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Synthesis and Characterization of Eucalyptus

Pulp by Kraft Process for Paper Sheet
Formation

Article January 2015

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www.iaard.net eISSN: 2455 4472
International Association of Advances in Research and Development
International Journal of Environmental
Science and Technology
International Journal of Environmental Science and Technology, 2015, 1(2),20-26
Synthesis and Characterization of Eucalyptus Pulp by Kraft Process for Paper Sheet
Formation
Atnafu Guadie1*, Agraw Mulat1, Addis Kokeb1, Nigus Gabbiye2
1
Department of Chemistry, University of Gondar, P.O. Box 196, Gondar, Ethiopia
2
School of Chemical and Food Engineering, P. O. Box 26, Bahir Dar University, Bahir Dar, Ethiopia
*
Corresponding Authors email: atnafuguad@gmail.com
................................................................................................................................................
Abstract: In contrast to the highly growing demand of paper and paper products, paper product in Ethiopia is at
its infant stage where there are only paper mills producing an annual output of 10-15 tones in aggregate. This
number is very low as compared to other African countries by importing the raw material pulp outside the country
and in some extent from recycled paper. This study deals with the synthesis and characterization of eucalyptus pulp
by the Kraft process. The separation of the cellulose pulp from eucalyptus chips were performed in three stages:
Prehydrolysis, cooking (digestion) and bleaching steps. The results indicate that Kraft process is considered to be
more suitable to extract pulp from eucalyptus chips since higher yield of cellulose (46.4 %) and low lignin content
pulp was obtained that demonstrated a better pulp quality with lower value of kappa number (5.9). The Fourier
transform (FT-IR) spectrum of single and sequential bleached pulps specified that the chemical treatment
successfully remove the lignin and hemicelluloses content. The UV-visible spectrums of single and sequentially
bleached eucalyptus pulp shows transparent at visible region that confirms the characteristic indicator of
satisfactory brightness of the bleached pulps. In this study, the Kraft process was found to be a suitable process for
pulp synthesis and making high quality writing and printing papers with low cost due to the cheapest raw material
and recovery of the chemicals used.
Keywords: Eucalyptus Pulp, Kraft process, Paper, Kappa number, Lignin Content

1. Introduction the proportion of resin is higher. The molecular mass of

Paper making industry is a huge industrial branch with hardwood lignin is also apparently lower than the
high capacities, complicated equipment and processes softwood lignin. Thus, hard wood is a better raw
influenced by variety of factors. Paper has become is a material for producing the expected pulp yield with the
crucial substance in our day to day activities. The range required quality. Cellulose is the main component of
of possible uses of paper is infinite and alternative wood carbohydrates polysaccharide consisting of
means of using it are being devised daily. The most glucose units. The cellulose molecule easily forms
commonly used paper types are stationary paper (i.e. hydrogen bonds with neighboring molecules, thus
printing and writing), news print, covering, packaging, giving xylem cells mechanical support that makes it
and paper card. Pulp and paper are manufactured from suitable for paper making [4-5]. In terms of quantity,
wood, recycled paper and many types of farming cellulose is the most abundant renewable polymer
residue. Now a day, the main raw material for paper resource available worldwide. It has been estimated
making is wood fibers which are called wood pulp. that, by photosynthesis 1011 to 1012 tons are synthesized
Both soft and hard wood species can be used for annually in a rather pure form but mostly in
producing fibrous material [1]. Most lingo-cellulosic and combination with lignin and other polysaccharides
cellulosic materials of fibrous structure of wood may be (hemicelluloses) in the cell wall of woody plants [6].
processed into various grades of papers and paper Pulp is the raw material for the production of paper,
board. Fibres from different raw materials are differing paperboard, fiberboard, and similar manufactured
considerably in their morphological and chemical products. Pulp is obtained from plant fiber (cellulose)
characteristics, which make them more or less and is, therefore, a renewable source. Pulp is the most
appropriate for paper making [2, 3]. Hardwood fiber is important product of chemical conversion of
considerably shorter and thinner than the softwood lignocelluloses materials [7]. It can be obtained by
fibers. Generally, hardwood contains more cellulose digesting wood chips in acidic, neutral or alkaline
and hemicelluloses and less lignin than softwood while conditions. There are many types of pulping processes

