Lecture:

Wash Deinking
 Deinking Washers

 Definition: a separation device that rinses

small particulate contaminants away from
fibers (opposite of screening)
 Deinking Washer:
 Dilutepulp with wash water
 Disperse small contaminant in water phase,
sometimes aided with a dispersant chemical
 Remove contaminant laden water
 Deinking Washers

 Washers in recycling remove all of the

following small contaminants
 fines
 filler
 inks
 dissolved species
 In order for washing to be successful,
the intended contaminant must be small
and must be detached from the fibers
Washers Wire Mesh Sizes
Mesh Wire Open Opening
Size Diam, Area, % Size,
mm mm
40 .254 36 0.425

60 .191 30.5 0.250

80 .140 31.4 0.180

100 0.114 30.3 0.150

 Inks & Toners
Note: wash wires around 250 micron openings

Type Component Drying System Ink Resin Film Particle Size End Products
(microns)
Simple Letter Pigment + Absorption Weak 1-15 Letterpress
Press Mineral Oil into Web Early
Newsprint
Newsprint and Pirgment + Penetration of Soft Film 2-30 Newsprint,
Offset Soft Resin & Vehicle into Books
Mineral Oil Web + Resin
Oxidation Hard Film We Offset,
Letter Press
Rotogravure Pigment Solvent Hard Film 2-250 Magazines,
+Hard Resin & Evaporation Catalogues
Solvent
Flexographic Pigment + Amine Water N/A Newsprint
Resin & Water Absorption, Resistant Film inserts,
Emulsification Evaporation Corrugated
UV Cured Pigment UV Non swelling, 50-100 High Speed
+Monomer Photopolymeri Non saponif. Coated
zation Hard Film Papers
Specialty Various Heat set or Hard, 40+-500 Xerography
Pgiments and Other Coherent Laser Printers
Rosins Films Electronic
Forms
 Sizes of fibers and inks:
Note: wash wires around 250 micron openings

0.001 inch = 1 Mil = roughly 25 microns = .025 mm

 Sizes of Clay Fillers
Note: wash wires around 250 micron openings
 Clay, from Hubbe (left). Clay particles magnified by an electron microscope.
drainchem.com.au (right)

Thickening vs. Dilution Washing

 Thickeners
 purpose to increase consistency
 fiber mat formation ok
 lower yield losses
 Deinking (Dilution) Washers
 purpose is to remove contaminant particles
 fiber mat formation avoided
 higher yield losses
 Pulp mats prevent the removal of small
particles in washing.

Ash Ash
Type Inlet % K Outlet % K Removal %, Removal %, Pulp Mat
Theoretical Actual Formation
Sidehill Scrn 0.8 3 74 60 Minimal
Grav Decker 0.8 5 85 55 Yes
Incl. Screw 3.0 10 72 45 Extensive
Horiz. 4.0 28 89 35 Extensive
Screw Press
Belt Washer 1.0 10 80 Minimal
Vario Split 0.8 10 85 80 Minimal
 Types of Washers

 Low Consistency Washers

 Intermediate Consistency Washers
 High Consistency Washers
 Low Consistency Washers

 Up to 8% discharge consistency
 side-hillscreen
 gravity decker
 DSM screen
 Hydrasieve
Sidehill Screen
 Gravity Decker

 Pulp enters at 0.8%

and leaves at 5%
 Water passes
through wire mesh
cylinder
 Vacuum created by
liquid falling
increases water
removal
Gravity Decker
 Intermediate Consistency Washers

 8-15% discharge consistency

 high speed belt washer
– DNT
– Vario-split
 Vacuum filter
 inclined screw extractors
Double Nip Thickener
 Double Nip Thickener

 DNT Washer
 “double nip
thickener”
Disk Filter:

Filtrate
Laden
With
Ink
Vacuum Disk Filter
Mainly for thickening
 Overview

Overview
Disks
 High Consistency “Washers”

 Not really designed as washers, but

more designed to thicken
 Above 15% discharge consistency
 screw press
 belt press
 Wet lap pulp machine

 Low to small contaminant (ink) removal

efficiency
Screw Press
 Pressing

 HC-Press
 Wet-Lap Pulp Machine

A double-wire press is utilized for initial dewatering of the stock

to achieve up to 40% bone-dry consistency. The dryness is raised
to 48-50% bone-dry by a heavy duty press. The pulp web is then
slit and cut into sheets by a rotating knife drum. The sheets drop
onto a pallet.
 General concepts in washing:

 There are several equipment variables

and operating variables that determine
the washing efficiency
Washers Wire Mesh Sizes
Mesh Wire Open Opening
Size Diam, Area, % Size,
mm mm
40 .254 36 0.425

60 .191 30.5 0.250

80 .140 31.4 0.180

100 0.114 30.3 0.150

 Pulp mats prevent the removal of small
particles in washing

Ash Ash
Type Inlet % K Outlet % K Removal %, Removal %, Pulp Mat
Theoretical Actual Formation
Sidehill Scrn 0.8 3 74 60 Minimal
Grav Decker 0.8 5 85 55 Yes
Incl. Screw 3.0 10 72 45 Extensive
Horiz. 4.0 28 89 35 Extensive
Screw Press
Belt Washer 1.0 10 80 Minimal
Vario Split 0.8 10 85 80 Minimal
Washing Performance:
Particle Removal Efficiency
Washing Performance
Theoretical Ink Removed In One Washing Stage

Outlet %K
 Washing Performance

 Countercurrent washing
Pulp
Pulper
Filtrate

No. 1 Washer

No. 2 Washer

No. 3 Washer

Clarifier
 Washing Performance:
Counter Current Flow of Pulp and Water
Theoretical Ink Removed In Multiple Counter Current Washing Stages
Lecture:

