Deinked pulp in high grade graphic papers : advantages and limits

Bruno Carré, Benjamin Fabry, Elisa Zeno

Centre Technique du Papier
Domaine Universitaire BP 251
38044 Grenoble Cedex 9
France
Email : bruno.carre@webctp.com (to which correspondence should be addressed)

Summary

Recycled fibres have become a main fibre resource for the paper industry. New increases in recycled
fibres uses are possible, but need certain technological adaptations. In Europe, the paper grade in
which recycled / Deinked Pulp (DIP) can be increased is mainly the graphic papers. Uncoated and
coated papers of high brightness from DIP pulp can have a promising future. Some mills are already
manufacturing such grades from deinked pulp, however the economical interest of producing such
grade is not always obtained because the raw materials are sometime not available in sufficient
quantity, the contamination can be high and therefore the process is quite complex with an insufficient
yield. In order to improve the situation, several challenges need to be solved to be successful : among
others (i) means to improve further the ink and speck removal are necessary to fulfil the high optical
characteristics required, (ii) ink separation selectivity needs to be improved to limit the deinking sludge
production, (iii) if recovered papers are not of a sufficient quality, the deinking process need to be able
to handle several possible contamination in the recovered papers (mechanical pulp, brown kraft fibres,
colored papers…)... therefore, the high DIP pulp properties required (brightness < 80 % ISO, specks :
1 – 5 ppm) usually call for a quite sophisticated deinking process. In the present paper, solutions have
been studied to both answer all the previous listed challenges and to rationalize the deinking process
at higher yield, lower energy consumption and identical properties. The first part of the paper explains
how the pulp properties will be affected by different contaminants and which treatment will be able to
handle these contaminations, the last part will review the different approaches proposed to improve
this high quality DIP economical interest.

Keywords : Deinking, Graphic papers, Flotation, Ink removal, Sludge valorisation

Introduction

Today, at the end of 2007 according to the last

120
available statistics, the European paper industry
recycling rate is 64,5 %.
100
This percentage has regularly increased during
80
the last two decades, the utilisation of recovered
paper increasing of 123 % since 1991 for a paper
& board production increase of 56 % (Ringman 60
1
2009 ).
40
The European industry is on the way to reach the Woodpulp Pulp Other than Wood
66 % recycling rate in 2010, as reported in the 20
Recovered Paper Non-Fibrous Materials
European Declaration on Paper Recycling
(www.cepi.org). 0
1991 1993 1995 1997 1999 2001 2003 2005 2007
Figure 1 : European Paper & Board production (MT)
during the last decades – share between the use of
1
different raw material utilisation (Ringman 2009 ).

1
However, this rather high percentage of the recycling rate hides significant differences in the utilisation
of recovered papers, as illustrated in Figure 2. If high utilisation rate and significant volumes of
recovered papers are used for the production of case materials (using mainly corrugated and kraft
board) and for the production of newsprint (using essentially old newspapers & magazines), the
utilisation of recovered papers is particularly low in the production of “other graphic papers”. Under this
descriptor, there is mainly the production of wood containing magazines, mainly SC papers and a few
of LWC papers (from old newspapers & magazines). The usage of high grade wood free old papers
for the production of high grade wood free paper is indeed very limited. This is really the grade in
which there is a potential of adding more old recovered papers.

Mixed Grades Corrugated and Kraft Newspapers and Magazines High Grades
100
Case materials
Newsprint
90

Wrappings, other
80

Household &
pack.paper
Carton Boards
70

sanitary
Utilisation rate (%)

Others
60

50

40

30

20
Other graphic papers
10

0
1 11 21 31 41 51 61 71 81 91
Share of total paper & board production (%)

Figure 2 : Utilisation rate & type of recovered papers versus the total European Paper
& Board production. www.cepi.org

To succeed to increase the utilisation rate of recovered papers in high quality wood free papers,
several challenges need to be solved :

o Sufficient volume of wood free recovered papers must be collected. If the household collection
is more or less well organised and allows to recover large volume of recovered papers (20
MT), only 5 MT are collected through the office collection out of a consumption of roughly 9
MT (4,3 MT Coated Wood Free and 4,8 MT Uncoated Wood Free - www.cepifine.org). Today
out of these 5 MT, roughly 2,2 MT are used for the production of hygienic papers, 2,1 MT are
used to produce white layer in multiply board and 0,8 MT only are used to produce again
wood free fine papers.
o Collection of the office recovered papers must avoid as much as possible the presence of
contaminants which would not allow to recover high quality target :
• presence of lignin containing fibres (wood containing magazines or newsprint),
reducing the brightness which can be reached, and inducing brightness reversion
• presence of water based prints, and especially water based pigment prints such as ink
jet prints reducing significantly the brightness
• presence of high proportion of colored papers, which otherwise will give a shade to
the deinked pulp
• presence of UV over print varnishes or UV inks, leading to high speck contamination
• presence of brown board leading to visual contamination : mottling
o From a recycling / deinking process point of view, the challenges are also numerous :
• very high ink and speck removal are necessary to fulfil the high optical characteristics
required,
• efficient bleaching / color stripping sequences need to be implemented, without a too
large release of dissolved and colloidal substances ,
• ink separation selectivity needs to be improved to limit the deinking sludge production,
• new reject treatments have to be found,

2
 o Finally, the economical interest to use recovered papers for such a production needs to be
balanced.

In the following paper, some of the most problematic challenges to solve will be discussed, especially
those dealing with the process point of view.

Recover a high quality DIP : limitations to solve

Achieve a high ink removal :

Among the main limitations to solve, the first one is how to recover a high brightness DIP. In order to
recover values higher than 80 % ISO, it is absolutely necessary to remove very efficiently the ink
particles. A remaining ink content as low as 0,1 % in weight can induce a significant brightness drop
especially at such high brightness level. It is rather clearly illustrated in Figure 3 showing the incidence
of remaining ink in a 100 % wood free chemical pulp or in various TMP pulps, bleached at different
levels. When brightness to recover is high (> 80 % ISO), a low content of ink is absolutely necessary,
with ERIC values below 50 ppm.

This is why deinking lines 90

to produce high brightness
85
DIP are made up of several Bleached Chemical pulp
ink removal steps : 80
combination of flotation and
Brightness, %

washing stages. 75

70
The number of stages in the 100 % TMP
65
process depends on the
grade of the recovered papers 60
and the quality requirement of
the deinked pulp to be 55
produced. 50

45
0 200 400 600 800 1000 1200 1400
E.R.I.C., ppm

Figure 3 : Brightness variations versus residual ink, added in pulps of

different brightness (TMP bleached at different levels, bleached
chemical pulp).

To show how detrimental can be the residual ink on brightness, deinking experiments were performed
with increasing share of water based pigment based inkjet prints in a office recovered paper mixture.

The presence of water based, pigment based, inkjet prints leads to too high residual ink content :

Inkjet prints should be found, currently, mainly in wood free mixtures since this type of prints is found
mainly in office waste papers. To study the impact of various inkjet prints ratio on deinking of wood-
free mixture, increasing rates of black inkjet prints (black pigment water based ink) were introduced at
various rates from 0 to 30% in a mixture containing 50% of toner prints and 50% of sheet fed offset
prints.

The various mixtures were deinked with the following conditions:

• Pulping with neutral condition (Lamort Helico pulper, 15 min, 45°C, concentration 12%, 0.04 Liptol
S100),
• Flotation in laboratory Voith cell at 1%
• Washing in Degussa laboratory cell (64 µm) at various time. The washing stage was added
because the majority of the chain for tissue or commercial pulp contain these washing steps.

