in recycle systems

• Hydrogen Sulfide- Detected by the human nose at 0.1 ppm- 3 ppm the odor is objectionable- 10 ppm health affects are noticeable (headaches)pp ( )- 100 ppm people lose their ability to smell.- By 300 ppm life threatening.

1000 ppm the person goes into irreversible respiratory failure- 1000 ppm the person goes into irreversible respiratory failure- Found at 55 ppm in gypsum mill- Linerboard 45-300 ppm over walk space & chests

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ORP/oxidative reductive potential• Available electrons measured with an

ORP probe (platinum electrode) to i RELATIVE V di f give RELATIVE mV readings of

oxidizing (+mV) or reducing (-mV) conditions.

• Typically a fine paper oxidizing program will have ORPs in the headbox in the range of +200 to +300 headbox in the range of +200 to +300 mV

• Closed reductive systems will be lower

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RPTA & IPST Survey of board millsSurvey of board mills

• Corrosion- Not as severe as

predicted• Presence of corrosion

• Minimize Problems by:• Presence of corrosion

elements- didn’t correlate to:

- Treating Recycled water

didn t correlate to: • extent of corrosion • degree of closure

- Upgrading construction materials

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Acidic microbialodors (VFA)

Miscellaneousmicrobial odors

Chloranisoles

Figure 1. Examples of odors found in paper and paperboard products causing organoleptic complaints

Butyricrancid butter Geosmin

musty 2-methylisoborneolmusty

Chloranisolesmusty

Valericdirty socks

Aceticvinegar

examples of

PropionicSwiss cheese

Putresceneputrid, nauseatingH2S

rotten eggsat machine & air

manure

e a p es omalodors in paper

productsHexanal

green, fruity Cleaning agentscitrus, green

Butanalsharp, pungent

Oilb d i k

Heptanalgreen, soapy

Pentanalrancid, green

M th l i thi t

PetrochemicalKerosene

Oilbased inkspetroleum

Chlorophenolsmedicinal

from printing solvent 4-methyl-4-mercaptopentan-2-1

"catty"

Octanalcitrusy, sweet,

fruity

Autooxidized wood

Methyl isothiocyanatefishy, sulfur

Aminesrotting fish

Styreneplastic

Nonanalcitrusy,

sweet, fruity

Perfume (recycle) flowery, spicyDecanal

fatty, sweet

medicinal

resins Miscellaneousodors

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White water system

• Water is recovered and reused on machineW t filt d• Water filtered through saveall

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Microbiologically

• Treated whitewater for pulp dilution excellent

• Stagnant recovered water for dilution a serious problem

f• Treated whitewater for starch makeup is still a problem due to endospores and amylase producers

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Volatile Fatty Acid Odor Case St dStudy

• Recycle mill with 2 machines with same yfurnish, water and additives

• Odor increased when water discharge decreased from 946 m3/day to 340 m3/daydecreased from 946 m day to 340 m /day

• Paperboard from cylinder machine (#1 PM) had foul aroma- heavyweight stock (535 g/m2) with a moisture content

averaging 6%• Paperboard from Fourdrinier (#2 PM) p ( )

acceptable- lighter weight board (150-g/m2) had slightly lower

moisture content (5%)moisture content (5%)

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VFA levels in finished board made from each machinemachine

PM#1 board had complaints

1200

1400

PM#1 board had complaints

800

1000

fatty

acid

matog

raph

y

400

600

ppm

volat

ilevia

gas

chro

m

0

200

v

acetic propionic butyric total VFAPM#1 Board 1006 142 192 1340PM#2 Board 800 110 124 1034

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VA levels in process waters conducted at the mill site for 5conducted at the mill site for 5 months

1600

1400

1500

1200

1300

ds in

ppm

1000

1100

Vola

tile

Aci

800

900

#1 PM Cylinder #4 vat

700

26-Ju

n

29-Ju

n

1-Ju

l

6-Ju

l

12-Ju

l

14-Ju

l

25-Ju

l

2-Aug

7-Aug

21-A

ug

7-Sep

2-Oct

19-O

ctav

erage

#1 PM Cylinder #4 vat#2 PM Fourdriner tray

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VA & VFA matched set comparison of process fluidscomparison of process fluids and board

volatile acids*

"total" VFA** Acetic** Propionic** Butyric**

PM#1 vat cylinder water 2025 1895 1400 160 335

PM#2 tPM#2 tray water 2088 1860 1370 160 330

PM#1 Board no data 2545 1930 175 440PM#2 Board no data 1530 1140 130 260 *HACH method **GC method

Reported as parts per million

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Key Discoveries• Board formed on #1 machine had higher VFA

concentrations and odor complaints• Both machines had:

- Similar populationsSi il ORP R- Similar ORP Ranges

- Similar VFA levels in the fluids- Similar biocide programs- Similar biocide programs

• Moisture content:- #1 is 6%#1 is 6% - #2 is 5%

• Less VFA is volatilized during drying in theLess VFA is volatilized during drying in the high odor paperboard

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VFA Case Study

• Understanding machine operations, microbial metabolism and how this influenced odor in the finished board led to changes in biocide programto changes in biocide program

• Lower VFA targets needed on machine producing the heavyweight board due toproducing the heavyweight board due to higher carryover of VFA.

