PAPER PHYSICS
Nordic Pulp & Paper Research Journal Vol 31 no (1) 2016
Deinking by flotation under neutral condition using fatty
alcohol ethoxylates
Belkis Sulbaran-Rangel, Hader Alzate, Ezequiel Delgado, Alma Rosa Saucedo, and José Turrado
KEYWORDS: neutral deinking, fatty alcohols
ethoxylates, hydrophilic-lipophilic balance, DBO5 and
COD
SUMMARY: The aim of the present research was study
deinking flotation process under neutral condition using
biodegradable surfactants type fatty alcohol ethoxylated
(FAE). The deinking generally is performed in alkaline
conditions and demands the use of alkaline chemical
reagents to improve the process. The deinking process in
alkaline suspension due to its chemical nature generates
dissolution of fiber components that are negatively on the
environment. In the actuality neutral deinking is the
subject of interest about new technologies, because is
friendlier with the environment than the alkaline
deinking. In this research, we characterize the deinking
flotation process under neutral condition for recovered
paper using surfactants type FAE at different hydrophilic-
lipophilic balance (HLB). Optical properties such as
brightness, color components (L*, a*,b*) and dirt
particles count were studied. The results of optical
properties in neutral conditions were better than the one´s
obtained in the alkaline process. The effluents generated
in the deinking process under neutral condition are more
biodegradable (≈10%) than the deinking process under
alkaline condition. These results show that the neutral
deinking for recovered paper (magazine paper, office
paper and newspaper) using FAE is more effective in
removing pigment inks and cleaner effluents than the
alkaline deinking.
ADDRESSES OF THE AUTHORS: Belkis Sulbarán-
Rangel (belkis.sulbaran@cutonala.udg.mx):
Departamento de Ingenierías, Universidad de
Guadalajara, CU Tonalá, Tonalá, México. Hader Alzate
(hader.alzate@correo.upb.edu.co): Grupo Pulpa y Papel.
Universidad Pontificia Bolivariana. Medellín, Colombia.
Ezequiel Delgado (ezedelfor@gmail.com), Alma Rosa
Saucedo (asaucedo@dmcyp.cucei.udg.mx) and José
Turrado (jturrado@dmcyp.cucei.udg.mx) Departamento
de Madera, Celulosa y Papel. Universidad de
Guadalajara, Guadalajara, México.
Corresponding author: Belkis Sulbarán-Rangel
The use of recovered paper as raw material for paper
production has many environmental, economic and social
benefits, such as the reduction of paper waste in landfills
and the reduction of use of wood for paper production
(Villanueva, Wenzel 2007). It has also been demonstrated
in several studies that paper recycling may offer
significant environmental benefits in a lifecycle
perspective (Laurijssen et al. 2010; Pivnenko et al. 2015).
However, increasing concerns related to the presence of
potential harmful chemical substances in paper and water
waster (Pivnenko et al. 2015).
Recycled paper presents significant challenges to its use
because of aging of the fibers and the presence of
170
contaminants. The presence of contaminants is caused by
the additives used in manufacturing of the primary
process (loads, fillers, adhesives, etc.), type of printing, as
well as conditions of use and final disposal (Monte et al.
2012; James et al. 2014).
The deinking of recycled paper so far is usually
performed under alkaline conditions and demands the use
of alkaline chemical reagents (Allix et al. 2011; Bajpai
2014; Beneventi, Carré 2000; Ferguson 1992). This has a
negative impact on the environment, as it is the effluents
generated that are difficult to treat because of
contaminants such as adhesives, ink pigments, resins,
chemicals and fine organics (Monte et al. 2012; Sulbarán
et al. 2014). A new trend for certain processes and mills
in the deinking of newspaper and magazine based in raw
materials is to move away from traditional alkaline
deinking and towards lower pH levels which are
commonly referred as: “true neutral” deinking (pH about
6.8-7.2) and “reduced or low alkali” deinking (pH about
7.2-8.8) (Jobbins, Heise 1996; Rosencrance 2007;
Rosencrance et al. 2005). In reduced/low alkaline
deinking sodium silicate is added besides the surfactant.
