Environmental Engineering and Management Journal March 2012, Vol.11, No.

3, 681-686
http://omicron.ch.tuiasi.ro/EEMJ/

“Gheorghe Asachi” Technical University of Iasi, Romania

ENVIRONMENTAL FRIENDLY PULPING AND BLEACHING

OF RAPESEED STALK FIBERS

Bogdan Marian Tofanica, Adrian Catalin Puitel, Dan Gavrilescu

“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection,
Department of Natural and Synthetic Polymers, 73 Prof. dr. doc. D. Mangeron Street, 700050 Iasi, Romania

Abstract

The research focuses on the characterization and evaluation of agricultural residue as pulping raw materials with the aim of
improving the production of high quality papers in which they are used. The material selected includes delignificated nonwood
fibers from rapeseed stalk, a fiber little-known in the pulp and paper industry. The pulps obtained from these raw materials by
soda/anthraquinone pulping, followed by a totally chlorine free (TCF) and elementary chlorine free (ECF) bleaching, were
characterized by pulp yield, kappa number, viscosity and brightness of pulps. The differences between TCF and ECF bleached
pulps was also examined by comparing pulps bleached with sequences containing different combinations from oxygen, hydrogen
peroxide, peracetic acid and chlorine dioxide. The effects of cooking and bleaching agents on the selected raw materials were
studied. This investigation offered valuable information for improving the pulping and bleaching processes by the use of
environmentally friendly technologies. In addition, they contributed to reduce the high amounts of reagents used in conventional
bleaching and to increase the quality and properties of the final paper products. This knowledge will lead to a better utilization of
these lingo-cellulosic raw materials and to the developing of interest for these nonwood fibers. It is concluded that the rapeseed
stalk have the potential for being used for obtaining cellulosic pulp.

Key words: cellulose, nonwood, pulp, rapeseed stalks

Received: September, 2011; Revised final: February, 2012; Accepted: March, 2012

1. Introduction Rapeseed (Fig. 2), known scientifically as

Nonwood fibers have an extended history as
raw materials used in production of paper, long before
the wood began being utilized in papermaking
(Gavrilescu et al., 2009; Craciun et al., 2010; Sixta,
2006a). Today, the production of nonwood pulp in
worldwide pulp production is around 20 million
tonnes (Fig. 1), but evaluating forecasts and trends in
recent years, it is expected to grow at least until it
reaches maximum production capacity reached in the
90's of 25 million tones. Analyzing the share of
nonwood in world pulp production (Fig. 1) it can be
stated that the utilization increases continuously in the
last ten years. Overall, the ratio changed from 6% in
the ’60 to 11% in the last decade (Faostat, 2011).
Brassica napus L., a bright yellow flowering member
of the Brassicaceae family, is a very important and
widely cultivated arable crop throughout the world for
the production of animal feed, vegetable oil for
human consumption and production of biodiesel for
powering motor vehicles (Tofanica and Gavrilescu,
2010). Rapeseed, also known as oilseed rape or
canola, has achieved worldwide commodity status,
being cultivated extensively in Europe, Asia and
North America due to the policies to encourage the
production and use of bio-fuels (European
Commission, 2010).
Biomass productivity of winter oilseed rape is
the product of the growth rate and the duration of the
vegetative period (Diepenbrock, 2000). Winter
rapeseed total biological yield ranges from 10 to 20


Author to whom all correspondence should be addressed: e-mail: gda@tuiasi.ro.
 Tofanica et al./Environmental Engineering and Management Journal 11 (2012), 3, 681-686

metric tons of dry forage/ha. The harvest index of
rapeseed, the proportion of seed dry matter to total
biomass (seeds and stalks), varies between
approximately 0.28 and 0.50. Thus, seeds represent
28–50% of total biomass and the remaining crop
residues, especially stalks represent 20-72% of total
biomass (Rathke at al., 2006). In European Union, an
economic seed yield of winter oilseed rape is situated
in the range of 3 and 4 tons per hectare and
corresponds to 3 to 10 tons of stalks.
The seed is the valuable, harvested component
of the crop, while the stalks remain on the field and
serve in the crop rotation to increase the humus
content in the soil, but also for incorporation,
immobilization and bio-transformation of available
nitrogen and sulphur to stable organic forms in
nutrient-poor soils (Bhupinderpal-Singha et al.,
2006).
wood fibers in a variety of composites, paper and
paperboard products.
Chemical composition analyses showed the
lignin content was comparable to other nonwood and
hardwood papermaking fiber resources (Tofanica et
al., 2011). Rapeseed’s holocellulose content vary
between 70-75% (cellulose 38-42%), lignin content
between 17-21% and ash content of 2-5%. The
chemical composition of rapeseed is comparable with
chemical composition of cereal straws. The amount of
cellulose influences the properties of fibers,
economics of fiber production and the utility of the
fibers for various applications.