3
Figure 4 traces the brightness
versus the total yield (flotation +
Various ratio of ink jet prints- Brightness
85
washing). Beyond 10% of inkjet
80
print, and despite significant

Brightness %
75

Flo
additional washing loss, it is not
possible to achieve the brightness 70

ta

Pulping
of the floated mixture free of inkjet 65

tion
prints. The main explanation to 60
this phenomenon is the ink 55 Washing
redeposition on fibres. 50
50 60 70 80 90 100
Below 10% of inkjet print, it is Total yield %
possible to achieve the brightness
0% ink jet 5% ink jet 10% ink jet
of the floated mixture free of inkjet 20% ink jet 30% ink jet
prints but for additional losses
(approximately 20% of additional Figure 4: Effect of increasing rates of inkjet prints on the
losses). brightness of a wood-free mixture after flotation and washing

These results are clearly confirmed by the same curve with the residual ink content, Figure 5.

Figure 5 confirms that below 10

Various ratio of ink jet prints- ERIC % inkjet print, it is possible to
700
achieve a residual ink content

Pulping
600
Washing of the floated mixture free of
ERIC ppm

500 inkjet print (30-40 ppm) with

Flo

400 additional losses during

300 washing (around 20 %
ta

200 additional losses).

tion

100
0 But above 10 % inkjet print, it is
not possible to achieve residual
50 60 70 80 90 100
ink content of the floated
Total yield % mixture free of inkjet print.
0% ink jet 5% ink jet 10% ink jet
20% ink jet 30% ink jet
In addition to the brightness
Figure 5: Effect of increasing rates of inkjet prints on the residual problem, the presence of water
ink content of a wood-free mixture after flotation and washing. based, pigment based, inkjet

prints in the washing waters will concentrate the little particles in the process water and their
elimination will generate some supplementary cost in coagulant. Finally, we can also notice that the
simple presence of ink jet prints induce lower flotation yield because of higher foaming, ink jet prints
certainly contain higher amount of surface active substances.
2
Pilot experiments have been performed by Huber et al. 2004 studying the effect of various raw
material on the ink content and on the brightness along a wood free deinking process. Four different
furnishes were studied using a mixture of these raw materials, designed by their specific raw material :

%toner %magazine %inkjet %2.08

"toner" furnish 60 20 0 20
"magazine" 40 40 0 20
furnish
"inkjet" furnish 40 20 20 20
"2.08" furnish 30 20 0 50
Table 1 : Composition of various wood free furnish tested
for their brightness potential

As expected, flotation and washing efficiently reduce ink concentration in the pulp (Figure 6).
Measurements on hyperwashed pulp (Figure 7), show that pre-flotation (probably due to the shearing
effect in pumps) and dispersion help to reduce ink attached to the fibres. In the case of inkjet furnish
however, ink removal is difficult to obtain : flotation is less efficient as pigment ink particle are very
small and less hydrophobic (Figure 6). A thorough post-deinking loop is required to achieve

4
acceptable residual ink values, where post-washing is essential. It is anticipated that inkjet removal
would be worst in an industrial case, as the laboratory washing procedure used here is very efficient.
ERIC on hyperwashed pulp after repulping ("screen" sampling point) is higher in the case of inkjet
furnish (Figure 7), indicating a very fast ink redeposition (considering water-based ink is instantly
"detached").
whole pulp E.R.I.C. (ppm)

hyperwashed pulp E.R.I.C. (ppm)

700 140
toner mag.
600 toner mag. 120
inkjet 2.08
500 inkjet 2.08 100
400 80
300 60
200 40
100 20
0 0

.
h.
w on

P hic ing

-w .
flo n

ch ing

po sp.

.
h.
w on

-w .
P hic ing
flo n

ch ing

po p.
ch
t

ch
t
po t-flo
e

po -flo
e
as

as
s
ti
re

ti
ea

re
h

di

ea
h

ea en

di
ta

ta
as

ke

as
sc

st
.+

sc
s

.+
bl

bl
k
st

st
Y

Y
ea
t

t
bl

bl
Figure 6: Evolution of pulp residual ink content Figure 7: Evolution of pulp (attached /
along a wood free deinking process for 4 different redeposited) residual ink content along a wood
raw materials free deinking process for 4 different raw
materials

Generally speaking, all the previous examples clearly emphasise that every process steps allowing to
improve the ink removal should be favoured : it includes pulping conditions with the appropriate
chemistry, flotation & washing conditions but also dispersing conditions. All these have been carefully
studied in the frame of CTP projects.

Avoid mechanical fibres :

Apart the presence of ink particles, and especially small ink particles, the second major parameter
affecting brightness of the DIP is the fibre mix, and particularly the presence of mechanical fibres.

Their impact is well illustrated by the following figures.

Figure 8 reports the incidence of

mechanical pulp share and of its
Chemical pulp brightness, 88 %
brightness on the brightness of a
mixture (chemical pulp /
Brightness of MP, %

mechanical pulp). It appears that

the lower the brightness of the
mechanical pulp the greater its
incidence on the mixture
brightness. For example, 20 % of
mechanical pulp at 60 % ISO
decreases the brightness from 88
% (pure chemical fibres) to 71 %
roughly.

In the range of interest for office

collected papers, mechanical pulp
may come through the presence
of some magazine or white papers
containing high brightness CTMP.
Mechanical pulp ratio, %
Figure 8: Effect of increasing share of mechanical pulp and of its
brightness on the brightness of a chemical pulp / mechanical
3
pulp mixture. Lachenal 1994

5
If there is 20 % magazine with TMP pulp bleached at 72 %, then its incidence on the mixture will be to
decrease the brightness from 88 % to 78 % which is still very significant. This effect has also been well
4
reported by Burnet et al. 2007 .

Figure 9 confirms that with up

amount of MP (56 % ISO) amount of BMP (72% ISO)
to 15 % mechanical pulp of
90 high brightness (72 % ISO),
Mixture brightness, %

85 which can be the situation for

mill using sorted office
80
recovered papers, a decrease
75
of brightness from 89 to 85 %
70 ISO can be seen.
65
60 Another side effect of this
55 mechanical pulp is also the
0 10 20 30 40 50 60 70 80 90 100 brightness reversion upon light
% mechanical pulp and heat.
Figure 9: Incidence of mechanical pulp ratio and brightness (56 %
ISO Mechanical Pulp (MP) and 72 % ISO Bleached Mechanical
Pulp (BMP)) on the brightness of a mixture “chemical pulp +
4
mechanical pulp”, Burnet et al.2007

2
The work by Huber et al. 2004 already discussed previously also illustrates the incidence of
mechanical pulp in the raw materials on the brightness potential of the 4 different furnish tested. If
brightness is logically mainly increased by flotation, washing and bleaching (Figure 10), the incidence
of a higher residual ink in the “Inkjet” furnish” (Figure 6) is clearly visible from that measurement. On
the other hand, the lower brightness obtained with the “magazine” furnish, richer in mechanical pulp,
was not visible from the residual ink measurement but is visible on both the entire and hyperwashed
pulps brightness, due to mechanical fibres. Brightness is similar for the “magazine” furnish than the
inkjet, for less ink present but a more “yellowish” pulp due to mechanical pulp. This is confirmed by the
hyperwashed fibre brightness, lower for the magazine at a low ink content.
hyperwashed pulp brightness

90 90 toner mag.
whole pulp brightness

85 inkjet 2.08
80
80
70
75
60
70
toner mag.
50
inkjet 2.08 65
40 60
.
bl .
w on

P hic ng

-w .
flo n

ch ng

po p.

ch
h
t

.
h.
n

P h ic n g

-w .
en

ch ing

po p.
po -flo

ch
e

t
as

tio
s

po -flo
ti

hi
re

ea eni

as
ea

s
di

i
re
ta

ea
h

di
as

st

ta
sc

.+

as

ke

st
sc
k

.+

bl
flo
st

st
w
Y

Y
t

ea
t
bl

bl

Figure 10: Evolution of pulp brightness along the Figure 11: Evolution of fibre brightness
deinking line for 4 different raw materials (hyperwashed pulp) along the deinking line for 4
different raw materials

The main recommendation is therefore to avoid as much as possible the presence of mechanical pulp
in the furnish, and especially the mechanical pulp of a low brightness provided for example by
Scandinavian newsprint, telephone book directories…

6
Avoid the presence of colored papers

In the office paper collection, there can be significant proportion of colored papers. If there is no
adapted bleaching treatments, the choice of recovered papers must be done very carefully to avoid
their presence.