Flotation
 Flotation

 Definition: a process in which

contaminants are preferentially removed
from a pulp stock by attachment to air
bubbles.
Ink particles
attached to air
bubble
 Flotation

 In 1992, about 80% of the de-inking

plants in the US used flotation
 Since the 1950’s flotation cell design
has steadily improved
 Example Flotation Cell
1. Air bubbles & low
consistency stock
introduced together.
2. Air bubbles & stock are
mixed. 5
3. Stock travels toward exit 3
4
of flotation device. 6
4. Air bubbles rise.
5. Foam removed as 2
rejects.
1
6. Accepted stock removed
from cell.
Voith Paddle Cell, 1960’s technology
 Flotation

 Mechanism: For successful flotation of a

contaminant (e.g., ink) several sub-processes must
occur:
1. The ink must be free from the fibers.
2. Ink must collide with an air bubble.
3. A strong attachment must form between the ink & the
bubble.
4. The ink-bubble must rise to the surface.
5. The ink-bubble must be incorporated into the foam.
6. The foam must be removed from the system.
 Flotation

 What determines the flotation efficiency?

 Contaminant characteristics

 Bubble characteristics

 Process conditions
Effect of Contaminant Characteristics on
Flotation Efficiency

 Given two types of particles suspended

in water, which one will attach and be
removed by an air bubble?
– Hydrophobicity
– Detachment from fibers
– Size
– Shape
– Density
Contaminant Characteristics: Hydrophobicity

 Hydrophobic - lacking affinity for water

 Hydrophilic - having a strong affinity for water.

A hydrophobic material suspended in water has a

greater tendency to contact and adhere to air bubbles
due to its lack of affinity to water.

This causes a preferential separation of hydrophobic

material in a flotation process.
Contaminant Characteristics: Hydrophobicity

 Hydrophobic - lacking affinity for water

 Hydrophilic - having a strong affinity for water.

Water Drop
Air Air

Hydrophillic Surface Hydrophobic Surface

 Contaminant Characteristics:
Detachment from Fibers

 Typical Cases
 Fibers attached to toners,
sometimes referred to as
“hairy particles.

 Inks or toners attached to

surface of fibers.

 Pigments from inks lodged

into wall of fiber.
 Contaminant Characteristics:
Ink size

 Ink very small: the ink travels around the

bubble in the stream line, does not have
enough momentum to cross stream line
and attach to bubbles
 Ink very large: ink’s weight and large
size promotes detachment from bubble
surface due to gravity and fluid forces
 Collector Soaps
 Historically, for ONP deinking,
salts of fatty acids combined
with calcium ions in the flotation
cell have been used to collect
fine ink particles into
agglomerates
 OMG added to provide ash for
agglomerates
 The agglomerates, because of
their size, are removed at
higher efficiency
 Synthetic Collectors

 Non-ionic and ionic surfactants

 Also called displectors because they can
disperse in washing and collect in
flotation
 Do not require calcium, reduces
deposits
 Lower dosages needed (0.2% rather
than 0.7% of fatty acids)
 Bubble Characteristics
 Size of bubble :
 If bubble is too small then the buoyancy force may not be
large enough to carry particle.
 If bubble is too small, then bubbles tend to adhere to fibers,
causing excessive fiber losses.
 If bubbles are too large, then the area of bubble surface is
small ( compared to smaller bubbles with same total volume )
and the probability of collision with contaminant is less.
 If bubbles are too large, then the bubbles tend to rise rapidly,
not offering many opportunities for contact with contaminants.
 The large, fast rising bubbles disrupt flow patterns in the
flotation cell causing channeling of bubbles and disruption of
the foam.
 Bubble Characteristics
 Quantity of Bubbles
 Increased number of bubbles have a higher
probability of contacting a contaminant.
 Too many bubbles may cause agglomeration of
the bubbles into larger bubbles, see proceeding
slide for problems with large bubbles.
 Air to stock ratio used depends on the type of
equipment, can be 0.3 : 1 or as high as 10 : 1 air :
stock
 Process Conditions

1. Consistency
The consistency is typically around or less than 1%. If the
consistency is too high, then the fibers tend to knock off (or
filter) the ink from the bubble surface.
 High consistency also causes a poor mixing/distribution of
bubbles in the stock. Bubbles tend to form channels in
which bubbles short circuit the flotation cell.
 High consistency can lead to excessive amounts of fibers
being rejected with the foam.
 Process Conditions
2. Foam Generation
 Foam is generated by adding a foaming agent to the stock
before the stock enters the flotation process.
 Too much foam causes excessive fiber losses, and increased
amounts of foam to destroy.
 Too little foam or an unstable foam will allow contaminants to fall
back into the stock and not be removed.
 The amount of foam is usually controlled by the flowrate of
foaming agent.
3. Flow Rate
 Too high a flow rate through a flotation cell generates large
turbulent forces which can detach inks from bubbles. It also can
disturb the foam. The required production rate sets a minimum
value on the flow rate.
 Process Conditions
4. Retention Time
 Longer retention times increase the likelihood of bubble-
contaminant collisions. Retention time is limited by production rate
demands and volume of existing equipment. Flotation cells are
often put in series to increase retention time.
5. Quality and Quantity of Air Bubbles
6. Waste Paper Furnish
 In the past, a certain percent of old magazine or coated material
has been added to old news print to enhance flotation.
 Suspected that the filler acted as a collection site for inks that were
more effectively floated.
 Fillers can also act to consume chemicals and break foam.
 Flotation Equipment

 Equipment
• Voith
• Fiberprep
• Sulzer
• BC
• Beloit
• Shinhama
• Kamyr
• Wemco
 Flotation Cell

 Black Clawson Flotator

Foam

Feed
Accepts
 Flotation Cell
 Voith-Sulzer Flotation Machine, each pump
in series, stock follows: feed->1->2->3>Acc.