Fig. 2. Brassica napus

Fig. 1. Share and production of nonwood pulp in total world

production (FaoStat, 2011)

The stalks status as a solid waste in many

instances means that they could be a cheap raw
material. It can be processed to obtain fibers,
chemicals and energy via various chemical
conversion processes, into a lignocellulosic feedstock
biorefinery (Tofanica and Gavrilescu, 2010).
The morphological studies showed that rape
stalks contained short fibers with similar
morphological properties to the common nonwood
and hardwood fibers (Tofanica et al., 2011). The
mean fiber length, 1.2 mm, is similar with those for
other nonwood fibers such as esparto grass and
common reed, and hardwood species such as
eucalyptus and common beech. A maximum Fig. 3. Rapeseed stalks remain on the field after
seed harvesting
dimension fiber length was found 1.99 mm and
minimum fiber length was found 0.71 mm. Rapeseed
The use of these agricultural residues for
fibers width ranges between 9.10 μm and 19.60 μm,
production of cellulosic fibers deserves serious
with an average value of 13.1 µm. Cell wall thickness
consideration. The low lignin content of these
ranges from 1.77 to 3.08 μm, with 2.25 μm average.
residues means lower energy and chemical demand.
Maximum lumen diameter was found as 13.44 μm
Their status as a waste product in many instances
and minimum was found as 4.34 μm.
means they could be a cheap raw material compared
Fiber length and width, cell wall thickness and
with wood that need to be kept in the forests.
lumen diameter of fibers from rapeseed stalks, a fiber
The manufacture of pulp from nonwood
little-known in the pulp and paper industry, are very
fibrous raw materials has been done exclusively
similar with those from hardwoods and can replace
utilizing chemical and chemo-mechanical methods.

