PTS Symposium Applied Interface Chemistry, Munich 2010

Water quality effect on retention aids efficiency in the paper

industry

Ruth Ordóñez, Daphne Hermosilla, Elena Fuente, Ana Moral, Ángeles Blanco, Madrid, Spain

ABSTRACT
A compromise between product quality, machine runnability, and process water quality is
needed to reduce fresh water consumption in paper mills. As 10-15% of the fresh water
intake is used for feeding and diluting retention aids, important savings could be achieved by
replacing fresh water with process water.
This study was conducted in a 100% recovered paper mill located in Madrid (Spain). A dual
system, consisting of a cationic polyacrylamide (cPAM) and bentonite, was selected as
retention aid and its efficiency, in connection with the quality of the water used in its
preparation, is assessed. Both cPAM and bentonite were prepared using different water
qualities: fresh water (coming from the region’s water utility), outflow from an internal
ultrafiltration (UF) and the outlet from a membrane bioreactor (MBR). Results were analyzed
in terms of flocculation, drainage, retention efficiency and final paper properties.
The optimum dosage of cPAM was the same for the three different types of water tested, but
the use of UF and MBR waters to dissolve cPAM reduced the floc size obtained and,
therefore, flocculation efficiency. While the behaviour of bentonite was not significantly
affected by the water quality used in its preparation, the efficiency of the cPAM was reduced
about a 12% when it was prepared with water with high anionic trash content and
conductivity. The effect of non-ionic COD on cPAM efficiency was negligible.

INTRODUCTION
A great part of the fresh water intake (10-15%) of a paper mill is used for feeding and diluting
wet-end chemicals (Ryöso and Manner, 2001). As white water is highly reused, detrimental
substances (coming from wood, paper recycling and chemicals added) accumulate in the
water circuit (Hubbe, 2007) generating the following problems (Berard, 2000): wet-end
deposition (58%), mill odors (55%), foam and corrosion (47%), final product odor (45%),
decreased machine operability (38%) and losses in drainage (33%). For all these reasons,
the implementation of different internal purification strategies (e.g., chemical coagulation
(Hodgson et al., 1998), dissolved air flotation (Miranda et al., 2008; Miranda et al., 2009a;
Miranda et al., 2009b), membrane filtration (Dal-Cin et al., 1997; Hamann and Bachner,
2002), biological (Driesen et al., 2007), enzymatical (Zhang, 2000) and oxidative treatments
(Augustina et al., 2005), are necessary to improve the closure of water circuits in the mills.
Nowadays, researchers aim to further reduce fresh water consumption in the paper industry,
without affecting product quality and paper machine runnability. One of the main uses of
fresh water in paper mills is the preparation of chemicals; in this way there are mainly two
different approaches of research (Joore et al., 2000). The first one covers the study of how
detrimental substances, present in the pulp suspension, affect the performance of retention
aids (Hubbe, 2007); and the second approach is focused on analyzing the effects of the
quality of preparation water on the efficiency of retention chemicals (Ryösö, 2001a; Ryösö,
2001b).
In this way, the main objective of this research is to evaluate the effect of different types of
water quality, outflowing from different water treatments available in a recycling paper mill, on
the preparation of the retention aid system from powder. Results are analyzed in terms of
flocculation, drainage and retention efficiency, and the properties of the final paper product.

R. Ordóñez, D. Hermosilla, E. Fuente, A. Moral, A. Blanco 1

PTS Symposium Applied Interface Chemistry, Munich 2010

MATERIALS AND METHODS

Fresh de-inked pulp from a newsprint paper mill in Madrid (Spain) was used in the
experiments. This mill uses 100% recycled paper as raw material and tap water coming from
the regional water utility, as fresh water.
The retention chemicals dual system under evaluation consists of a cPAM and bentonite.
The cPAM used is PERCOL3320 and the bentonite is HYDROCOLOM2LS, both were
supplied by Ciba, Basel, Switzerland (now part of BASF, Ludwigshafen am Rhein, Germany).
cPAM suspensions of 1 g/L were prepared by adding the powder to the tested waters and
mixing the solution for 1 h. The bentonite was prepared in the same way at a concentration
of 5 g/L. Maturation time was 1 day for both chemicals.
Three different qualities of water, from different sources inside the mill, were used to prepare
and compare the behavior of the retention system: fresh water (FW), the outflow from an
internal ultrafiltration (UFW) placed in the machine circuit (process water), and water from a
membrane bioreactor (MBRW) used to treat the final effluent of the paper mill. All the waters
were analyzed to compare their quality (APHA, AWWA and WEF, 2005) (Table 1).