Acc.
3
Foam Feed 2

Most prominent type of flotation unit with over 200 installations in the early 1990’s.
Overview
Trace Lines
Foam
 Flotation Cell
 Lamort - Fiberprep Flotation Cell
Flotation Cell
 Flotation Cell

 Pressurized Deinking Module

 Major Parameters Impacting
Flotation Efficiency

 Particles: number, size, shape, density,

surface chemistry, agglomeration
 Bubble: type of gas, number, size, surface
chemistry, nature (dispersed or dissolved)
 Mixing: Nature, intensity, time
 Process Conditions: Recovered paper,
type/amt ink, type/amt ash, fiber
characteristics, consistency, temp, retention
time, cell design, pH, chemical environment,
foam characteristics
Secondary Fiber Recycling, Tappi Press, 1993
 Washing vs. Flotation

Flotation Washing
Chemistry-Sensitive more less
Water Use lower higher
Yield higher lower
Ash Removal No Yes
Tensile Str. Lower Higher
Opacity Higher Lower
 Lecture:

Dispersion and kneading

 Dispersion of Contaminants in
Recovered Paper Stock

 Definition: The use of mechanical action to decrease

the particle size of contaminants and release the
contaminants from the fiber surfaces (below, an
example of pulp before and after dispersion).
 Dispersion of Contaminants in
Recovered Paper Stock

 Contaminants: inks, toners, coatings, wax, bitumen,

varnish, hot melts, glues
 Dispersion assisted by heating, contaminants soften
from 60 – 120 C
 Visible size (40 microns) to sub-visible size
 Disk Dispersion
 How does it work?
 Pulp at high consistency is passed between disks that have
bars or teeth protruding from the surface.
 Rotation of one of the disks causes intense shearing action
on the fibers breaking down the contaminants.
 Typical Conditions
 Consistency = 30% K
 Temperature = 95 C
 Retention Time = 2 seconds
 RPM = 1200-1800
 Gap between disks = 0.5-1.5 mm
 1.6-4.0 hp days / ton
 Dispersion

Exit

Teeth
Rotating Shaft

Feed
 Dispersion
 Dispersing System:
 Process stock is
dewatered to 30%K
 Clods of stock are
broken in the
breaker screw
 Steam introduced
into a heating screw
to increase
temperature to 85-
120 C (above 120 C
damages fibers)
 Stock fed to
dispersing unit
 Stock is diluted and
agitated for further
processing
Screw press
Steam Preheater
 Dispersion Unit

Motor

Disperser
 Kneading
 How does it work?
 Pulp at high consistency is mixed between moving bars on a slow-
rotating shaft and stationary bars attached to the housing.
 Strong shear forces (mainly fiber-fiber rubbing) break the
contaminants.

 Typical Conditions
 Consistency = 30% K
 Temperature = 40-50 C
 Retention Time = 10-60 seconds
 RPM = 100-900
 Gap between bars = 10-40 mm (compare to dispersion at 1 mm gap)
 3.0-4.5 hp days / ton
 Single Shaft Kneader
 Process stock is dewatered to 30% K
 Stock enters a feed screw, steam or bleaching chemical may be added
 Stock is kneaded
 Stock is discharged, diluted and agitated for further processing
 Double Shaft Kneader
 Operation principles the
same as the single shaft
kneader
 Contains two shafts rotating
in different directions at
slightly different speeds (20%
difference in RPM)
 The different speeds and
directions of the shafts
generate intense shearing
action.
Double Shaft Kneader
 Drawbacks to Kneading

 Energy intensive: 3.0-4.5 hp day/ton

 High initial capital cost
 Requires thickening equipment
 Does not reduce sticky size (this may be
an advantage)
 Rotors can wear out (1-2 years)
Kneading vs. Dispersion
Methods to decrease contaminant size.

Dispersion Kneading
Mechanism Shear Rub
Consistency 30% 30%
Temp. 95 50
RPM 1200-1800 100-900
Retent. Time 2 s 10-60 s
Gap, mm .5-1.5 10-40
 Kneading vs. Dispersion
Methods to decrease contaminant size.

Effect Dispersion Kneading

Tappi Dirt Reduct. 75% 85%
Toner Reduct. yes better
Stickies Reduct. better no effect
Fiber Cutting substantial none
Fines Generation yes no
Lecture:

Bleaching
 Bleaching

 Bleaching is the chemical process applied to

cellulosic materials to destroy chromophores,
increasing the brightness and reducing color
 Chemical reactions
 Oxidative,like peroxide
 Reductive, like Sodium hydrosulfite and
FAS
 Bleaching
 Dye destruction
 Fluorescent Whitening Agents (FWA) Destruction
 Destruction/modification of lignin from lignin-containing fibers
 Does not affect pigments, which have color due to the lattice structure
of molecules (like carbon black or titanium dioxide)
C
CH2 OH
CH2 OH
HC O
CH3 O HC O
CHO HCOH
CH
HC
O CH CH2 OH
CH
OH
OCH3 Reflected Incident
CH2 OH
CH3 O
OH
HCOH CH3 O
O Light Light
CH3 O
O CH CH2 OH HOH2 C C CHO
OCH3
HC OH HC O O
H2 C CH
HCOH CH3 O
CH2 OH HC CH