In addition, usually a less successful approach, has been
adding sodium sulphite to the pulper to help deinking
(Lapierre et al. 2004; Rosencrance 2007). In true neutral
deinking only surfactants and a blend of different
synthetic surfactants are added to the pulper
(Rosencrance et al. 2005).
Surfactants are among the most common chemical
products. They contain a hydrophilic head group attached
to a large hydrophobic part. Typically, the hydrophobic
part is an alkyl group with at least eight CH2 units. The
head group can be cationic, anionic, zwitterionic, or non-
ionic (Martín et al. 2014; Szymanski et al. 2000). The
fatty alcohol ethoxylates (FAE) are the second largest
groups of surfactants in terms of manufacture and the
main group of non-ionic surfactants. The main area of
FAE application is in the manufacture of washing
powders, liquids etc. FAE are classified as easy
biodegradation surfactants (Szymanski et al. 2000). Some
authors have proposed mechanisms that occur during the
degradation of FAE such as: cutting the molecule into
two parts, one hydrophobic and other hydrophilic and
then an oxidation occurs in hydrophobic group. Some
characteristics of the surfactant as the ethoxylate chain
length and position of the link with the hydrophobic
chain influences the biodegradation rate (Castillo et al.
2000; Marcomini et al. 2000).
The aim of this study was to do deinking by flotation in
neutral condition of a mixture of recovered paper such as
magazine, newspaper and office paper, using bio-
degradable surfactants type fatty alcohol ethoxylates with
different hydrophilic lipophilic balance (HLB). The
Hydrophilic-lipophilic balance of a surfactant is a
measure of the degree to which it is hydrophilic or lipo-
 PAPER PHYSICS
Nordic Pulp & Paper Research Journal Vol 31 no (1) 2016
philic, determined by calculating values for the different
regions of the molecule, as described by Griffin (1954).
HLB is an important parameter when using nonionic
surfactants, because of their great influence on optical
properties and efficiency in washing and flotation
processes (Alzate et al. 2013; Theander, Pugh 2004).
Other important aim of this research is to obtain
efficient biodegradation of the pollution in a neutral
condition. We evaluated the pollutants generated in the
process and compared with the alkaline deinking.
Pollutants are determined by biochemical oxygen demand
(BOD5), chemical oxygen demand (COD), suspended
solids, toxicity and color. When untreated, or poorly
treated effluents are discharged to receiving waters
(Pokhrel, Viraraghavan 2004).
Materials and Methods
Selection and preparation of waste paper
The waste paper used in this study was a mixture of three
types of secondary fibers to simulate what paper industry
does. Magazine paper 40%, office paper 40% and
newspaper 20% were used. Magazine and office paper
came from bleached chemical pulp and the basic
newsprint furnish comprises mechanical pulp and
chemical pulp (Waterhouse 2001). The printing inks
present in the waste paper were: flexographic for
newspaper, toner for office paper and offset for the
magazine paper. The waste papers were manually sorted
to remove nonpaper objects and were shredded into small
pieces.
Selection and preparation of surfactants
Fatty alcohols ethoxylates (FAE) at differences HLB
were used at purity grade. These products were supplied
by the company OXITENO S.A. de CV from Guadalajara
city, Mexico. The FAE have linear chain of lauric acid
(C12H24O2) and a variable number of molecules of
ethylene oxide (C2H4O) (Table 1).
Pulping
Waste paper was disintegrated in water at a consistency
of 4%. This operation was performed in a standard
disintegrator as indicated in Appendix A of the Technical
Association for Pulp and Paper Industry (TAPPI) T205
sp-02. It was carried out with water with hardness of
180 mg/l, rotation speed of 3500 rpm during 10 min, at
room temperature.
Deinking in alkaline condition (pH 11)
It was performed as control treatment. Different
chemicals were pulped together for a total of 10 min in
blender. The water temperature 40°C did not change
appreciably during pulping, even though there was no
heating element connected to the blender. The reagents
used were: NaOH at 1%, Na2SiO3 at 0.5%, H2O2 at 1.0%,
diethylene triamine pentaacetic acid (DTPA) at 0.3% and
commercial surfactant (nonylphenols ethoxylate) at 0.5%
(all dosages are given with respect to dry paper). The
reagents were purchased from Sigma Aldrich
(Milwaukee) and used at purity grade. Later, the pulp
was diluted at 0.8% consistency and stored at 40°C.