The colour is given by the presence of dyes, which, in papermaking, are most often synthetic organic
dyes, soluble in waters. These are divided in basic (but more used for mechanical pulp), acid or direct
(often used for wood free pulp) dyes. In order to discolor these molecules, it is necessary to remove
the conjugated bounds responsible of the color or to break down the colored molecule in smaller unit
less conjugated. To remove the conjugated bounds, it is recommended to reduce or oxidize the azo
bounds, the ethylene bounds and sometimes the carbonyl bounds. If colored papers are accepted in
the raw materials, then an adapted efficient discolouring treatment should be implemented, using most
often both oxidative and reducing agents.
5
To illustrate the effect of colored papers, Magnin et al. 2000 introduced 20 % of colored papers in a
wood free furnish. Colored papers were a mixture of various colored papers sampled in different tissue
deinking mills using wood free recovered papers.

Pulp containing Pulp free of coloured

20 %coloured papers papers (pulp NFW)
Brightness 0 % UV 61.6 78.3
L* a* b* 0 % UV 87.2 0.9 8.6 91.6 -0.2 1.6
Brightness 100 % UV 76.6 102.9
L* a* b* 100 % UV 88.3 3.8 -3.6 93 3.9 -14.5
Fluorescence Index 15 24.6
Kappa number 5.2 2
ERIC ppm 44 42

Table 2 . Optical properties of the wood free deinked pulp containing 20 %

coloured papers. Pulp NFW states for Neutral Pulping followed by Flotation &
Washing.

The optical properties of the pulp containing colored papers are reported in the Table 2. Compared to
the pulp free of colored papers, the brightness without UV has dropped by 17 points. The fluorescence
of the pulp is decreased but remains high due to the large quantity of pulp free of colored papers
which is strongly fluorescent.

Avoid the presence of brown fibres

Due to increasing volume of office recovered papers, the sorting quality is unfortunately expected to
decrease and may lead to the presence of corrugated board contaminating the furnish. To study this
5
effect and evaluate the effect of bleaching treatment on such contamination, Magnin et al. 2000 have
also looked at the effect of 5 % brown fibres in a wood free furnish.

5 % brown fibres (kraft envelopes composed of 80 % softwood kraft pulp and 20 % hardwood semi-
chemical pulp) have been mixed with 95 % deinked pulp from white office waste (pulp NFW, Table 2).
The optical properties of the pulp (measured on pads) are given in Table 3.

The presence of only 5 % kraft fibres lead to a pronounced decrease of brightness, roughly – 10 %
ISO, associated also to a slight decrease of fluorescence. The main effect however is mottling, brown
fibres being visible to the naked eye in the white handsheets.

7
 Pulp containing Pulp free of
5 % brown fibres brown fibres
Brightness 0 % UV 70 79.6
L* a* b* 0 % UV 89.4 0.6 4.6 92.1 -0.9 2.3
Brightness 100 % UV 90.6 105.2
L* a* b* 100 % UV 90.7 4.3 -10 93.6 3.9 -14.8
Fluorescence Index 20.6 25.6

Table 3: Optical properties of the wood free deinked pulp containing

5 % brown fibres. Magnin et al. 20005

Achieve a high speck removal

Among the main difficulties encountered to manufacture a high quality DIP liable to be introduced in
high quality fine paper, another quality parameter is the cleanliness of the pulp, usually quantified by
the surface of visible contaminant per surface unit in handsheet of hyperwashed pulp (mm²/m² or
ppm).

Specks are generally issued from the presence of resistant coating particles, from fused toner
particles found in electro-photography prints, by overprint varnish and especially UV varnish…. As the
requirement for a high quality DIP is around a few ppm, 1 to 5 mm²/m² of speck particles larger than
150 µm, it is absolutely necessary to remove or fragment them very efficiently. This is especially true
when considering the initial contamination which can range between 10 000 to 50 000 mm²/m²
depending on both the recovered paper types, on the threshold size of what is a speck (100, 150 or
200 µm), on the image analysis system as well as on the brightness of the background !

However, the speck removal efficiency to reach is very high (> 99 %) This is why most deinking
process producing high quality DIP for fine paper generally includes, apart cleaning stages, 2 or even
3 flotation to remove the specks and 1 or even 2 dispersing / kneading stages (Figure 15) to fragment
them into small particles invisible to the naked eye. Dispersing energy input is generally between 50 –
80 kWh/T depending on the speck contamination. Dispersing temperature is usually around 70 –
80°C, it can be even higher since, without mechanic al pulp there is not risk of brightness reversion.

When specks are issued from toner particles, it is of prime importance to avoid too high temperature,
especially during pulping and in low speed kneader, otherwise toner are re-fused onto fibres and
become impossible to float.

Average size of specks at pulping Specks contamination- Flotation

400 20°C
100000
45°C
diameter µm

350
area (mm²/m²)

10000 65°C
300 20°C
45°C 1000
250
65°C
200 100
150
10
0 5 10 15 20 25 30 35 40 45
0 5 10 15 20 25 30 35 40 45
Pulping time (min)
Pulping time (min)

Figure 12 : Effect of pulping time and temperature Figure 13 : Effect of pulping time and temperature on
on specks particles average diameter specks particles flotation

This effect is clearly visible in Figure 12 showing the incidence of pulping temperature and time in a
pilot Helico pulper on speck particles average diameter. As a first approach, this re-agglomeration
could be said to be positive (to remove specks by cleaners) however the subsequent speck
contamination after flotation, Figure 13, clearly illustrates the poor flotation associated to the toner
refusing on fibres.

8
A similar phenomenon has been observed at the dispersing unit.

The incidence of all process parameters need therefore really to be studied in order to avoid such
phenomenon and improve the removal or fragmentation efficiency of each steps.

Achieve a high stickies removal

Among the DIP quality criteria, one of them, encountered by all the mills worldwide is the stickies
6
contamination. According to Delagoutte 2009 , stickies originate from various types of adhesive
materials found in recovered papers which are broken down into small particles during re pulping.
Primary stickies result from insoluble and non-dispersible adhesives which are not removed during the
stock preparation process and move to the papermachine and into the paper sheet. Finally, primary
stickies can be considered as solid adhesive fragments which remain in the pulp. Depending on the
7
size of these particles it is possible to distinguish (Doshi 1997 ) :

Macro stickies which are large primary stickies rejected by a 100 µm slotted laboratory screen.

Micro stickies which are those going through the screen and consequently having a size lower
than 100 µm.

Due to their inherent properties (tackiness or ability to develop tackiness in particular conditions)
primary stickies are liable for a lot of problems in papermaking : Paper & board quality (holes &
specks, adhesion points in reels, defect during coating…), Deposits all along the papermachine,
papermachine runnability…

Considering the specific case of wood free furnish used to manufacture fine paper, the stickies
contamination is therefore also of high importance. Every possibilities to reduce first their presence in
the raw material, and secondly their removal by the process should be optimised.
As an example, the following graph shows the primary stickies (large > 4 in the image analysis and
small ≤ class 4 – also called mini stickies) along a wood free deinking process.