CH2 OH HO CH HC
O
CH2
Paper Sheet (Absorption)
O CH CH O OCH3 HCOH
3
HC O
OCH3
“Chromophore
HOCH2 HOH2 C
CH3 O
O
Absorbs Light”
HC
C O
OCH3 HC O Transmitted
HCOH

Light
CH2 OH H2 COH
CH3 O
O CH OCH3
HC O
HCOH C O

CH3 O OCH3
OH OH [O-C]
 Brightness Measurement
 Tappi Method T452
 Specifies illuminating light at 45o to the sample and the reflected
light measuremement at 90o to the sample. Reflectance compared
to magnesium oxide powder.
Units: % GE brightness
 Technical Section, CPPA Method E1
 Specifies the sample should be diffusely illuminated using a highly
reflecting integrating sphere. Reflected light measurement is at 90o
to the sample. Reflectance is compared to absolute reflectance
from an imaginary, perfectly reflecting diffusing surface.
Units: %ISO brightness
Brightness Scales
 Color Measurement
 Several color coordinate
systems
 L, a, b color space
 L light or dark
 The a coordinate: red or green
 The b coordinate: yellow or
blue
 Dye removal index uses L*,
a*, b* coordinates to
determine dye removal
effectiveness
 http://www.zeiss.de
 Fluorescence Measurement
 Fluorescent whitening agents: ultraviolet energy is
absorbed and re-emitted as visible light,
increasing the brightness

 To measure Fluorescence:
 Measure Normal Brightness with UV light shining on
sample
 Measure Brightness with UV filter that blocks the UV
light from shining on the sample
 If there is a difference in the two brightnesses, there is
FWA present
 Paper Fibers
 Cellulose and hemicellulose:
 white, colorless, do not absorb light
 Lignin and extractives:
 have some color, especially when modified
 alkaline environments increase the color producing
groups in lignin
– kraft chemical pulping
– Semi-chemical pulping
– Alkali used in ONP recycling to liberate inks and swell fibers
 Dyes absorb light causing color and decreasing
brightness
Chemical structure of colored extractives
and groups in wood and lignin

 It is the conjugated
double bonds
(alternating single and
double bonds) that
cause color

 Ref: Papermaking Science and

Technology, Book 7, Recyled Fiber
and Deinking, Tappi Press.
Dyes
 Dyes and printing inks
contribute to the color of
fibers
 It is the conjugated
double bonds that cause
color

=
 Peroxide Bleaching (P)
 The most important bleaching agent for
mechanical recovered paper pulps
 A clear, colorless liquid soluble in water at any
concentration
 HOO(-), perhydroxyl anion acts as a
nucleophilic bleaching agent
 H2O2 + H2O <-> HOO(-) + H3O(+)
 H2O2 + OH(-) <-> HOO(-) + H2O
 Oxidation reactions are irreversible
Peroxide Bleaching (P)
 The most
important
bleaching agent for
mechanical
recovered paper
pulps
 Bleaches in a non
delignifying
manner by
destroying the
chromophore
 Irreversible
 Peroxide Bleaching

 Sodium hydroxide (NaOH) is added to increase

the perhydroxyl anion concentration, the active
bleaching agent, HOO(-):

 H2O2 + H2O <-> HOO(-) + H3O(+)

 H2O2 + OH(-) <-> HOO(-) + H2O
Peroxide Bleaching
 There is a non linear
relationship between
H2O2 and bleaching
performance
Peroxide Bleaching
 There is an optimized
amount of NaOH to add,
 too little and not
enough activation,
 too much and the alkali
yellows the pulp
 Peroxide Bleaching Process
Conditions
 Application: 1-3% on pulp solids, typically less than 2%
 Time: 30-90 minutes
 Consistency: 10+%
 Temperature: 60-90 C
 pH: 9.0-11.5
 Good mixing
 Peroxide Bleaching Process Conditions: Consistency

Two reasons

Higher concentration of bleaching

chemical

Less liquid phase, less trash to

interfere with bleaching
 Peroxide Bleaching
 Heavy metal ions or enzymes (catalases) can
decompose the peroxide
 H202 -> 2H0* -> -> H2O + ½O2
 Must stabilize the peroxide so it won’t form HO*:
 Chelating agents: form complexes with the heavy metal ions to
deactivate them
 Most common: EDTA and DTPA

 HO* does two bad things

 Itsgeneration decreases the available
bleaching agent
 Can damage the cellulose in the fibers
 Peroxide Bleaching:
Decomposition of Peroxide
 Causes of hydrogen peroxide decomposition
 Metal Ions
 Catalase:
– an enzyme produced by microorganisms and animal and
vegetal cells to destroy peroxide which is toxic to the cell
– Must thermally denature the catalase by use of a biocide
 Too High pH
 Too High temperature
Peroxide Bleaching: Chelating Agents
Peroxide Bleaching: Sodium Silicate
 Heavy metal ions can
decompose the
peroxide
 H202 -> 2H0* -> ->
H2O + ½O2
 Where HO* is a
radical, not the
bleaching chemical
desired
 Must stabilize the
peroxide so it won’t
form HO*:
 Sodium Silicate or water
glass, Na2SiO3
 Forms a colloidal structure
with metal ions and
deactivates them
 Also added to pulper as a
surfactant, penetrant and
anti-corrosion agent
 2-3% is normal
 Peroxide Bleaching: Pulper
 Not used as a true bleaching
chemical in the pulper
 Used to actually compensate for the
darkening due to alkali in the pulper
 Used to decolorize chromophores in
groundwood generated by alkaline
pH – prevents alkali darkening
 Much of the contaminants in pulper
render the bleaching action poor
 Peroxide Bleaching: Disperser or Kneader