TABLE 1. Characterization of the water used to prepare the retention system.

parameter Units pulp suspension fresh water UF water MBR water

pH 8.04 7.58 7.50 7.65

conductivity mS/cm 1.16 0.11 2.30 3.19

TSS g/L - 0 0 0
a
CD mequiv/L 0.216 0 0.340 0.988
turbidity NTU - 0 4.22 1.77
alkalinity mequiv of CaCO3/L 8.49 0.45 12.47 15.29
hardness mequiv/L 2.0 1.2 2.8 5.6
b
soluble COD mg/L 586 0 952 431
BOD5 mg/L 250 0 360 20
2-
SO4 mg/L 276 <10 130 375
2+
Ca mg/L 38 21 40 75
Dissolved SiO2 mg/L 80 <0.2 140 100
a
CD, cationic demand; CODb, chemical oxygen demand.

Flocculation studies were performed with a M500L FBRM probe manufactured by Lasentec,
Mettler Toledo, Seattle, WA (Blanco et al., 2002a; Blanco et al., 2002b). All the experiments
with the FBRM were programmed to obtain a chord length distribution every 5 s. The optimal
dosage of cPAM was determined by adding 0.3 mg of polymer/g of dried pulp every 30 s,
while stirring the suspension at 400 rpm, until the mean chord size reached a constant value
(saturation level). cPAM and bentonite were combined in a 1:1 weight ratio. Flocculation
trials were performed following the scheme showed in Figure 1.

2 R. Ordóñez, D. Hermosilla, E. Fuente, A. Moral, A. Blanco

 PTS Symposium Applied Interface Chemistry, Munich 2010

400 rpm 800 rpm 400 rpm

MEAN CHORD LENGTH (μm)

2
bentonite
addition

CPAM
addition
4

3
1

20 50 250 500 600

TIME (seconds)

FIGURE 1. Procedure followed in the flocculation trials.

Drainage was measured using MütekTM DFR-04 (BTG) equipment, where the evolution of
the filtrate weight versus the drainage time evolution is determined. Filtrates were collected
to measure turbidity and total solids. The quality of the type of water used to prepare the
retention system was also compared in terms of the characteristics of the final paper product.
Paper hand sheets of 60 g/m2 were formed with a FRET Retention Tester (Techpap, Saint
Martin D’Heres, France) to analyze several parameters according to normalized trials: tensile
strength (ISO/FDIS 1924-3:2005), the percentage of elongation (ISO/FDIS 1924-3:2005),
ISO brightness (UNE 57062:2003), formation and the ash content ((UNE 57050:1994). The
first three parameters were measured with an Autoline 300 (Lorentzen & Wettre, Kista,
Sweden) and formation was measured with a Beta Formation Analyzer (Ambertec, Espo,
Finland).

RESULTS
Theoretically, when the cPAM is added to the pulp, suspended particles are flocculated.
Flocs are slowly broken down by shear forces, and when bentonite is added, a three-
dimensional microfloc structure is formed, which favors drainage and retention of fines and
fillers without affecting formation (Asselman et al., 2000).
The optimum dosage of cPAM was determined by the FBRM according to Blanco et al.
(2002a; 2002b), and it resulted in 1.5 mg/g for the three types of water used to prepare the
retention chemicals. As much polymer is added to the suspension, flocs increased in size
gradually until a certain value. The optimal dosage is selected when the floc size is kept
constant. This dosage was adopted to perform the flocculation experiments. Water quality
did not affect the optimal dosage of cPAM, but it reduced the MCL obtained for each dosage.
When UF or MBR waters were used to dissolve the cPAM, the ratio between the anionic
compounds content and the cPAM is higher. Although anionic trash does not cause an extra
consumption of cPAM chains, it affects some cationic groups of each chain, leading to a
slight reduction of the efficiency of the polymer.
The quality of the water used to prepare the bentonite did not influence flocculation (Figures
2) or drainage (Figure 3) significantly. The specific surface of bentonite is very high and
anionic. Therefore, electrostatic repulsive forces act between this surface and the anionic
trash contained in the water used to disperse the bentonite (Schouten et al., 2007).

R. Ordóñez, D. Hermosilla, E. Fuente, A. Moral, A. Blanco 3

PTS Symposium Applied Interface Chemistry, Munich 2010

28 FW-FW
FW-UFW
FW-MBRW
26
UFW-FW

MEAN CHORD LENGTH (mm)

UFW-UFW
24 UFW-MBRW
MBRW-FW
MBRW-UFW
22 MBRW-MBRW

20

18

16

14
0 100 200 300 400 500 600
TIME (s)

FIGURE 2. Evolution in time of the mean chord length after flocculating the pulp with
the retention aid system prepared with different types of water quality.

According to Figure 2, the highest MLC values were obtained when the cPAM was prepared
with fresh water; and the lowest floc size was achieved when it was dissolved in MBR water.
The quality of water affected significantly the efficiency of the cPAM. In terms of drainage,
the best results were also shown when the cPAM was prepared with fresh water (Figure 3).
The use of UF or MBR waters to prepare the cPAM reduced drainage rate and increased
turbidity and solids content of the filtrate (Figure 4).
Cationic demand (CD), conductivity, hardness, chemical oxygen demand (COD), and
sulfates content were the parameters presenting the most significant differences among the
three types of water (Table 1). Anionic substances contents, measured by CD, shows a
partial polymeric character that makes them sparingly soluble in water and able to interact
with the cationic groups of the cPAM, reducing its effective cationic charge density.
Therefore, the interaction with fibers, fines, fillers, bentonite, and other colloids in pulp
suspensions will be weaker. As a result of the weaker interaction of the cPAM with the
bentonite, a higher amount of bentonite does not interact with the cPAM and behaves as a
filler, passing through the wire during water drainage and increasing the turbidity of the
filtrate. The reduction in floc size and the increase of the amount of non-flocculated fillers and
fines result in a closer mat structure than the one obtained when fresh water was used to
prepare the flocculant, which reduces the drainage rate.