14000
< = Class 4 W& P
12000 > Class 4
Total
10000
Stickies content mm²/kg

8000

6000

4000

2000

0
Post-flotation

Post-flotation

Inlet DF 2
Outlet disc

disperging
Pre-flotation,

Pre-flotation,
Outlet Dump

Inlet fine

Accept fine

Inlet fine

Inlet disperging

Outlet storage

Machine Head
Machine chest
Pre-screening
Coarse screen,

Coarse screen,

Kneader inlet

Kneader outlet

screen

screen
screen

Outlet
filter
accept
accepts
tower

outlet
inlet

tower
inlet

box
inlet

acc

Figure 14 : evolution of the primary stickies contamination along a wood free deinking process. Share of
8
primary stickies in large and mini stickies. Delagoutte & Kumar 2008 .
A specificity of wood free recovered papers is the large proportion of small macrostickies (ministickies,
9
see also Galland et al. 2009 ) which are very poorly removed all along the deinking process. Care
should thus really be taken to avoid their presence in the raw material and to remove them as
efficiently as possible.

9
Producing a high quality DIP requires a complex deinking process :

The processes proposed by the machinery supplier to produce such a high quality pulp (brightness >
80 %, specks : 1 – 5 ppm) include nowadays at least 2 flotation stages and often at least one washing
stage. These process are less complicated than those which are today on the market, including 3
flotation stages and 1 to 2 washing stages.

According to the previous requirements, the deinking process proposed today combines :

• Very efficient ink removal stages : that is why there is at least 2 flotation stages, and one
washing stage.
• An efficient bleaching sequence to handle the presence of mechanical pulp, eventually of low
amount of brown fibres and colored papers. This is why there is 2 bleaching stages : a
combination of oxidative (peroxide, to bleach) and reductive (hydro or FAS to both bleach and
color stripping) stages.
• An efficient speck removal and speck fragmentation : for that the two flotation stages are
necessary as well as one or two dispersing stages, in addition to cleaners
• Flotation and washing also to remove mineral fillers particles, associated to an efficient
process water clarification.
• Efficient screening systems to remove all large contaminants, and especially stickies particles.
• Two efficient thickening stages with counter current washing to limit the flow of process waters
sent to the papermachine / wet lap.

Figure 15 : Flow sheet for DIP for high grade printing & writing grades (wood containing, LWC)
proposed by Voith Paper (2009).

10
Figure 16 : A DIP pulp process proposed by Kadant - Lamort for Fine Paper or Copy paper (2009).

Improve contaminant removal selectivity.

When producing high quality DIP, as explained previously, the DIP process is generally quite complex
with 2 and sometimes 3 deinking loops combining flotation and washing. One of the main drawback of
such complex process are the loss generated during the different phases of the process and
particularly during flotation and (washing + process water clarification).

100 40
toner
90 toner mag.
ash content (%)

mag.
yield (%)

30 inkjet 2.08
80 inkjet
2.08
70 20

60 10
50
0
ke g
w ion

h.
- w t.
po ing
flo en
sc r
e

th hin

po t-flo

as
lp
re

.
t

w a on

h.
n

P hic ng

-w .
en

ch ing

po p.

ch
t
ta
pu

p o - fl o
as

as
s
s

ti

i
re

ea
sh

di
ta
st

ke
ic

st
sc

.+

bl
fl o

st
Y
ea
t
bl

Figure 17 : Effect of different wood free recovered Figure 18 : Evolution of the mineral filler content
papers on deinking process yield. Evolution along along a deinking process for different wood free
2 2
the process. Huber et al. 2004 recovered papers. Huber et al. 2004

Depending on raw materials, on process configuration and on the final requirements of the DIP,
deinking process yield can range between 50 up to 65 – 70 %. Deinking process yield versus 4
different raw materials, already discussed previously (Table 1) are reported in Figure 17.

To complement this information, it is necessary to report the mineral filler content versus the process.
A very high filler removal is obtained, especially during flotation and washing in the first loop.

11
The yield values explain why huge volume of rejects are generated, especially during flotation and
(washing + process water clarification). These rejects, thickened onto a double wire or screw press at
50 – 60 % dryness, are called the deinking sludges. They are rich in mineral fillers, containing up to 70
10
% fillers. Their utilisation can be manifold as illustrated by Hanecker 2009 .

cement other building

Building industry material
material 15% 0%
38 %

on-site thermal
utilisation
45%
brickworks
23%
Agriculture
Thermal
1% utilisation
62 %
external
Landfilling thermal
0% utilisation
10
Figure 19 : Utilization and disposal of Deinking residues (Germany 2007), Hanecker 2009 ,
representing 1,5 MT roughly.

One of the challenge would be really to decrease the deinking process loss because these are
expensive ! An approach is to try to increase the ink flotation selectivity, provided that more filler can
be introduced in the final DIP & produced paper.

Conclusions :

As illustrated previously in the different paragraph, producing a high quality DIP requires a number of
criteria which are not that easy to fulfil. To summarise :

• Ink content :
o If the ink content is to high, for example around 200 ppm such as it can be the case for a
badly deinked pulp, brightness will never be higher than 74 % whatever the bleaching
treatment.
o To recover brightness values higher than 80 % ISO, ERIC should be lower than 50 -
80 ppm
o The process must therefore include several ink removal stages, by flotation and washing

• Mechanical fibres :
o The presence of 30 % mechanical pulp in a wood free furnish induces
 brightness decrease from 89 to 79 % ISO with mechanical pulp of 72 % brightness
 brightness decrease from 89 to 68 % ISO with mechanical pulp of 56 % brightness
o A loss of fluorescence
o A pronounced brightness reversion upon light
o The process must therefore include appropriate bleaching treatment to handle this
contamination

• Colored papers :
o The presence of colored papers in the raw materials induces a significant brightness &
luminance decrease.
o 20 % of colored papers in a wood free furnish (issued from a mixture of colored papers
collected in different tissue deinking mills) induces
 a loss of 17 % brightness (0 % UV)
 a loss of 26 % brightness (with UV)

12
  less fluorescence (25 to 15)
 a color shade
o The process must therefore include appropriate bleaching treatment to handle this
contamination

• Brown / kraft fibres

o Brown / kraft fibres are particularly detrimental to recover a high brightness pulp without
any mottling.
o For example, the presence of 5 % brown / kraft fibres induces :
 A brightness loss of 10 % ISO, and 15 % (with UV)
 Less fluorescence
 And especially a pronounced mottling
o The process must therefore include appropriate bleaching treatment to handle this
contamination

• Speck contamination
o High quality DIP is particularly demanding in terms of speck contamination, values
requested are between 3 – 7 ppm (specks > 150 µm), initial contamination varying
between 5 000 to 50 000 ppm depending on raw materials and pulping conditions
o Some customers are even searching for 1 – 2 ppm.
o The process to reach these values is therefore quite complex, based on cleaners,
flotations and dispersing treatments.

• Stickies contamination
11
o Stickies contamination in the recovered papers is increasing (Hamann 2009 ) but the
final content should be maintained very low.
o It should be as low as possible, for all types of stickies : macro & mini, below 500 mm²/m²
with CTP methodology.
o The process should be as efficient as possible including very well designed screening.

• Yield
o Deinking process yield is very low (values from 50 to 70 %) depending on raw materials,
process and pulp properties target
o This low yield is partly explained by the filler content of the final pulp to reach : it should be
very low, similar to virgin pulp ?

• Sludge
o Too high volume of sludge, 1 T DIP generating 1 T of sludge (even 2 T considering the
humidity), for low yield DIP process – 50 %

According to all the contaminants to remove, it clearly explain why the deinking process is so complex.

How to improve the economical interest of high quality wood free DIP
All the requirements necessary for producing a high quality wood free deinked pulp listed previously
illustrate that the economical interest of such a pulp may not be always found. This is especially true
when looking at the sludge volume generated.

Several possibilities to increase the interest of such pulp have been studied at CTP, some of them will
be shortly reviewed.