682
 Environmental friendly pulping and bleaching of rapeseed stalk fibers
Soda-anthraquinone (Soda-AQ), a sulphur-free
process, is one of the main chemical pulping methods
applied to nonwood raw materials, adapted from
processes for the delignification of wood raw
materials (Leponiemi, 2008). Soda-anthraquinone
pulping is seen as an alternative process for producing
nonwood pulps. Using the soda-AQ process
simplifies the recovery of pulping chemicals and
eliminates undesirable emissions of odorous sulphur
compounds to the air (Finell and Nilsson, 2004).
The current research focuses on the
characterization and evaluation of rapeseed
agricultural residue products as raw materials for
pulping and papermaking industry. The cellulosic
fibers obtained from these raw materials by
soda/anthraquinone pulping (soda-AQ) (Tofanica and
Gavrilescu, 2011), followed by a totally chlorine free
(TCF) or elementary chlorine free (ECF) bleaching
stages with sequences containing different
combinations from oxygen (O), hydrogen peroxide
(P), peracetic acid (Paa) and chlorine dioxide (D),
were characterized by pulp yield, kappa number,
viscosity and brightness of pulps (Bajpai, 2005;
Suess, 2010).
This investigation offered valuable
information for using and improving the rapeseed
stalk pulping and bleaching processes by the use of
sulphur-free pulping and environmentally friendly
bleaching. In addition, the obtained data will
contribute to reduce the high amounts of reagents
used in bleaching stages and to increase the quality
and properties of the final paper products.
This knowledge will lead to a better utilization
of these lingocellulosic raw materials and to the
developing of interest for these nonwood fibers.
Rapeseed stalks as agricultural residues, may have
potential in the future as raw materials for fiber
production for different paper products.
2. Experimental
2.1. Materials
The rapeseed stalks, free of leaves and roots,
were collected after seed harvest from Vaslui County,
Romania. The stalks were air dried and stored in a dry
location. For pulping, the stems were manually cut
into pieces of about 3-5 cm in length. All results were
reported on oven-dry weight basis.
2.2. Methods
2.2.1. Pulping
Soda-AQ pulps were obtained in a laboratory
rotating batch reactor with a volume of 10 L,
equipped with electric heating and automatic
temperature control. 300 g of rapeseed stalks (on dry
basis) and corresponding white liquor were used, so
that pulping was performed with the desired active
alkali charge.
The following experimental conditions were
applied in soda-AQ pulping:
- alkali charge was 18, 20 and 22% as NaOH,
based on oven-dry weight of stalks;
- ratio of rapeseed stalk to cooking liquor was 1:5
(water was added);
- after 100ºC, the heating rate was realized to
reach the cooking temperature in 60 minutes;
- pulping time was 60 minutes at maximum
temperature of 170°C;
- anthraquinone in 0.1% charge on oven-dry
weight of stalks was used in all processes.
The cooking parameters were selected in order
that pulp lignin content being below the fiber
liberation point. The corresponding H-factor (Sixta,
2006b) for current cooking profile at 170°C and 60
minutes was 1038. After digestion, the brown stock
was washed thoroughly with water until no color in
the resulting water was observed and the alkali
residue removed. Then, pulp was screened on a
vibratory screen with 0.25 mm slots.
The total yield was determined as percentage
of dry matter obtained after pulping based on oven-
dried raw materials. The fiber yield was the screened
fraction, while the unscreened portion was the
rejected yield.
Kappa number, determined according to
TAPPI Test Method T236 - Kappa Number of Pulp,
analyzed the screened pulp for degree of
delignification. The limiting (intrinsic) viscosity of
selected pulps was measured according to ISO
standard 5351:2010 Pulps – Determination of limiting
viscosity number in cupri-ethylenediamine (CED)
solution.
2.2.2. Bleaching
All tested pulps were bleached in ECF and
TCF series with a simple three-stage sequence. The
bleaching procedure was as follows:
- oxygen delignification (O stage) was carried out
in the same reactor as pulping. Pulp samples were
mixed with 1% magnesium sulphate (on o.d. pulp),
3% sodium hydroxide (on o.d. pulp) and then
adjusted to 3% consistency using distilled water. In
all bleaching experiments, reactor was pressurized
with oxygen at 0.5 MPa and heated at 100°C for 60
min.
- hydrogen peroxide bleaching (P stage) was
realized in 500 ml closed glass bottles immersed in a
water bath at 80°C and heated for 2 hours. Pulp
samples were treated with 3% charge on o.d. pulp of
35% H2O2 solution. Charges of 1% MgSO4 (on o.d.
pulp) were applied in order to avoid or delay the rate
of peroxide decomposition and cellulose degradation.
The consistency of the pulps was adjusted to 10%
with distilled water.
- peracetic acid bleaching (Paa stage) was done in
glass bottles immersed in water bath at 80°C and
heated for 2 hours with 2% charge of peracetic acid
(solution with concentration of 39%). The pH was
adjusted at 6-7 with H2SO4 1M standardized solution.
Distilled water was added until 10% consistency
pulps were obtained.
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 Tofanica et al./Environmental Engineering and Management Journal 11 (2012), 3, 681-686