 Used to compensate for graying

of pulp due to the dispersion of
the ink
 Advantages
 Newly exposed fiber surfaces
 High consistency
 Good mixing
 High temperature
 Disadvantages:
 Short residence time
 Too high a temperature can
degrade pulp
 Must use chelating agent as silicate
may build up on disks
 Peroxide Bleaching: Tower
 More efficient than pulper
 Controlled reaction time
 Added to suction of medium
consistency pump to upflow
tower
 Caustic and silicate added
to conveyor to medium
consistency standpipe
Peroxide Bleaching: Post-bleaching

 In the high density storage chest/tower

 Pulp is thickened and heated with steam to 60 C
 High shear mixer with chemicals added at one addition
point a preparation
 1-3 hrs at 15 % consistency
 If market pulp, must be neutralized to pH of 7 to avoid
degradation
High Density
Storage Tower
 Dithionite Bleaching (Y)
 Common reductive bleaching chemical that can be
used for wood containing pulps
 Good at color stripping dyes
 Often called hydrohydrosulfite bleaching, which is the
incorrect term
 Na2S2O4 + H2O -> 2Na(+) + S2O4(-2)
 Sodium Hydrosulfite, Na2S2O4
 Dithionate ion S2O4(-) is active
 Reductive reactions are reversible
 Oxygen decomposes the bleaching agents, need to
keep air out
 Calcium or magnesium precipitates the bleaching
agent, need to add chelant
 Dithionite Bleaching (Y)
 Can be done in the pulper
 Added to disperser at 30% consistency, 80-100 C,
then diluted and pumped to an upflow tower
 Added to a MC pump feeding an up-flow tower at
10-12 % consistency

 Application: 0.5-1.0% on pulp, 50-70 C,

30-90 min,pH =5.5-6.5 (acidic), consistency 3-5%,
must be oxygen free
 FAS Bleaching
 Formamidine Sulphinic Acid
 Low odor, crystalline powerful reducing agent
 Effective decolorizing for colored paper and carbonless
paper
 Excellent dye stripping
 Decomposes with oxygen
 Used in place of and is stronger than dithionite
 Slightly soluble in water
 Must be used soon or else decomposes in water
 FAS Bleaching
 Application: 0.3-1%, 30-90 min, 3.5-12 %K,
40-65C, pH=8-11, must be oxygen free
 Need 1 part FAS to 0.5 parts NaOH
 Initial pH=9, Final pH=7-8 is optimum
 High filler content, calcium carbonate, requires
less NaOH
 Can be applied in a disperser or in post
bleaching
FAS: Post bleaching
FAS Disperser Bleaching
 Bleaching Sequences:
 Single stages are not effective in reaching 80% ISO
brightness on MOW furnish
 Need two stages for MOW
 Variable incoming recovered paper requires multiple
stages
 Combination of oxidative followed by reductive bleaching
is most successful
 Must be careful to remove oxidative bleaching chemical
so it does not consume the reductive bleaching chemical
 Not common to do reductive bleaching first as the
reductive products are susceptible to being oxidized
 Common 2 stage processes: Peroxide-Peroxide,
Peroxide-dithionite, Peroxide-FAS
 Lecture:

Treatment of waste streams from paper recycling

operations
 Paper Recycling Mill Waste

 The generation of acceptable recycled

pulp is accompanied with significant
waste streams
DI Pulp Solid Waste Generation
Mill Yield % Sludge
OD Tons/day
AFR 65 340
GLPF 70 220
SF 75 60
FUF 72 140

Most sludge is around 50% MC, so wet

sludge flows are double this.

Progr. Paper Recycling 6(1), 1996.

 Types of waste from recovered paper mills:

Stock Sludges Inciner. Other

Prep. Waste Waste
Rejects
Ragger Tails Deinking Sludges Ashes Chemicals
Drum Rejects Clarifier Sludges Cinders (slags) Used Oils
Screening Rejects Biological Sludges Flue Ashes Cleaners
Cleaner Rejects Gypsum Wires
…. Felts
Hazard. Waste
….

Ref: Papermaking Science and Technology, Book 7,

Recyled Fiber and Deinking, Tappi Press.
Amount of Rejects and Sludges for
Production of Paper Grades
Amount of Rejects and Sludges for
Production of Paper Grades
 Composition of Reject Samples

Newsprint Packaging Paper

Composition of De-inking Sludge Samples

Printing Paper (Flotn) Tissue (Washing)

De-inking Sludges
Treatment of Wastewaters

Pulp
Pulper
Filtrate

No. 1 Washer

No. 2 Washer

No. 3 Washer

Clarifier

Sludge
 Water Treatment

 Re-use filtrates (often from thickening or washing

process) to conserve water
 Clarifier objective: take filtrate and make a sludge
and a filtrate
 Filtrate to Clarifier: 2000 ppm suspended solids
 Clarified water: 100 ppm suspended solids
 Sludge: 3-7% solids
 No change in colloidal or dissolved species
 DAF Clarifier

Floated Sludge

Scoop
Air

DAF Clarifier
Settled
Sludge

Raw Water
Clarified Water
Chemicals
Clarifier
Clarifier Rejects Scoop
 DAF Clarifier