Achieve a better control of the incoming recovered papers

As already listed, the key to reduce the high quality wood free DIP cost is first to ensure that the
recovered papers are free of “contaminants”.
Recent work has shown that possibilities exist to have a better on-line control of the incoming
recovered papers to refuse very early the bales which are of a poor quality.

Among the incoming contaminants to avoid, some can be easier to remove. With recent development
12
of the Near Infra Red spectroscopy analysis (Cochaux et al. 2007 ), it is now possible to measure
rapidly in incoming bales of recovered papers, before their unloading from the trucks, their humidity,

13
the content of plastic & metal material, and more recently the mineral filler and lignin content.

Correlation between the measured values by NIR and by usual methodology shows a very good
correlation for both mechanical pulp content and mineral filler content. These measurements were
obtained with 25 industrial magazines (SC to LWC) and with 21 industrial newsprints on a quite large
range of fillers (3 to 18 % for news, 5 to 45 % for magazines) and mechanical pulp (45 to 85 % for
both news & magazines) content.

Figure 20 : Correlation between NIR and filler Figure 21 : Correlation between NIR and
content in 25 representative industrial magazines. mechanical pulp content in 21 representatives
industrial newsprints.

Similar types of measurements would be required to control wood free grades but this should be
possible.

These information would be of great interest to limit the wood containing raw materials in wood free
grades as well as to control (and limit ?) the mineral filler content added into the pulper.

As far as brown fibres are 12

11.5
11.3
concerned, another online sensor NewsMag (Weight)
was developed at CTP. The initial Gravimetric controls
goal was to measure the ratio 9
Board content (%)

8.6
between Old Newspaper and Old 7.7
Magazine in the household
collected papers, but another 6
5.5 5.3
5.0 5.1 5.1
4.8
measurement was developed : the 4.7 4.6
4.5 4.3 4.3 4.5
4.4
4.0
4.5
4.4 4.1 4.3 4.5
3.8
proportion of brown papers. 3 3.2
2.6
1.8
The information delivered by the
sensor (NewsMag) was controlled 0
as well with usual manual 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
counting, the correlation is
reported in the following graph. In Figure 22 : Correlation between the brown board measured by
this particular mill, board content image analysis (NewsMag sensor) and the real board content
was quite large, varying between 3 (weight). Ruiz 200613.
to 12 %.

A similar measurement to quantify the proportion of colored papers in a wood free furnish is still under
development.

14
Choose the appropriate bleaching treatment to handle the presence of mechanical pulp :

As the mechanical pulp (M.P.) content was reported to increase significantly in said wood free
14
recovered papers, up to 30 %, Magnin and Chirat 2004 studied the incidence of this mechanical pulp
(coming from magazine) on brightness and stability upon light. The impact of the mechanical pulp is
reported in the following table.

The impact of mechanical fibres on brightness is significant, decreasing it from 80 to 70 % (UV

excluded) inducing also a significant brightness reversion upon light and a loss of fluorescence
probably masked by the lignin from mechanical pulp.

Pilot wood -free pulp DIP with 30 % M.P

DIP WF DIP30%M.P
Mechanical pulp content 10 % 30 %
Brightness 0 % UV 79.9 70.2
Brightness D65 90.9 74.8
Fluorescence index D65 11 4.5
Brightness C/2° 86.5 72.5
Fluorescence C/2° 6.6 2.3
Total ash content (425°C) 6.8 5.4
14
Table 4 . Characteristics of deinked pulp DIP 30 % MP to be bleached. Magnin & Chirat 2004

Bleaching treatments by conventional single stage bleaching allow to recover up to 79 % ISO (with 2
% Peroxide) brightness and 80 % ISO (with 1 % FAS + 2 % P), i.e. recover the initial brightness with
10 % mechanical pulp (named wood free). Brightness reversion upon light is however still present.

Sun reversion - mixture with 30% M.P

Brightness 0 % UV
14
85
83
12
10
PC number

81
79 8
77 6
75 4
73 2
71 0
69 0 1 2 3 4 5 6
67 Ageing, hours
65 Unbleached with 30 % MP 2 %H2O2
Initial Initial 2 % FAS 1% D4% + Z 2% Z2% + FAS + P Z2% + P
pulp pulp H2O2 +P P HC + Popt +
with 30 Popt FAS D4% + P Reference pulp
% MP

Figure 23: Effect on brightness of various
bleaching treatments of a furnish including 30
% mechanical pulp in a “wood free furnish –
14
with 10 % MP”. Magnin & Chirat 2004
Figure 24: Effect on brightness reversion of various
bleaching treatments of a furnish including 30 %
mechanical pulp in a “wood free furnish – with 10
14
% MP”. Magnin & Chirat 2004

A preliminary delignification treatment by chlorine dioxide or ozone allowed to gain even 3 %

additional brightness points without UV and reduce significantly the brightness reversion upon light.
With UV illumination however, brightness gains were lower since D especially and Z, to a lower extent,
destroys whitening agent.

Choose the appropriate bleaching treatment to handle the presence of brown fibres :

As illustrated in Table 3, the addition of brown fibres in deinked white office recovered paper pulp
induces a decrease of the brightness (UV excluded) but also a mottled effect which is not easy to
characterise. Besides an evaluation of the different bleaching agents by brightness measurement (UV
excluded) which does not give any indication on the optical homogeneity of the handsheet, a visual

15
assessment to note the mottled effect without considering the background whiteness of the handsheet
5
has been performed (Magnin et al. 2000 ). Marks have been given by 11 examiners after visual
examination of thin handsheets under artificial illumination (Level 3 : brown fibres are clearly visible ;
level 2 : mottled effect, level 1 : traces ; level 0 : brown fibres are not visible).

In Figure 25, each bleaching stage has been ranged versus the brightness value 0 % UV and the
marks given by the 11 examiners are also reported.

The reductive agents and potassium permono-sulfate are not efficient to reduce the mottled effect.
The oxygen (5 bars O2) clearly reinforces the ability of peroxide (at 90 °C) to decolourise brown fibres
and the effect is more pronounced at lower peroxide dosages.

Peracetic acid at high pH, hypochlorite are effective to eliminate the appearance of brown fibres. Only
traces are mentioned.

The addition of a conventional peroxide stage after the ozone stage is necessary to achieve a total
elimination of the appearance of the brown fibres.

Chlorine dioxide alone is able to eliminate completely the appearance of the brown fibres but with
yellowing of the pulp that can be caught over by a subsequent conventional peroxide stage.

Finally a complete elimination of the appearance of the brown fibres combined with the highest
brightness gains can be achieved with the following sequences :

• Chlorine dioxide followed directly by a conventional peroxide stage at 60°C : DP 60

• Ozone followed directly by a conventional peroxide stage at 60 °C : ZP 60
• Peroxide at 90 °C and peroxide under oxygen pressur e (90°C, 5 bar O 2) with a high peroxide
dosage (2 %) : P90 2% and O/P 2%.

3.5 85

Brightness 0 % UV
Visual level
3 Brightness 80
Visual level

2.5
2 75
1.5 70
1
65
0.5
0 60
%

O 2%

%
ph s
.5

D 0
0
0 Z
Y

H
p D
0. O

0
S

/P .5
5 bre

6
P6
P6
FA
10

O h10
5

2
ZP
0.

/P
SO fi

P9
0
H n

P9

Pa
K ow
br

- Brightness +
%
5

Figure 25 : Comparison of the bleaching stages according to brightness values and visual estimation of
the mottling – Wood free deinked pulp containing 5 % brown fibres.

Out of all those giving interesting results, the most realistic bleaching treatment to implement in a
deinking process is therefore peroxide treatment at 90°C with significant peroxide dosage (2 %). This
treatment is efficient to bleach mechanical fibres and to remove the mottled effect induced by the
presence of brown fibres. Combined with FAS or hydrosulfite, it is also very efficient as colour stripping
agent.