- chlorine dioxide bleaching (D stage) was done in pulping is reached to the residual stage and should not
500 ml closed glass bottles immersed in a water bath exceed this value of alkali charge, because further
at 80°C and heated for 2 hours. On-site generation increase with 2% will only decrease total pulping
from sodium chlorate in acid medium (pH≈3-5) was yield.
realized to ensure a charge of 2% ClO2 on o.d. pulp at
10% consistency. Table 1. Pulping conditions and yields in Soda-AQ
- alkaline extraction – when needed, pulps were experiments
immersed in 1% NaOH solution and thoroughly
shaken. After a 10-15 minutes treatment, the pulps Alkali Fibers Total
Temperature, Rejected,
Sample charge, yield, yield,
were filtered and washed with distilled water. %
°C
%
%
%
After each bleaching stage, the liquor was B-6 18 170 38.4 0.5 38.9
separated from the pulp and the pulp was thoroughly B-9 20 170 38.6 0.0 38.6
washed. The kappa number and viscosity of the B-12 22 170 38.5 0.0 38.5
bleached pulps were determined according to the
same standard test methods as used for the cooked Delignification proceeded quickly with
pulps. increasing the alkali charge, due to the rapid
Sheets for brightness testing of bleached pulps dissolution of lignin in the cooking liquor. For every
(as in TAPPI Test Method T452 - Brightness of Pulp, 2% alkali charge, the kappa number drop 25% and at
Paper, and Paperboard - Directional Reflectance at 4% differences in alkali charge, the gap between pulp
457 nm) were prepared using a Büchner funnel (in samples reaches 50% in kappa number units. In the
accordance with TAPPI Test Method T 218 - same time, intrinsic viscosity decrease slowly with
Forming Handsheets for Reflectance Testing of Pulp - alkali charge addition. The results have shown that
Büchner Funnel Procedure). the delignification rate increase by increasing the
All experiments were replicated to obtain sodium hydroxide charge, delignification being
reproducible data. extended as proven from the low kappa number of the
cellulose fibers.
3. Results and discussion The pulp bleachability was assessed in simple
three-stage sequences: PPD, DPD, OPaaP and OPPaa.
The pulping potential of rapeseed stalks were Hydrogen peroxide was chosen in all sequences due
investigated in this study. Pulping conditions and pulp to its simplicity in use, efficiency and selectivity as a
yields obtained in Soda-AQ pulping are given in chlorine-free agent, but also to its successful use in
Table 1. Depending on pulping conditions, total bleaching of non-wood pulps. Bleaching and overall
yields vary between 38-39%. In all processes, pulp yields, kappa number, intrinsic viscosity and
total yields decreased with increasing alkali charge. brightness in ECF and TCF bleaching are summarized
This finding could be explained by the advance of in Table 2. Pulp yield increased and kappa number
delignification, which reduces the total yield, because decreased in all bleaching sequences of soda-AQ
of the dissolution of lignin in pulping liquor, and on pulps, due to the lignin removal. In addition, high
the degradation and solubilization of other alkali charge in initial pulping liquor result in lowest
components from plant tissue - especially the kappa number and highest overall yields in all
hemicelluloses. bleaching methods, as can be seen in Table 2. It is
In Soda-AQ pulping for every 2% alkali noteworthy, that all tested pulps showed similar yield
charge, the total pulp yield drop less than a point. At values after full bleaching sequence, despite the
18-20% alkali charge, processes had similar fiber substantial kappa number variation in the unbleached
yields, with no unscreened fraction. Therefore, state.

Table 2. ECF and TCF bleaching of soda-AQ pulps from rapeseed stalks

Yield Kappa number Intrinsic viscosity, mL/g Brightness

Pulping process
Bleaching, % Overall, % Before After Drop, % Before After Drop, % TAPPI, %
ECF
B-6-PPD 84.3 32.8 58 28 52 812 747 8 30
B-9-PPD 86.8 33.5 35 3 91 768 717 7 51
B-12-PPD 91.1 35.1 28 3 89 753 703 7 57
B-6-DPD 85.2 33.1 58 12 79 812 725 11 43
B-9-DPD 86.3 33.3 35 1 97 768 700 9 52
B-12-DPD 88.8 34.2 28 1 96 753 660 12 78
TCF
B-6-OPPaa 87.3 34.0 58 29 50 812 713 12 38
B-9-OPPaa 88.6 34.2 35 9 74 768 676 12 48
B-12-OPPaa 91.5 35.2 28 6 79 753 641 15 48
B-6-OPaaP 87.7 34.1 58 32 45 812 676 17 27
B-9-OPaaP 89.7 34.6 35 10 71 768 659 14 50
B-12-OPaaP 91.9 35.4 28 7 75 753 612 19 50