 DAF = dissolved air flotation

 most common clarifier for recycling
 raw water is treated with chemicals to form flocs
of suspended solids
 tiny air bubbles are mixed with the water and
attach to the flocs
 the flocs rise to the surface and are scooped out
 some of the flocs settle to the bottom and are
also removed
Dewatering Processes
 Dewatering of Sludges
 Ragger and
rejects from
pulper system
not dewatered
 Sludges use 2
step process:
 Gravity table
or drum or
disk thickener
 Followed by
belt filter
press or
screw press
 Dewatering of Sludges
 Ragger and
rejects from
pulper system
not dewatered
 Sludges use 2
step process:
 Gravity table
or drum or
disk thickener
 Followed by
belt filter
press or
screw press
 Dewatering of Sludges

 Sludges use 2 step process:

 Gravity table or drum or disk thickener
 Followed by belt filter press or screw press
Screw Press
De-watered sludge dumped into truck
 Sludge Final Fates:
 Final disposition
 landfill
 incineration
 composting
 Cement, brick, concrete, mortar and lime
brick, road construction
 others
 Example of Sludge Combustion
 Combustion:
 Volume
Reduction
 Inert organics
 Immobilize
harmful material
in ashes and
slags
 Generate
energy
 Increased interest:
 Increased cost
of fuel and
purchased
power
 Landfill costs
 Environmental
regulations
 New
combustion
techn. With flue
gas cleaning
 Summary: Paper Recycling Waste

 Recycling Generates significant waste

 Many different types of waste
 Rejects
 Sludge
 Sludge from clarifier must be dewatered
 Several modes of disposal
 Landfilling
 Incineration
 others
 Lecture:

Paper recycling system design strategies

 Paper Recycling Systems

 Learning objectives
 Appreciate the strategies involved in designing a
recycle process
 Recognize the relative number and types of sub-
operations in each type of recycle process
 Understand rejects, sludge and water management
in a recycle system
 Paper Recycling Operations:
A Balancing Act

Production Quality

Yield

Safety Environment
Profit
 Key Parameters for Cleanliness
White System Brown System
Optical Properties Stickies
Product Brightness Flakes
Quality Dirt Specks Sand
Color Fines
Parameters Stickies Ash Content
Ash Content
Susp. and Colloidal solids Susp. and Colloidal solids
Process Water COD COD
Management Cationic Demand Cationic Demand
Conductivity Conductivity
pH Biological Activity
Amount of Rejects and Sludges for
Production of Paper Grades
 Recovered Paper Prices
450

400
Sorted White Ledger
350
ONP
300 OCC
Mixed Paper
250
$/ton

200

150

100

50

0
1970 1975 1980 1985 1990 1995 2000 2005
Year
 System Design Considerations
 There are several objectives of a recycling mill
 Profitable
 Meet product quality specifications
 Environmentally acceptable
 Reliable and safe operations
 There are many variables that can be adjusted to meet the objectives.
 Type of wastepaper furnish
 Type and number of unit operations
 Order of operations
 There are several variables that impact a recycle mill that are largely
uncontrollable
 Price and availability of raw materials
 Price of products
 Changing governmental regulation
 The optimization of this multiple-input, multiple-objectives problem is
non-trivial -- in the 1990’s several deinking plants went out of business
and continue to put pressure on the recycling industry
Other System Design Considerations
 Raw Material
 availability
 cost
 suitability for process
 Usable fiber content
 Product Desired
 optical properties
 strength properties
 Environmental Constraints
 Solid waste
 Water effluents
 Gas effluents
 Space Requirements
 Capital Costs
 Operating Costs
 General Process Strategies

 The following concepts or strategies are often

implemented in system design :
 Keep out unremovable contaminants from the process
 Ensure that contaminants are well separated from the fibers
 Remove contaminants early in the process
 Keep contaminants large to enhance removal
 Repeat inefficient unit operations
 Save fiber by cascading unit operations
 Save water by using counter current operations and by
clarifying the water effectively
 Avoid excessive changes in consistency
 Major Recycling Systems
 Can be categorized by the products they produce
 Packaging Materials
– Typically, OCC materials are recycled back into linerboard, medium, tube
stock, and solid board products
– Mixed waste can be used in lower quality applications
 Newsprint
– Old newspapers and magazines are converted into newsprint
 Tissue
– Bleached printing and writing wastes are converted into tissue
– Wood containing papers can be used for lower quality applications
 Printing and Writing Materials
– Bleached printing and writing wastes are converted into new printing
and writing grades
Source: AF&PA, 2006 Recovered
Paper Annual Statistics
Source: AF&PA, 2006 Recovered
Paper Annual Statistics
Source: AF&PA, 2006 Recovered
Paper Annual Statistics
 Lecture:

Paper recycling systems

Production of Newsprint
 ONP-OMG
Recycling
 Used to produce recycled
newsprint
 May have batch, continuos
tub or drum pulping
 Note the strategy:
 1st remove coarse
contaminants
 2nd remove smaller
contaminants, deinking
 3rd disperse unremoved
contaminants
 Often bleaching is used to
increase brightness
 Problems with stickies may
be caused by OMG

Ref: Secondary Fiber Recycling, Tappi, 2003.