171
Table 1- Description of the surfactants
Type FAE HLB
C12H24O2(C2H4O)2OH 6
C12H24O2(C2H4O)3OH 8
C12H24O2(C2H4O)4OH 10
C12H24O2(C2H4O)6OH 12
C12H24O2(C2H4O)10OH 14
C12H24O2(C2H4O)17OH 16
The flotation deinking was done in a flotation cell
according to the procedure PTS Method 010/87 (Papier
Technische Stiftung 1987). The conditions were: flotation
time 10 min, consistency 0.8%, temperature 40°C and
water hardness 180 mg/l.
Deinking in neutral condition (pH 7)
In these experiments, only fatty alcohols ethoxylates at
0.5% for different HLB values (6, 8, 10, 12, 14 and 16)
were used. The addition of the surfactant was in the
pulping at 10 min in blender at 40°C. The suspension was
brought to the cell flotation at the same condition that the
alkaline deinking.
Evaluation of the efficiency of flotation deinking
The evaluation of the efficiency of the deinking was for
each condition (neutral and alkaline deinking). Hand-
sheets were made by standard method TAPPI T218 SP-
02 to determine the optical properties, such as:
• Brightness according to TAPPI T452 om-02
• Color components (L*, a*, b*) according to TAPPI
T524 om-02.
• Dirt particle count according to TAPPI T563 om-03
using Microtek Scan Maker i900 Domas 8.2 software that
quantifies the number of particles per m2.
Evaluation of the effluents
The effluent obtained in the deinking process in neutral
and alkaline condition were collected and evaluated. The
evaluation of the effluent consisted of: Chemical oxygen
demand (COD) according to standard method for water
analysis 5220-D, biochemical oxygen demand after
5 days (BOD5) according to standard method for water
analysis 5210-B and index of biodegradability (IB)
according to method proposed by (Eaton, Franson 2005)
it consisted in calculus of IB using the Eq 1.
IB  BOD5  100 [1]
COD
where:
- IB: biodegradability, %
- BOD5: biochemical oxygen demand after 5 days
- COD: chemical oxygen demand
Results
The objective of this work was to compare deinking
alkaline with deinking neutral using surfactants type FAE
at different hydrophilic-lipophilic balance (HLB). For
this purposed, optical properties were evaluated. Optical
properties of paper products are very important, with
respect to color and brightness of high quality printing
papers, tissue grades and also some special paper grades.
The results of the chromatic components of color are
shown in Table 2. Chromaticity measurement was based
 PAPER PHYSICS
Nordic Pulp & Paper Research Journal Vol 31 no (1) 2016

Table 2 - Components chromatic of handsheets made with of black dots (pigment inks) present per area and it is
deinking pulp expressed as the number of particles per meter square.
Components chromatic Usually is used a computerized image analyzer equip-
Deinking ment for measurement and quantification the black dots.
L* a* b*
Alkaline 84.38 -0.22 0.68 A high number of particles after deinking have influences
Neutral HLB 6 (N6) 82.17 0.15 -0.63 in the brightness of the sheet. In deinking process is
Neutral HLB 8 (N8) 84.35 0.03 -0.14 important to try to remove as many particles as possible
Neutral HLB 10 (N10) 84.83 0.11 -0.37 in the pulp and thus have more clean sheets.
In Fig 2 is shown the number of particle per meter
Neutral HLB 12 (N12) 85.06 0.02 0.07
square for handsheets made with deinking pulp, alkaline
Neutral HLB 14 (N14) 84.62 0.01 -0.16
and neutral. Neutral deinking with HLB 6 have more dirt
Neutral HLB 16 (N16) 84.61 0.03 -0.04
particle than the other deinking. Results presented in this
figure have good matching and confirm the result
on the most universally accepted system for measuring presented before, brightness and chromatic components
color, pattern known as CIE L*, a*, b*, in this system is depend on the HLB of the surfactants.