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 Environmental friendly pulping and bleaching of rapeseed stalk fibers
Depending on pulping conditions, overall
yields after bleaching stages vary between 32-36%. In
all processes, pulp total yields increased with
increasing alkali charge used in the initial pulping
stage (Fig. 4). These findings could be explained by
the residual lignin and other non-cellulosic
polysaccharides remained in pulp after pulping stage,
and their dissolution and solubilization in bleaching
liquors.
As can be seen from Table 2 and Fig. 4, after
three bleaching stages, the yield loss in ECF pulps
was bigger than in TCF pulps obtained under
identical conditions. The main contribution to yields
loss comes from substantial degradation during
peroxide and chlorine dioxide bleaching. In addition,
even at kappa numbers in the range 1-10, rapeseed
stalks pulps gave good pulping yields, corresponding
to 33-35% reported at initial rapeseed stalks.
The ECF treatment reduces the kappa number
significantly and improves the brightness of the pulps
considerably. As can be seen from Table 2, after three
bleaching stages the loss in kappa number units was
between 45 and 96%, better for ECF pulps and lower
for TCF pulps. Bleaching response of the 20 and 22%
alkali charge in pulping state was significantly better
than of the 18% alkali charge pulp. However, the
exception is the treatment with two chlorine dioxide-
bleaching stages (B-6-DPD), which eliminates the
distinction in original pulp’s lignin content.
Fig. 4. Effect of the initial alkali charge on the overall yield
after bleaching
The relationship between kappa number and
viscosity for the rapeseed pulps is observed in Fig. 5.
It should be pointed out that the viscosity is typically
higher at lower kappa numbers than at higher kappa
numbers, due to the enhanced carbohydrate
degradation. Within the same group of bleached
pulps, along with further delignification, viscosities of
soda-AQ pulps decrease. In contrast, in the kappa
number range from one to 10 units, the better intrinsic
viscosity value has the 20% alkali charge after a PPD
bleaching sequence.
Brightness increases simultaneously with
reduction of the kappa number during the course of
bleaching of pulps, as can be seen in Fig. 6. It is
obvious that the TCF stages cause a modest increase
of brightness, whereas the ECF stages produce the
main brightening step.
Fig. 5. Variation of overall yield with kappa number
After DPD bleaching the pulps with initial
alkali charge of 20 and 22% NaOH shows the same
kappa number but different values for brightness. The
same initial pulps, but in OPaaP bleaching have the
same brightness values, but different kappa number.
Reason may be specific chemical distinctions in
residual lignin after pulping and bleaching processes,
especially the differences in chromophore units,
which provide the uniform final degree of
delignification or brightness of the different bleached
pulps.
Fig. 6. Variation of pulp brightness with kappa number
Both ECF and TCF bleached pulps displayed
moderately good intrinsic viscosity values. No
significant differences were observed among the
various bleaching sequences within the TCF and ECF
groups. However, there were significant differences
between the TCF and ECF pulps. The intrinsic
viscosity results obtained from TCF pulps were
slightly lower than the ECF pulp.
The peracetic acid treatment after oxygen
delignification, the OPaaP group of pulps, showed the
lowest intrinsic viscosity, as a consequence of the
degree of carbohydrate degradation by the free
radicals formed in the decomposition of peracetic acid
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 Tofanica et al./Environmental Engineering and Management Journal 11 (2012), 3, 681-686
during bleaching stage. Following the oxygen
delignification with peroxide and peracetic as a final
stage, improves not only intrinsic viscosity values, but
also slightly decrease kappa number values.
The intrinsic viscosity of soda-AQ pulps from
rapeseed stalks measured after each bleaching
sequence is shown as a function of pulp brightness in
Fig. 7. The decrease in pulp viscosity with brightness
development is only 8-12% in ECF bleaching, and
12-19% in TCF bleaching, due to differences in
viscosity loss determined by carbohydrate
degradation reactions. At similar brightness values
around 50% TAPPI brightness, after full bleaching
sequences ECF pulps showed better viscosity, with
40-60 mL/g, despite the kappa number variation.
Fig. 7. Change in pulp viscosity with brightness
development during bleaching of soda-AQ pulps
4. Conclusions
In general, comparing ECF and TCF bleaching
of rapeseed stalk pulps it can be concluded that in
terms of the quality parameters the first pulps are
superior to the latter.
The soda-AQ pulps from rapeseed stalks can
be bleached to brightness values of 80% TAPPI in a
three-stage ECF bleaching sequence (DPD). Pulp
brightness and degree of delignification were
substantially improved by DPD bleaching in
comparison with others bleaching sequences without
affecting pulps yield and viscosity.
The application of ECF or TCF bleaching
sequence on soda-AQ pulps from rapeseed stalks
provides an alternative for a better utilization of this
fiber source, and could be considered as an economic
and environmental solution for pulp production.
686
Acknowledgments
This paper was elaborated with the support of BRAIN
“Doctoral scholarships as an investment in intelligence”
project, financed by the European Social Found and
Romanian Government.
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