Newsprint Recycle Process

Ref: Papermaking Science and Technology, Book 7,

Recyled Fiber and Deinking, Tappi Press.
Newsprint Recycle Process: Consistency
Newsprint Recycle Process: Ash
Newsprint Recycle Process: Stickies
Newsprint Recycle Process: Dirt Speck Area
Newsprint Recycle Process: Brightness
Newsprint Recycle Process: Rejects, Sludge
Water Systems
Newsprint Recycle Process: Rejects and
Sludge Components
 Production of High-Grade
Printing and Writing Grades
 Deinking of
Printing Grades for
Printing/Writing
 Used to produce new
printing and writing grades
 May use mixed or sorted
waste ($ vs production
trade-off)
 Note the strategy:
 1st remove coarse
contaminants
 2nd remove smaller
contaminants, deinking
 3rd disperse unremoved
contaminants
 4th bleach to high
brightness
 Most complex system to
produce highest standard
pulp
High Grade Printing and Writing Grades
Production of Tissue Grades
 Deinking of
Printing-Writing Wastepaper
Grades for Tissue
High Consistency Pulper
 Use sorted or non-sorted High Density Cleaning
office waste to make tissue Coarse Screening (Holes)
 For tissue making, filler Cleaning
level must be low for Fine Screening (slots)
creping (1-1.5%) (see 2
stages of washing) Washing I
Thickening
 Yield can be as low as 60% Dispersion
 Depending on quality of Bleaching (Oxidative)
tissue, brightness and dirt
count also important Flotation
 Lower grade tissue pulp Washing II
production omits 1 stage of Cleaning
cleaners, bleaching and Fine screening
washing. May also omit
flotation.
Storage

Ref: Tappi deinking short course, 1995.

Low grade Tissue
High Grade Tissue: Wood Free
Low-Grade Tissue: Wood Containing
Production of Packaging Grades
 Simple Repulping System for Packaging Product
 Used in filler systems in recycled-fiber boxboard mills
 Easy to operate, low capital cost, very high yield
 No capability to remove contaminants, must be removed before
pulping
 Product quality is simply a function of the input furnish
 Crude Cleaning System for Packaging Product

 Used to produce liner,

medium or tube stock
 Simple, high yield
process
 Ability to remove only
coarse contaminants
 Often used with a
continuous pulper
 Multi-ply Board Packaging Product

 Folding Boxboard Outside of box, visible to customer

 Stiff, have plybond
strength, clean on outside
 Top layer can be bleached Top Liner, 1
Underliner,3
chemical pulp or de-inked
white grade
 Underliner can be de-inked Filler, 4
wood containing pulp
 Filler layer has mixed waste Back Liner,2
 Back layer uses kraft
unbleached pulp Inside of box, appearance not so important
 Quality indicated by
number, 1 highest quality
 Excess water from each
loop goes to inferior layer
 OCC Recycling
for Higher Grades
 Used to produce linerboard
or medium
 Often have a continuous
pulper with cleaning system
 Note the strategy:
 1st remove coarse
contaminants
 2nd remove smaller
contaminants
 3rd disperse unremoved
contaminants
 Use alkali to swell fibers
and regenerate strength
 Problems with stickies
necessitate extra cleaning
steps
Test Liner Production
Test Liner Production: Macro-Stickies
Paper Recycling Systems: Summary
 Learning objectives
 Appreciate the strategies involved in designing a recycle
process
– Cleanliness/strength, production rate, yield
 Recognize the relative number and types of sub-operations in
each type of recycle process
– Depends on the quality of product and the incoming raw
material
– Need different operations to deal with inks, large junk, stickies,
fillers and brightness
 Understand rejects, sludge and water management in a
recycle system
– Counter-current flow water-pulp to improve quality
– Thickening to isolate water loops
– Large rejects easily drained
– Sludges are dewatered and pressed
 Lecture:

Cost to produce deinked pulp

Cost of Deinked Pulp (DIP)

 System
 MOW to deinked, bleached pulp (DIP)
 Flotation (2), washing, oxidative bleaching,
complementary processes
 Produce 200 ODTPD
 Yield = 67%
 Total Capital Cost Installed= $42 MM
 $6 MM/yr depreciation for 7 years
 MOW Cost =$220/ton delivered
High Grade Printing and Writing Grades
 Cost of DIP: Variable Costs
Description Quantity Unit Unit Cost, $ Contribution,
$/ton
Fiber 1.5 ton 220 330
NaOH 0.024 ton 400 9.6
Peroxide 0.024 ton 600 14.4
Sodium Silicate 0.022 ton 500 11.0
Flotation Aid 0.0027 ton 1000 2.7
Sludge Dewater Polymer 0.00115 ton 1200 1.4
Clarifier Flocculant 0.00014 ton 1600 0.2
Clarifier Bentonite 0.00085 ton 1600 1.4
Electricity 310 kWhr 0.045 14.0
Steam 790 kPa 0.25 mton 6 1.5
Waste Water Treatment 1.236 m3 0.53 0.7
Waste Disposal 0.984 mton 36 35.4
Process Water 4.8 m3 0.53 2.5
Total Variable Prod. Cost 424.8
 Cost of DIP: Fixed Costs

Fixed Costs $ Per Year $ / ton

Maintenance 4,000,000 57
Labor 2,000,000 29
Operating Materials 1,700,000 24
Depreciation (7 yr
straight line) 6,000,000 86
Business Overhead 1,100,000 16

Total Fixed Costs, $/ton 211

 Cost of DIP: ROI
Total Costs, $/ton produced 636
Total Costs per year, $ 44,532,716
Selling Price of ton DIP, $/ton 600
Income, $/yr 42,000,000
Profit before taxes, $ -2,532,716
Taxes (25%) -399,537
Profit after taxes, $ -2,133,179

Slightly
ROI (%) negative!
 Lecture:

Automated Image Analysis of Paper to Detect

Contaminants
Tedious Manual Method to Detect Dirt:
1.0 mm2

0.5
Standard Dirt Chart
0.25

0.1

Paper

 In the past, a technician would inspect paper samples for dirt specks.
The technician would match the size of the speck to a calibrated chart
and record the number and sizes of all the specks.
 Dirt Count reported as parts per million, PPM

 PPM = 106* (area covered by dirt) / (analyzed area)

Tappi Dirt Estimation Chart (mm2)
 Automatic Image Analysis (IA) to Detect
Contaminants

 Scanner: Eyes
 Computer: Brain
 Software Program: Rules for Decision Making
 IA: How it works

 Scanners digitize an image; the image is broken down into an array of pixels
 The size of the pixels depends on the resolution
 Resolution often reported as dots per inch (DPI)
 600 dots per inch square is equal to a square with edge of 0.04 mm or area of
.018 mm2
 The smallest size human sight can detect is an object with 0.05 mm longest
axis
 IA: How it works

 Each pixel is assigned a grey scale value (GSV) depending on how dark it is
 Black = 0
 White = 255

 Why go from 0 to 255 ?