indicated the coordinate transformations of color. The a* The alkaline deinking has similar number of particle per
axis measures the changes of (-) green to (+) red, b* axis meter square than the neutral deinking with HLB 14 and
measures the changes of (-) blue to (+) yellow and axis 16. The numbers of particle are low in neutral deinking
L* measures luminosity, a trend of (-) black to (+) white. when using surfactant with HLB 8, 10 and 12. The best
In general all the handsheets have gray colors but, in results was using surfactants with HLB 12 (10.535 N°
neutral deinking with using HLB 6 the handsheets were particle/m2) approximately 60% fewer particles in
more dark (L ≈ 82). Alkaline deinking have the value b* compered to alkaline deinking.
higher than deinking neutral, this suggest that the In general deinking in neutral condition using surfactant
handsheet tend to be yellow, this is because of the at different HLB showed better result in optical properties
addition of NaOH in the process. (referent to remove ink) than deinking in alkaline
Other important optical property in the papermaker is condition. These results can be explained as follows: The
brightness. In papermakers brightness is based on HLB of a surfactant is a measure of the degree to which it
measuring the light reflectance at 457 nm. The is hydrophilic or lipophilic, determined by calculating
measurement values are expressed as a percentage of values for the different regions of the molecule. As a
reflected light (0 to 100). The results of the brightness for result of these unique chemical compositions the sur-
the handsheet deinked in alkaline and neutral condition factants modify surfaces and interfaces between various
are shown in Fig 1. The results are in agreement with phases thus lowering the interfacial energy. This modifi-
results reported by other authors in the first stage of cation of the energetic at surfaces and interfaces allows a
deinking. They reported values between 60-65% for number of phenomenons to occur. One such example is
deinked pulp handsheets prepared in neutral and alkaline detergency and removal of contaminants from solid
conditions (Jobbins, Heise 1996; Carré et al. 2000). surfaces such as printed ink on a fiber surface in paper
Fig 1 shows that in general when using FAE in the recycling (Rosencrance et al. 2005; Rosencrance 2007).
deinking neutral condition have better efficiencies of In our experiment the better result was when using
brightness than obtained in alkaline condition. However, surfactant with HLB 12. In according to the scale of
when in deinking was used FAE with HLB 6 the Griffin, HLB 12 means that the surfactant have emulsifier
brightness was lower. property (Griffin 1954). Emulsifier is a substance which
The brightness increased when HLB was increased and both assists the formation of an emulsion and stabilizes it
was higher than the alkaline deinking. Brightness is when formed. One common framework suggested that
stabilized with HLB of 14 and 16. In the paper industry, the detergency assists a hydrophobic ink constituent to
increasing the degree of brightness in a point is energetically depart from a preferred solid fiber surface
important. With HLB 10 and 12 it was found an increase and disperse in a hydrophilic and uncomfortable aqueous
of brightness (2 points), this indicates that the neutral environment. The surfactant mediates this energetically
deinking is better. unfavorable process by altering the surface and interfacial
Brightness has a relationship with dirt particle count in
the handsheet. Dirt particle count is refers to the number

Fig 1 - Brightness of handsheet made with deinking pulp Fig 2 - Dirt particle count of handsheets made with deinking pulp
(alkaline and neutral).

172
 PAPER PHYSICS
Nordic Pulp & Paper Research Journal Vol 31 no (1) 2016
Table 3 - Evaluation of the effluents generated in the deinking
neutral and alkaline condition.
Deinking pH effluents BOD5 (mg/l) COD (mg/l)
Neutral 7.3 310.02 479.88
Alkaline 11 240.67 409.67
Fig 3 - Biodegradability of the effluents generated in the
deinking.
energy thus facilitating ink detachment and dispersion in
the water phase thus making possible subsequent
separation from the desired fibers dispersed as well in the
medium. Opposite of this was in the experiment when
using surfactant with HLB 6. Ours result shows lower
value in optical properties, because, HLB 6 have the
antifoaming property in according to the scale of Griffin
(1954), and affect the removal of ink.
In the deinking process the performance of the
surfactant is as important as the water pollution, because
recycling mills may have polluting by products like
sludge that could contaminate water. For that reason in
our investigation, besides, to obtaining efficient deinking
process in a neutral condition, we evaluated the water
pollutants generated in the process and compared with the
alkaline deinking (Table 3).