16
Choose the appropriate bleaching treatment to handle the presence of colored papers :
5
Magnin et al. 2000 studied the effect of various discoloring agents on a wood free furnish
contaminated by the presence of 20 % colored papers. Refer to Table 2 to see the pulp properties
with and without colored papers.

The different bleaching sequences have been performed at laboratory scale. Peroxide, peroxide under
oxygen pressure (O/P), hydrosulfite, FAS, ozone (Z), oxygen (O), chlorine dioxide (D), hypochlorite
(H), peracetic acid and potassium permonosulfate have been tested.

Bales of coloured papers came from 4 places in France which collect and sort out mixed office waste
and from a tissue producing mill.

The best results in one single stage are obtained by the reductive agents, followed by ozone, chlorine
dioxide and hypochlorite. No clear improvement of the P stage by oxygen pressure can be observed
for colour-stripping effectiveness (Figure 26). The best combinations are ZP60 – Y and DP60 - Y where
P60 is a hydrogen peroxide bleaching performed at 60 °C (Figure 27).

FAS 1% FAS 1%+ 2P90

Y 1% Y 1%+ 2P90
KHSO5 pH10.5 KHSO5 pH10.5 +Y
Pa pH 8 Pa pH 8+Y
H 1% H+Y

DP60 DP60+Y

D 1% D+Y
Bleaching agent

ZP60 ZP60+Y
Bleaching agent

Z 1.4% Z+Y Hyperwashed pulp

1P 60°C 1P 60°C+Y Entire pulp

O/0.5P90 O/0.5P+Y

Hyperwashed pulp 0.5P 90°C+Y

0.5P 90°C
Entire pulp O/2P+Y
O/2P90
2P 90°C+Y
2P 90°C
O,5b+Y
O, 5b
75 77 79 81 83 85 87 89 91
10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Dye removal index %
Dye removal index %

a15
Figure 26 . Percent colour removal for single Figure 27 . Percent colour removal for two stage
bleaching sequences – Wood free deinked pulp bleaching sequences – Wood free deinked pulp
containing 20 % coloured papers containing 20 % coloured papers
Furnish : 80 % deinked white office recovered papers + 20 % deinked pulp from coloured bales
FAS : FAS bleaching, 1 % FAS, 0.5 % soda, 1 hour at 80 °C (12 %)
Y : hydrosulphite bleaching, 3 % consistency, 1 % hydrosulphite, natural ph, 1 hour at 80 °C
P90 : Peroxide bleaching, 15 % consistency, 30 min at 90 °C, H2O2 %/NaOH% : 2/1,
silicate /DTPA : 2.5%/0.3%
OP : same conditions as P90 but 5 bars oxygen
P60 : 15 % cons, 90 min, 60°C, H2O2 %/NaOH% : 1/1, silicate /DTPA : 2.5%/0.3%
Pa : Peracetic acid bleaching, 10 % consistency, 1 % active peroxide, 90 min, 60°C, pH : 4-6-8-10.5
KHSO5 : potassium permonosulphate bleaching, 10 % consistency, 1 % active peroxide, 90 min, 60°C, ph 4-6-8-10.5
H : hypochlorite bleaching, 1 % NaClO, 4 % consistency, 60 min at 40°C, 1 % soda
Z : ozone bleaching, high consistency (38 %), 1 % consumed
D : chlorine dioxide bleaching, 15 % consistency, 60 min at 80 °C, 1 % applied
DP and ZP : no washing between the two stages

a
To evaluate the colour-stripping effectiveness of different bleaching agents without considering the effect of the
fluorescent whitening agents, a Dye Removal Index (DRI), besides the measurement of the brightness 0 % UV,
can be calculated referring to the achromatic white. The DRI is calculated from colorimetric coordinates L*, a*, b*
measured UV excluded and is referred to the perfect achromatic white (L* = 100, a* = 0, b* = 0). This dye removal
index is an indicator of the percentage of total colour removed but it does not give any indication of the residual
15
shade of the final product. The higher the DRI value, the best the colour-stripping. Sharpe & Lowe 1993 .

17
From Figure 26, it can be concluded that the different bleaching agents can be ranged in four groups
versus the colour-stripping effectiveness:

• 70 % < DRI < 75 % : FAS, hydrosulphite

• 60 % < DRI < 70 % : Ozone followed directly (without washing) by a conventional peroxide stage
(1 % peroxide, 60°C) and chlorine dioxide followed directly by a conventional peroxide stage.
• 50 % < DRI < 60 % : ozone, chlorine dioxide, hypochlorite
• DRI < 30 % : peroxide at 60 & 90 °C (P), Potassium permonosulphate, peracetic acid, oxygen.

From Figure 27, the following conclusions can be drawn :

• By combining a reductive stage and an oxidative stage, the best results in two stage bleaching are
obtained with hydrogen peroxide at 90 °C (2 % H 2O2), hydrogen peroxide under oxygen pressure
(90 °C, 2 % H 2O2 ) and peracetic acid (1 % equivalent active peroxide), reaching 83 % dye
removal index (83 % brightness). No significant difference appears between the combination
peroxide - hydrosulfite or the reversed combination.
• Examining the performances of a P and an O/P stages, there is no clear improvement of the P
stage by O2 pressure whatever the peroxide charge (0.5 % or 2 %) and for the following conditions
(rotary reactor, pressure 5 bar O2, consistency 15 %, temperature 90 °C, 30 min at 90 °C).
• The combinations of three stages ZP60Y or DP60Y allow 4 additional DRI points (and 2 additional
brightness points) to be obtained compared to the best two stage bleaching.

On a white office waste paper pulp containing both fluorescent whitening agents and colored papers,
the reductive agents are a good compromise in terms of color stripping (referring to the achromatic
white) combined with a good visual assessment (referring to a “chromatic white” under UV
illumination).

24
∆E* (versus pulp 5NFW)
DP60 + Y

22
D+Y

20
Inititial pulp

ZP60 + Y

18
Z+Y

KHSO5 pH10.5 + Y

16
14
Pa pH10.5 + Y

12
FAS + 2P90
O/2P90 + Y

1P60 + Y
O,5b + Y

10
2P90 + Y

H+Y

Y + 2P90

8
6
4
2
0
b
Figure 28 : Total colour difference (versus initial pulp free of colored papers – NFW)) under UV
illumination. Multistage bleaching - Wood free pulp containing 20 % coloured papers

Bleaching treatment on a wood free furnish free of colored papers is anyway interesting because it
can bring between 4 to 6 % ISO after deinking, on a pulp well deinked (low ERIC of 20 – 40 ppm). The
main interest of this bleaching treatment is to take care of the mechanical pulp, but as seen
combination of both reductive (Y or FAS) and oxidative (P) are interesting to also discolour the
residual shade.

b 2 2 2 0.5
∆E =[ (L*2-L*0) + (a*2-a*0) + (b*2-b*0) ] ,
Bleached pulp (L*2, a*2, b*2) ; Target pulp 5NFW (L*0 = 93, a*0 = 3.9, b*0 = -14.5)

18
Improve the flotation selectivity

Deinking process yield, as reported previously, is rather low, between 50 to 65 %. If we consider the
filler content at the pulper, between 25 to 30 %, an ideal yield value, assuming a total removal of filler,
would be 70 to 75 %. There is thus at least 10 to 20 % material, cellulosic fines & fibres which are
lost. The interest of keeping these elements in the final pulp is quite clear provided that these do not
disturb the process and do not impair the properties of the produced paper.