• The problem-solving approaches and program changes used at this mill nearly eliminated odor complaints.

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Biocides and closure

• Certain biocides may not function as well under changed ORP conditionsORP conditions- Isothiazolins/DBNPA/etc.

• O id t d d i d ti ll• Oxidant demand can increase dramatically- Chlorine/bromine/and other oxidants

Odif bi id lik b t b ti bl• Odiferous biocides like carbamate may be more noticeable

• Tolerance or resistance may develop more rapidly- Glutaraldehyde/quaternary ammonium

compounds/peroxides/isothiazolins/etc.

• R i k l d t d id bl• Requires knowledge to manage and avoid problems

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Water Sources• W ll i i• Well, reservoir, river

- Normally easiest to treat and purestUse for chemical dilution nutrients: protein starch- Use for chemical dilution---nutrients: protein starch

• Water reused within mill- Known quantity- Known quantity- Best used for pulp dilution, showers

• Biologically stabilized waterBiologically stabilized water- Reduces sugars/BOD- Reduces VFA odor on machine- Purple water in California

• Reverse Osmosis- Closest to freshwater

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Summary

• Water Reuse is achievable with proper p pplanning

• This avoids• This avoids- Anaerobe problems- Odors- Hazardous gases

• Biocides• Biocides- may need to change type- may need to increase dosey

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Chapter 6:pBoilouts –

Chemical Cleaning Programsg g

Author: Doug CaulkinsAuthor: Doug Caulkins

Presented by: Janet H WoodwardPresented by: Janet H. Woodward

Commitment makes the best chemistry.

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Definition - Boilout

• Noun: A chemical cleaning solution composed of alkaline, acid or enzymatic cleaning agents in combination with penetrants, dispersants and water

• Verb: A periodic chemical cleaning of the p gpapermaking system under controlled pH and temperature conditions

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Goals of a Boilout

• Remove organic and inorganic build-up in and on process equipment, tanks, lines, filters, chests etc

• Remove deposits that can break loose and cause holes and breaks

• Clean the forming fabricg• Housekeeping = Runnability

- Regular boilouts combined with simple- Regular boilouts combined with simple housekeeping measures can account for up to 60% of the overall success of a deposit control program

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Benefits of a Boilout• Prevent premature buildup of

microbiological deposition- Reduce costs associated with slime control

program• Prevent corrosion pitting• Prevent corrosion pitting

- Anaerobic activity underneath scale, stock, and biofilm cause microbiologically induced g ycorrosion

• Control/eliminate scale formation- Long term scale deposits can restrict flow

• Removal of organic deposits- Can cause sheet defects if not removed

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Boilout Components• C ti (S di H d id )• Caustic (Sodium Hydroxide)

- 2-5% typical use levelDo not exceed pH 13- Do not exceed pH 13

- Enables saponification and emulsification of hydrophobic organic components

- Kills slime forming bacteria and fungi• Acid (Sulfuric)

- Use level dictated by consumption during boilout- Critical to monitor pH and temp during boilout as

potential for corrosion is higher than with causticpotential for corrosion is higher than with caustic boilout

- Mostly used to dissolve CaCO3

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Boilout Components• O i t t & di t• Organic penetrants & dispersants

- 0.1-0.5% typical usage rates- Main purpose is to speed up process by softening- Main purpose is to speed up process by softening

inorganic deposits• Inorganic dispersants & chelants

- Wide variety, tailored to specific types of inorganic deposits Most act through anionic dispersion and crystal- Most act through anionic dispersion and crystal modification

• Foaming agentsg g- Carry boilout solution to areas not normally reached

• Fiber- Scrubbing action

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Typical Boilout ProcedureP b il t h• Pre boilout wash-up

• pH of 12 - 12.5- P alkalinity must be maintained between

10,000-15,000 ppm• pH 2 – 3 for acid• Temperature of 130° - 145° Fp• Re-circulation for 1 to 3 hours• Post boilout wash up very important!• Post boilout wash-up - very important!• Neutralization of boilout solution during

dump to effluentdump to effluent

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Alternatives to Traditional Boilouts• E• Enzymes

- 0.1-0.5% typical usage ratesProprietary combinations of dispersants and- Proprietary combinations of dispersants and surfactants such as Buzyme® Boilout Programs

- Effective in removing MB, starch, cellulosic and protein containing deposits

- Alternative if high or low pH solutions are problematic• N t l H B il t• Neutral pH Boilouts

- Use of dispersants and penetrants with standard temperature and timetemperature and time

- No adjustment of pH

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Pre‐boilout

After enzyme boilout

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Summary

• Successful boilouts depend on:- Adequate timeAdequate time- Proper pH (alkalinity)- Correct temperatureCorrect temperature- Solution formulation- Proper wash up after the boilout- Proper wash-up after the boilout

PaperCon 2011 Page 2401


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