The results in Table 3 shows low values of COD in
relation to the values usually present in the industrial
effluents. The results obtained in the laboratory cannot be
scaled directly to the plant level. At industrial scale,
water is recirculated and already contained numerous
dissolved materials. Therefore, the usefulness of them is
setting trends that provide point of reference for the
design of industrial scale process.
The values of BOD5 and COD of the effluent for neutral
deinking are greater than the alkaline deinking. This is
because the surfactants applied FAE contributes to the
effluent BOD5 and COD. However, it is important to note
that the difference in pH is important because, not is
necessary adjustment to enter into the treatment plant
effluent.
Fig 3 shows the results of the biodegradability. This was
calculated with the results of BOD5 and COD of the
effluents generated in the process of flotation deinking
under neutral and alkaline conditions. The alkaline
deinking (58%) are less biodegradable than neutral
deinking (66%), this is because in deinking neutral did
not use a lot of chemical than deinking alkaline and the
effluents generated is more clean. The application the
fatty alcohols ethoxylated in neutral deinking, increasing
173
COD, but, the effluent generated are easier to biodegrade
over time.
Conclusions
The use of biodegradable surfactants (fatty alcohols
ethoxylated) in deinking of a mixture of recovered paper
(magazine, newspaper and office) in neutral condition
can achieve a higher efficiency in removing ink pigments
that conventional alkaline deinking. The use of fatty
alcohols ethoxylates in neutral conditions allow a
deinking process which is in accordance with
environmental sustainability. In accordance to the results
of the brightness and dirt particle count for the handsheet
deinked was demonstrated that neutral deinking method
using surfactants with HLB values of 10 and 12 was
better than deinking under alkaline chemistry. The
effluents generated in the neutral deinking are more
biodegradable than those generated in the alkaline
deinking therefore neutral deinking is a more
environmentally friendly.
Acknowledgements
The authors are grateful for the support of the Department of
Wood Pulp and Paper "Dr. Karl Augustin Grellman "at the
University of Guadalajara and the German Academic Exchange
Service Deutscher Akademischer Austauschdienst (DAAD) for
the scholarship.
Literature
Alzate, H., Dovale, A., Chala, V., Muñoz, O., Casas, A.,
Quintana, G., and Velasquez, J. (2013): Study of the
enzymatic/neutral deinking process of waste photocopy paper.
O’Papel 74(8), 61 - 65.
Allix, J., Zeno, E., Nortier, P., and Beneventi, D. (2011):
Roles of surfactant and fibres on fibre transport in a small
flotation deinking column. Chem. Eng. J., 168(2), 525 - 534.
Bajpai, P. (2014): Recycling and deinking of recovered paper,
Oxford, pp. 55-83.
Beneventi, D, and Carré, B. (2000): The mechanisms of
flotation deinking and the role of fillers. Prog. Pap. Recycl., 9(2),
77 - 85.
Castillo, M., Martínez, E., Ginebreda, A, Tirapu, L, and
Barceló, D. (2000): Determination of non-ionic surfactants and
polar degradation products in influent and effluent water
samples and sludges of sewage treatment plants by a generic
solid-phase extraction protocol. Analyst, 125(10), 1733 - 1739.
Eaton, A.D., Franson, M., (2005): Standard Methods for the
Examination of Water and Wastewater: American Public Health
Association. USA, pp.1200
Ferguson, L. (1992): Deinking chemistry: part 1. Tappi J.,
75(8), 75-83.
Griffin, W. (1954): Calculation of HLB Values of Non-Ionic
Surfactants. J. Soc. Cosmet. Chem, 5, 249-256.
James, W., Venditti, R., Pocock J. and Jerome Andrew
(2014): Neural network modelling and prediction of the flotation
deinking behaviour of industrial paper recycling process. Nord
Pulp Paper Res. 29(3), 521-532.
 PAPER PHYSICS
Nordic Pulp & Paper Research Journal Vol 31 no (1) 2016
Jobbins, J, and Heise, O. (1996): Neutral deinking of mixed
office waste in a closed-loop process. The Recycling
Symposium TAPPI Proceedings, March 5-7, 1996, New
Orleans, LA, USA pp. 27-32.
Lapierre, L, Bouchard, J, Dorris, G, Pembroke, C, Allen, J,
and Hill, G. (2004): Mill trials on near-neutral sulphite deinking.