Among the main reasons explaining the high removal of fillers & fines during the flotation process, one
of them is the high foaming of the pulp suspension. This foaming is induced by the presence of
surface active substances, generally released by recovered papers. It can be surfactants added in the
coating colour formulation, surface active substances released by mechanical pulp during an alkaline
treatments…. Whatever their sources, all these substances are particularly detrimental to a high
flotation selectivity. This is why, a flotation treatment, performed on the deinking process waters allow
to remove these substances which contribute then to reduce significantly the flotation loss, as
illustrated by the following graphs (Figure 29).

Lab experiments with a rotogravure printed Flotation

16
magazine (Carré et al. 1999 ) aiming at (i) losses (%)
repulping recovered papers, (ii) separating the Ashes inlet Total Filler
process waters by thickening, (iii) floating the (%)
process waters to remove released surface active
substances, (iv) and finally used these “surfactant Without 40.2 33.6 51.2
free” process waters to float the thickened pulp removal
allow to reduce significantly the flotation losses : With removal 39.9 24.4 35.8
Figure 29 : Removal of surface active substances
• - 27 % for total loss,
from the process waters : effect on flotation yield
• – 49 % less ash loss. 16
(Carré et al. 1999 ).

Similar experiments were repeated more recently in a wood containing recovered papers mill with
17
deinking process waters from the first deinking loop (Carré. 2008 ). The mill had a significant load of
surface active substances since having a high share of old magazine in the furnish .

70 Flotation experiments, performed with the

Continuous Flotation Cell (Beneventi et al.
18
Ink removal efficiency (%)

60 2006 ) was used to remove the surface active

substances from the first loop deinking process
50 waters in a mill producing newsprint from
ONP.OMG mixtures. A methodology has been
40 developed to quantify the surface active
substances removal, applied in several mills
30 19
(Zeno et al. 2008) . Thanks to the process
20
Reference flotation : dilution without waters flotation experiments performed with
process water flotation different froth thickness it was possible to plot the
Trial flotation : dilution with floated ink removal efficiency, versus the total solid loss.
10
process waters

0 At identical ink removal efficiency, it was thus

0 10 20 30 40
possible to reduce the flotation loss from roughly
30 % to 17 %.
Total Solid Loss (% )
Most of this reduction was explained because
more fillers and fines were kept in the pulp and
Figure 30 : Removal of surface active substances entrained, floated, in the froth.
from the process waters : effect on flotation yield A first mill trial, too short (6 hours), was thus
17
(Carré 2008 ). performed confirming the lab trend observed.

Because of the interesting possible gain in yield, the removal of surface active substances from the
20
deinking process water has been patented (Carré 2006 ).

Another effect of the surface active substances present in process waters is their impact on speck
particles flotation, as explained hereafter :

19
Lab flotation experiments were performed with
Specks contamination versus losses
toner based prints, repulped in conventional
Helico pulper at 15 % consistency. Pulp was 16000 100 %
then diluted for flotation, either with tap water 14000
(0 %) or with increasing proportion of an 12000 after flotation
industrial wood free deinking mill process

mm²/m²
10000
waters. Flotation was then performed on a
8000 50 %
conventional Voith laboratory flotation cell for 7
6000 Increasing share of
min (200 % air). Results clearly show that 0%
4000 25 % industrial process
when the pulp is diluted with industrial waters,
2000 waters
foaming is much more significant and speck
removal is much lower despite the higher loss. 0
0 5 10 15 20 25 30 35
flotation losses %
This large reduction of selectivity is due to (i)
the much higher foaming stabilising entrained
elements in the froth, (ii) smaller & more Figure 31 : Effect of increasing proportion of a wood
hydrophilic air bubbles much less efficient for free deinking mill process water on speck flotation
speck collection and flotation. and loss.

The surface active substances removal is therefore also very useful to improve the speck flotation
selectivity.

Simplify the deinking process

Deinking processes proposed some years ago to produce high quality wood free DIP were quite
complex, including up to 3 deinking loops with 1 or 2 washing treatments, 1 or 2 dispersing treatments,
2 or 3 flotations and 2 bleaching. The diversity of process being explained by the different type of
recovered papers used and the final DIP requirements.

Nowadays, process proposed generally include only 2 deinking loops, with 2 flotation and one or 2
washing stages, 2 bleaching treatments, 2 dispersing stages. Two examples were reported in Figure
15 and Figure 16.

In order to simplify the deinking process, a large work, performed in the frame of an European project,
c
Ecotarget , has been performed. The objectives were (i) to rationalise the pulping stage to avoid any
irreversible phenomena at that stage, (ii) to develop innovative and new unit operations (the work was
focused on a simplified screening system reducing the number of screening stages, (iii) to improve ink
flotation selectivity through the implementation of surface active substances removal treatments (Cf
previous paragraph), and (iv) on fractionation and recombination of the unit operations.

The rationalized process proposed is the following :

c
www.ecotarget.com

20
 Coarse & Free Ink Fractionation
Drum pulping
Pre screening

0,15mm
Compact system Fine
Helical 4mm screening Flotation
pulping
Simplified Washer
Bleaching, for market DIP screen
Dispersing
HC Thickener
Disc filter

Filtrate Flotation
clarification
& Flotation Cleaning

17
Figure 32 : Rationalized deinking process, Carré 2008 .

The rationalized process, initially developed for wood containing applications, consists in :
• a pulping stage as soft as possible to keep a sufficient size to the contaminants and therefore
facilitate their subsequent removal. At that stage all fragmentation phenomena, for any
contaminant as well as for ink, should be avoided.
• A simplified screening system substituting both holes and slots screens.
• A free ink fractionation to separate very early in the system all the ink particles which have
already been detached during the pulping stage. Their separation is especially necessary to
avoid sending these detached particles to the dispersing unit.
• On the long fraction :
o A fine screening stage on the long fraction to remove very efficiently the remaining
contaminants, large and rigid enough.
o A washing stage to separate even more all the detached ink particles in the water
flow.
o A dispersing stage on the long fraction to detach the remaining attached ink and to
break down the speck particles.
• On the short fraction :
o After being mixed with the washing waters, the short fraction is submitted to dispersed
flotation to remove the detached ink particles without removing the fillers & fines
particles
• On the re-mixed long and short fractions : online flotation to remove all the remaining ink
particles (not well removed from the water phase and detached in the disperser)
• Cleaning stage on the diluted whole pulp followed by thickening on a disc filter and a screw or
double wire press.
• The thickening waters can then be treated differently according to the required filler content of
the pulp, but the ideas are first to remove some suspended solids if necessary by dissolved air
flotation and then to float, by dispersed air flotation, the surface active substances to improve
the other dispersed flotation selectivity. Such removal is also very efficient to improve the
speck flotation which discharge the dispersing treatment.
• Bleaching is (are) then applied on the thickened pulp

This “rationalized” deinking process was initially designed for a wood containing deinking process, for
the production of newsprint or SC papers. If fillers have to be removed partially (for LWC application)
or totally (for tissue or market pulp application) then, part of the flotation accept performed on the
water phase may be introduced at the dissolved air flotation inlet with the thickening waters to control
the filler removal. Another option is to substitute the final disc filter by a washer.

21
The implementation of a second dispersing unit at the outlet of the screw or double wire press will
depend on the cleanliness required and on the raw materials used, but the dispersing treatment on the
long fraction and the better speck flotation selectivity thanks to the surface active substances removal
may avoid its use.
At the end of the process, when all the ink has been removed, the process is terminated by 2
bleaching treatments, oxidative followed by reductive bleaching with an intermediate neutralisation of
residual peroxide. This will allow to handle the presence of mechanical pulp, colored papers and a few
% of brown fibres.

Define the minimum DIP quality requirement for coated paper.

When DIP is used for the production of wood free coated paper, DIP is generally used as a substitute
to hardwood virgin fibres. In that sense the required DIP quality criteria are those more or less of
hardwood virgin fibres. Due to the sometime low added value of high quality wood free DIP, it may
however be possible to hide some DIP pulp defects by coating.