4 R. Ordóñez, D. Hermosilla, E. Fuente, A. Moral, A. Blanco

 PTS Symposium Applied Interface Chemistry, Munich 2010

600
FW-

500

WEIGHT OF FILTRATE (g)

UFW-

400
MBRW-

300
FW-FW
FW-UFW
FW-MBRW
200 UFW-FW
UFW-UFW
UFW-MBRW
100 MBRW-FW
MBRW-UFW
MBRW-MBRW
0
0 20 40 60 80
TIME (s)
FIGURE 3. Drainage trials, as filtrate weight evolution in time, for every water
combination used in the preparation of the retention aid system.

As the behaviour of bentonite was not influenced by the quality of the water used for its
preparation, the studies analyzing the final paper quality were performed by preparing the
bentonite with fresh water. Results related to paper quality are shown in Figure 5. Both, ISO
brightness and grammage were not different for the three types of water used. All the other
studied parameters were similar for fresh water and UF water, but were very different for
MBR water. As has already been mentioned, when drainage results are analyzed, if MBR
water is used, the retention of fines and fillers is reduced considerably, so the paper sheet
shows a lower ash content.

400
TOTAL SOLIDS CONTENT IN FILTRATE (%)

70
350
60
300
TURBIDITY (NTU)

50
250
40
200

30
150

100 20

50 10

0 0
W

FW

W
W

FW FW

FW

W
-F

BR

-F
-F

BR

BR
-U

-U

-U
FW

FW

W
-M

-M
-M

FW

W
FW

BR
U

W
BR
FW

BR
M
U

FIGURE 4. Turbidity (vertical bars) and total solids content (squares) of the filtrate
obtained in drainage trials of every preparation water combination.

R. Ordóñez, D. Hermosilla, E. Fuente, A. Moral, A. Blanco 5

PTS Symposium Applied Interface Chemistry, Munich 2010

On the other hand, a higher tensile strength and elongation percentage is attributed to a
lower amount of fillers (Thorp, 2005; Baker, 2005) and to a lower formation index. It is
important to consider that although fillers reduce the strength of the paper sheet, they are
also used to reduce the cost of raw materials and to increase the quality of the paper.
Moreover, when flocs are large enough, the attachment of fillers to them is favoured. If flocs
are small, the aggregation of colloidal particles themselves is improved (Fuente et al., 2003)
forming small flocs that are not easily retained. As formation refers to the uniformity in the
spatial distribution of fibers, fines and fillers in the paper sheet, large fiber flocs deteriorate
formation because of the relatively large diameter of the pores formed in the wet sheet
(Mabee, 2001). Figure 5 shows that formation index decreases when the cPAM is prepared
with MBR water. Moreover, the use of fresh water and UF water in the preparation of the
cPAM leads to worse formation. These results were expected, as the flocculation efficiency
shown by the cPAM prepared with MBR water was lower than that in the other cases.
Consequently, the sheets of paper manufactured when MBR water was used for the
preparation of the cPAM showed better mechanical properties (tensile strength and
elongation), but lower ash content and grammage.

70 3.5
ISO BRIGHTNESS/GRAMMAGE (g/m2)/FORMATION (g/m2)/ASH (%)

60 3.0

TENSILE STRENGTH (N/m )/ELONGATION (%)

50 2.5

40 2.0
ISO Brightness
Grammage
Formation

2
30 1.5
Ash content
Tensile strength
Elongation
20 1.0

10 0.5

0 0.0
FW-FW UFW-FW MBRW-FW

FIGURE 5. Final paper properties related to the water quality combination

used in the preparation of the dual retention aid system.

CONCLUSIONS
The optimum dosage of the cPAM was the same for the three different types of water quality
tested. But the use of UF and MBR waters to dissolve the cPAM produces a reduction of the
flocs sizes and, therefore, a decrease in flocculation efficiency. MBR water contains the
highest anionic trash, which results in a partial neutralization of the charged groups of the
cPAM. Consequently, a reduction of its efficiency is observed, as reflected by the lower
retention of solids and drainage rate and the improvement of formation that are shown. Thus,
tensile strength and elongation show higher values. The effect of nonionic COD on cPAM
efficiency was negligible. Therefore, the re-use of water from the mill to prepare cPAM
solutions requires previous neutralization and removal of anionic trash. On the other hand,
bentonite was not significantly affected by the type of water used in its preparation in any
case.

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 PTS Symposium Applied Interface Chemistry, Munich 2010

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