 IA: How it works

Threshold GSV
# of pixels
of that
GSV Pixels assigned
as paper
Pixels Assigned
as Contaminant

0 GSV of pixels 255

 A threshold GSV is input into the computer by the operator

 If pixel GSV < threshold GSV computer recognizes it as contaminant
 If pixel GSV > threshold GSV computer recognizes it as clean paper
Real life:
bleached
white
paper
with black
specks
 IA: How it works

 Computer groups adjacent pixels with GSV < threshold together and then can
determine size of dirt specks and total area covered by dirt and PPM
 IA: How it works

 If the threshold GSV for the above sample is set to 175, then what is the PPM
of the sample?

 Area covered by dirt = 4

 Area analyzed = 15

 PPM = 1,000,000 * 4/15 =

Real life: bleached white paper with black
specks
Real life: bleached white paper with black
specks
 Example of Other Uses of IA:
Adhesive Deposits on Paper Machine Wires
Following slides did not appear in
presentations.
 Left them here to not lose them.
 Types of Papers
 Chemically pulped and bleached fibers:
 have 0% lignin
 Only cellulose and hemicellulose, white
 Chemically pulped unbleached fibers (linerboard):
 have 5-15% lignin
 Brown
 Condensed lignin, extended conjugated structures, aromatic groups,
several double bonds of carbon
 Electrophilic agents such as oxygen, chlorine dioxide, chlorine can
oxidize, interrupting conjugation and color
 Mechanically pulped fibers (newsprint):
 Have 20+ % lignin
 Lignin is in natural, non-condensed condition
 Are brighter than chemically-pulped, unbleached fibers
 Carbonyl groups are responsible for the yellowing
 Can be bleached with non-degrading, lignin preserving chemicals
 Bleaching
 If the color is due to conjugated carbonyl
groups, as in mechanical fibers, lignin
preserving chemicals should be used
 Peroxide, dithionate, FAS
Bleaching
 If the color is due to azo
groups, conjugated
carbon-carbon double
bonds or condensed
aromatic structures, only
lignin degrading
chemicals can be used
 Oxygen, ozone, chlorine,
chlorine dioxide, sodium
hypochlorite
 Sodium Hypochlorite (H)
Bleaching
 Oxidative bleaching that degrades lignin
 Advantages: inexpensive, very effective, can be
added to pulper to remove color
 Disadvantage:
 no chlorine free label,
 prepared by dissolving chlorine gas in caustic
solution,
 generates chloroform (carcinogen),
 can not be used for pulps with greater than 10%
mechanical pulp, causes coloring
 Has been mostly phased out due to
environmental concerns
Sodium Hypochlorite (H) Bleaching
 2NaOH + Cl2 -> NaOCl +NaCl+H2O
 NaOCl is sodium hypochlorite
 HOCl  H(+) + ClO(-), pKa =7.5
 Need pH greater than 9.5 for ClO-
 If pH 6-7 hypochlorous acid HOCl, which
attacks and degrades cellulose
 If pH less than 3 generate chlorine gas, Cl2
Sodium Hypochlorite (H) Bleaching
 Sodium Hypochlorite (H)
Bleaching
 Application: 0.5-2.5% on pulp
 Time, 30-90 min
 Consistency: 3-12%
 Temperature: 35-70 C
 pH=9.5-11.0
Chlorine Dioxide Bleaching (D)
 Oxidative bleaching with excellent color
stripping and large brightness gains
 Disadvantages: no chlorine free label
 Process Conditions
 Application: 0.2-1.0% on pulp
 Time: 60-180 minutes
 Consistency: 10-15%
 Temp: 55-70 C
 pH: 6.5-9.5, with 6.0 optimum
 Oxygen Bleaching (O)
 Oxidative bleaching that improves brightness, lowers
chemical costs, removes color, detackifies stickies
 Disadvantages: will not tolerate mechanical pulps, need
pressurized vessel of 60-115 psig
 Oxygen produces radicals that degrade lignin and also
form peroxide which reacts with the chromophores
 Only system is Oxypro, patented by Air Products
 Conditions
 1.0 % on pulp application, 60 min, 10-15 %K, 85-95 C, 1.0 %
H2O2, 0.7-1.0 % NaOH, Na2SiO3 1.5-2.0%, DTPA 0.2%,
pressure 60 psig
 Ozone Bleaching (Z)
 Destroys dyes and optical whiteners
 Toxic and high capital cost
 Not frequently used
 Ozone decomposed by metal ions
 Uses low pH to solubilize and remove metal ions and
chlating agents used to remove metal ions
 Conditions: 0.25-3.0% on pulp, 1-5 min, 10-40 %K, 20-
60 C, pH=2.5-10, Ozone concentration: 2-12% in gas
applied to pulp
 Ozone: most effective TCF bleaching reagent for
removing fluorescence