Part I. Pulp Pap Can, 105(2), 42-46.
Laurijssen, J., Marsidi, M., Westenbroek, A., Worrell, E.,
and Faaij, A. (2010): Paper and biomass for energy?: The
impact of paper recycling on energy and CO2 emissions.
Resour. Conserv. Recycl., 54(12), 1208-1218.
Marcomini, A., Zanette, M., Pojana, G., and Suter, M. (2000):
Behavior of aliphatic alcohol polyethoxylates and their
metabolites under standardized aerobic biodegradation
conditions. Environ. Toxicol. Chem, 19(3), 549-554.
Martín, V., de la Haba, R., Ventosa, A., Congiu, E., Ortega-
Calvo, J.o, and Moyá, María L. (2014): Colloidal and biological
properties of cationic single-chain and dimeric surfactants.
Colloids Surf., B, 114, 247-254.
Monte, M. C., Sánchez, M., Blanco, A., Negro, C., and Tijero,
J. (2012): Improving deposition tester to study adherent
deposits in papermaking. Chem. Eng. Res. Des., 90(10), 1491-
1499.
Papier Technische Stiftung (PTS) (1987): Testing of waste
paper identifications of the flotation deinkability of prince waste
paper.PST-RU010/87 Munich, Alemania.
Pivnenko, K., Eriksson, E., and Astrup, Thomas F. (2015):
Waste paper for recycling: Overview and identification of
potentially critical substances. Waste Manage. 45, 134-142
Pokhrel, D., and Viraraghavan, T. (2004): Treatment of pulp
and paper mill wastewater-a review. Sci. Total Environ, 333(1-
3), 37-58.
Rosencrance, S. (2007): Non-sulfite neutral deinking for
recycled fibre. Pulp Pap Can, 108(9), 15-18.
174
Rosencrance, S, Horacek, B, and Hale, K. (2005): A unique
new ONP/OMG “true- neutral” deinking technology. The Annual
Meeting Preprints - Pulp and Paper Technical Association of
Canada, 91st, Montreal, QC, Canada, February 8-12, 2005 pp.
D211-D214
Standard methods for the examination of water and
wastewater. (1999): 5220-D and 5210-B. pp 4-131.
Sulbarán, B, Turrado, J. Delgado, E. Rojas, O. and Venditti,
R. (2014): Destintado en medio neutro de papel reciclado
aplicando mezclas de enzimas celulasa y α-amilasas. Eur. Sci
J. 10(12), 1-6
Szymanski, A., Wyrwas, B., Swit, Z., Jaroszynski, T., and
Lukaszewski, Z. (2000): Biodegradation of fatty alcohol
ethoxylates in the continuous flow activated sludge test. Water
Res., 34(16), 4101-4109.
Technical Association for Pulp and Paper Industry (TAPPI).
(2002): Forming handsheets for physical tests of pulp. T205 sp-
02. TAPPI Methods. TAPPI press Atlanta.
Technical Association for Pulp and Paper Industry (TAPPI).
(2002): Brightness of pulp, paper, and paperboard (directional
reflectance at 457 nm). T452 om-02.TAPPI methods. TAPPI
press Atlanta.
Technical Association for Pulp and Paper Industry (TAPPI).
(2003): Equivalent Black Area (EBA)and count of visible dirt in
pulp, paper and paperboard by image analysis. T563 om-
03.TAPPI methods. TAPPI press Atlanta.
Technical Association for Pulp and Paper Industry (TAPPI).
(2002): Color of paper and paperboard (45/0, C/2). T524 om-
02.TAPPI methods. TAPPI press Atlanta.
Theander, K. and Pugh, R. (2004): Surface chemicals
concepts of flotation de-inking. Colloids Surf., A:Physiochem.
Engng Aspects, 240, 111-130. .
Villanueva, A. and Wenzel, H. (2007): Paper waste –
Recycling, incineration or landfilling? A review of existing life
cycle assessments. Waste Manage, 27(8), S29-S46.
Waterhouse, J. F. (2001): Paper Products: Classification A2 .
Encyclopedia of Materials: Science and Technology (Second
Edition). Elsevier, Oxford, pp. 6685-6696.
Manuscript received December 21, 2015
Accepted February 15, 2016