A lower brightness and a lower cleanliness may be accepted provided that coating, with adapted
formulation, coating technique and coating layer grammage, is able to mask the defects.

The answers to these questions are currently under investigation in the frame of an open project at
CTP. If coating is able to hide some defects, it may change significantly the economical interest of
producing high quality wood free DIP and render it less sensitive to the market variations (price of
recovered, price of virgin pulp, price of market DIP pulp and price and possibilities to use the deinking
sludges) !

Conclusions
Even if it is not common, the utilisation of wood free recovered paper for the production of high grade
DIP in order to produce fine paper is today possible, some mills are running like that. This high grade
DIP is generally used as a substitute to hardwood virgin pulp and it has shown some advantages over
virgin pulp such as (i) lower refining energy, (ii) better opacity, (iii) better paper formation…

Several reasons however explain why this trend is not widely spread. Among these, the first one is the
availability of these high grade wood free recovered papers : the office collection is not well developed
and needs some improvements. The second one is that the recovered papers contamination can be
very detrimental, several unwanted papers must for example be rejected during the sorting, such as
those containing mechanical pulp (especially those with a low brightness), papers made from brown
kraft fibres coming for example with envelopes, colored papers, …all giving difficulties to recover high
brightness and requiring adapted bleaching treatments (2 % P at 90°C followed by a reductive
treatment Y or FAS seem to handle more or less all the possible contamination). The third reason lies
in the fact that the pulp properties requirements are quite high, such as a very low residual ink content
(< 50 ppm) associate to a high brightness (> 80 % ISO), a very high cleanliness (< 2 – 5 ppm specks),
a very low stickies content and this, apart having a careful selection of the recovered papers, requires
a very efficient and complex process. Fulfilling these requirements is economically not easy,
considering the price variations of recovered papers, of the final product (pulp), and the cost of the
process necessary to handle all the various contaminants and the sludge produced.

To increase the competitiveness of this high quality DIP, some possibilities have been identified : (i)
the on line control of the incoming raw materials, either to reject some bales, or to adapt the process
conditions to these raw materials, (ii) rationalize the deinking process by implementing adapted
treatments on each fraction, and by separating as early as possible the detached inks, (iii) improve the
flotation selectivity by removing disturbing surface active substances which has however some
consequences : an increase of the cellulosic fines content and an increase of the filler content that the
paper machine will have to handle.

Finally, other alternatives to increase the competitiveness of this pulp would be : (i) to try to sell the
market DIP with the recycled fillers instead of trying to compete with virgin hardwood pulp !, (ii)
evaluate the possibilities to reduce the DIP market pulp quality criteria provided that coating can hide
the defects (brightness & specks).

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Abbreviation list

DIP : Deinked Pulp

ERIC : Effective Residual Ink Concentration, ppm
SC : Super Calendered Paper
LWC : Light Weight Coated paper
NFW : Neutral Pulping followed by Flotation & Washing.
FAS : Formamidine sulfinic acid
NIR : Near Infra Red Spectroscopy
DRI : Dye Removal Index
ONP : Old NewsPaper
OMG : Old Magazine

1
Ringman, J. (2009) : “The Recycling industry, European perspectives, facts and figures”,
th
Proceedings of the 9 Advanced Training Course on Deinking Technology, June 3-5 2009, Centre
Technique du Papier, Grenoble, France
2
Huber, P., Carré, B., Petit Conil, M., Fabry, B. and Bhattacharjee, S. (2004) : “Effect of the deinking
th
process on physical properties of various wood-free recovered paper furnishes”, Proceedings of the 7
th
PAPTAC Recyled Fibres Research Forum, Quebec, September 27 – 29 2004.
3
Lachenal, D. (1994) : “Bleaching of secondary fibres – basic principles”, Progress in Paper
Recycling, vol. 4, no. 1, Nov. 1994, pp 37-43
4
Burnet A., Carré B., Ayala C., Fabry B., Marlin N. and Chirat, C. (2007) : “Influence of fibre mix on
the recycled pulp brightness and influence of Na2SiO3, NaOH, H2O2 during hydrogen peroxide
bleaching on effluent quality”. Proceedings of the International Symposium "Present and Future of
Paper Recycling Technology and Science", Bilbao, May 24-25 (2007)
5
Magnin, L., Angelier, M.C. and Galland, G. (2000) : “Comparison of various oxidising and reducing
agents to bleach recycled fibres”. PTS CTP Deinking Symposium 2000, May 2000, (München)
Proceedings : Paper 12
6 th
Delagoutte, T. (2009) : “Contaminants impact and management in recycled pulps”, 9 Advanced
Training Course on Deinking Technology, June 3-5 2009, Centre Technique du Papier, Grenoble,
France
7
Doshi, M. R. (1997) : "Quantification of micro stickies ", Progress in Paper Recycling, 3(4) : 80-83
(November 1997).
8
Delagoutte, T. and Kumar, S. (2008) : “Stickies balance: an efficient tool to improve your process
th
efficiency”, Proceedings of the 13 PTS - CTP Deinking Symposium, Leipzig, April 15 – 17, 2008
9
Galland G., Fernandez de Grado A., Delagoutte T., Lascar A., Kumar S. (2009) : "Mini-stickies or the
challenge of small macro-stickies management: characterization, mill survey and removal strategy",
Paper accepted and to be published in Progress in Paper Recycling
10 th
Hanecker, E. (2009) : “Treatment and utilisation of deinking sludges” 9 Advanced Training Course
on Deinking Technology, June 3 – 5, 2009, Grenoble, France.
11 th
Hamann, L. (2009) : “Stickies : definition, origin and characterization”, 9 Advanced Training Course
on Deinking Technology, June 3 – 5, 2009, Grenoble, France.
12
Cochaux, A., Borel, P., Eymin Petot Tourtollet, G. and Rech, D. (2007) : “The New Techpap NIR
th
spectroscopy for Recycled Bale Inspection”, Proceedings of the 8 PAPTAC – TAPPI Research
Forum on Recycling, Niagara Falls, September 2007.
13
Ruiz, J. (2006) : “On line composition assessment of the recovered papers
th
to be deinked: industrial trials”, Proceedings of the 12 PTS – CTP Deinking Symposium, Leipzig,
April 26, 2006.
14
Magnin, L. and Chirat, C. (2004) : “Use of delignifying agents for bleaching of DIP containing 10 to
th
30 % mechanical pulp”, Proceedings of the 4 CTP Recycled Fibres Forum, Grenoble, February 26 &
th
27 2004.
15
Sharpe P.E. and Lowe R.W., (1993) : “The bleaching of colored recycled fibers”, Pulping
Conference 1993,Tappi Proceedings.
16
Carré, B., Vernac, Y. & Beneventi, D. (1999) : “New insights in the reduction of flotation losses :
input of dynamic interfacial tension measurements”, Proceedings of the PAPTAC Research Forum on
Recycling, Ottawa, September 28-30, 1999.
17
Carré, B. (2008) : “Simplified Deinking Process : From lab to mill trials”, Proceedings of the final
Ecotarget open conference, Stockholm, Nov 12, 2008.
18
Beneventi, D., Rousset, X., Zeno, E., (2006) : “Modelling transport phenomena in a flotation de-
inking column. Focus on gas flow, pulp and froth retention time”, International Journal of Mineral
Processing 80, 43-57. 2006

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19
Zeno, E., Angelier, M.C., Beneventi, D., Carré, B. (2008) : “Surfactant mass balance in industrial
deinking plants: a tool for flotation control”, PTS-CTP Deinking Symposium, Leipzig, 15-17 April 2008
20
Carré, B. (2006) : « Procédé de réduction de la teneur en substances tensioactives au cours du
désencrage du papier et dispositif de désencrage mettant en œuvre ce procédé », French patent n°
06 53060, European patent n° 07301077.9.

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