Atnafu Guadie et al., Page No. 27

 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
viz., chemical, mechanical, semi-chemical and recycle
among which chemical pulping is the most common
process [8]. Chemical (i.e., Kraft, soda, and sulfite)
pulping involves cooking of wood chips using aqueous
chemical solutions at elevated temperature and pressure
to extract pulp fibers [9]. Generally, paper is made by
pulping wood, bleaching this pulp and then spreading it
out into sheets to formulate paper. At various stages of
the process, chemicals are used to give the paper
particular properties such as the bleaching chemicals
that make paper white (and which also enable it to
subsequently be colored). Kraft pulping is by far the
most common pulping process in the world for virgin
fiber, accounting for more than 80 percent of the total
world pulp production [10].
The major reason why there are no additional paper
mills with better capacity in Ethiopia is estimated to be
the huge capital investment that paper mills normally
require and significantly high cost of raw material that
is imported from different countries of the world. These
make the local production of paper inefficient and less
competitive when compared to other sectors in the
industry, which significantly affects the overall
economic growth of the country. For this reason, the
country should produce the raw material for paper
making from the available wood products. Eucalyptus
wood produces quickly to meet societys needs, and
also helps preserve indigenous forests. Eucalyptus trees
are highly profitable and take a shorter period to reach
at the harvesting age and require little human action on
the land during this period [11].
It is clear that in Ethiopia, pulp is imported from abroad
for paper factories. In order to overcome this problem it
seems promising to establish pulp factory at a national
wide. If so, eucalyptus can met the problem of highly
increasing cost of paper as alternative source of raw
material for paper synthesis [3]. In order to overcome the
challenges of the paper industry, a special attention
should be given facilitating the productions of the
major raw material (pulp) locally and discouraging
importation so that the local manufacturers will be
competent enough on the market. The main objective of
this work is to synthesize and characterize eucalyptus
pulp by chemical Kraft process with investigation of
the recovery mechanism of the consumed chemicals.
2. Materials and Methods
2.1. Raw material preparation and Pulp extraction
Seven up to nine year eucalyptus wood was collected
from Debark at around North Gondar, Ethiopia. The
eucalyptus wood was debarked, chipped and grinded in
to the range of 0.2-2 mm. The ground chips were
Atnafu Guadie et al.,
screened with 0.8 mm mesh and 1.5 mm mesh sieves to
eliminate over sized and fine chips. Then, the chips
were washed several times with distilled water to
remove dirties and dried with electric oven and stored
in moisture free place until analysis.
100 grams of accepted chips with 0.8 mm mesh sieve
size were fed in to the autoclave at a pressure of 6 bar.
The extraction (prehydrolyzed) experiments were
performed with white liquor (21.948 grams of NaOH
and 14.88 grams of Na2S) to wood ratio of 4:1 at 100
o
C for 100 minutes. The wood chip was then washed
with distilled water. Then, the washed pre-hydrolyzed
chip heated in an oven drier at 105 oC for 180 minutes
to remove the moisture gained during prehydrolyzed
process. The weight loss during digestion and washing
process was determined by subtracting the dried weight
from the weight of chips feed to autoclave with
moisture.
The yield was calculated by the formula:
(1)
2.2. Digestion of extracted pulp
100 gram of dried pre-extracted wood chips was
cooked with an autoclave at 131 oC for 140 minutes
with 4:1 liquor to wood ratio. The cooked pulp was
washed with deionized water to remove black liquor
composed of digested lignin, Na2SO4 and Na2CO3.
Then the pulp was dried in an open air and weighed to
know the losses during cooking and washing processes.
Finally the yield was calculated using equation (1).
2.3. Bleaching Experiment and Pulp sheet formation
processes
Bleaching of Kraft pulp were performed in two
bleaching methods; single (temporary) bleached by
hydrogen peroxide and sequential (true or permanent)
bleached by a sequence HEHP which are a combination
of three types of chemicals H(sodium hypochlorite,
used in two different stages to accomplish two quality
parameters: high brightness and high delignification
(residual lignin removal), E(sodium hydroxide) and
P(hydrogen peroxide).
In the first place, the dried pulp was bleached by using
hydrogen per oxide as bleaching agent in the ratio of 1:
100, hydrogen peroxide (mL) to pulp (g). The solution
was prepared from ingredients 2% sodium hydroxide,
1% sodium sulfide and distilled water. Then, 0.08 mL
hydrogen peroxide and 8 grams of dry pulp was added
to the solution and bleached for 60 minutes at 80 oC.
Then, the bleached pulp was washed with distilled
water, filtered and dried in an open air until the
moisture content removed. Finally, the dried bleached
Page No. 28
 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
pulp was weighed to determine the amount of final
product and determine losses during bleaching and
washing processes.
In sequential (true) bleaching method all tested pulps
were bleached under equal conditions with a simple
four-stage process, without pre-bleaching. The
conditions applied (including time, temperature and
chemical charge) were kept almost the same for each
stage in different sequences. The dried cooked pulp was
bleached by a sequence HEHP.
In the first stage (sodium hypochlorite, H) the pulp with
10% consistency was treated with NaOCl solution
(charge of 2.5% based on pulp weight) at a pH of 10 for
60 minutes at 60 C. The product was then filtered and
washed with distilled water until free of chlorine ions.
In the second stage (sodium hydroxide, E) the product
of the first stage were suspended in an aqueous
solution with 10% consistency which contained NaOH
(5% based on pulp weight) the suspension was agitated
for 90 minutes at 60 C , filtered and washed with
distilled water until reaching neutral condition.
In the third stage (sodium hypochlorite, H) the product
of the second stage with 10% consistency was mixed
with a NaOCl solution (5% based on pulp weight) pH
of 10, which contained the remaining 5% of the active
chlorine requirement for 70 minutes at 70 C and the
product was filtered and washed with distilled water till
free of chlorine ions. In the last stage (hydrogen
peroxide, P) the product of the third stage with 10%
consistency was filtered and treated for 60 minutes at
60 oC with H2O2 (2.2 % based on pulp weight) , at a
pH range of 9-11. Then, it was filtered, washed with
distilled water until reaching neutral condition and
dried in air.
For pasting, 400 grams of oven-dry pulp which was a
mixture of prehydrolyzed, cooked, single and double
bleached pulps were mixed and beaten at a range of
3000-4000 rpm and squeezed and pounded
mechanically the cellulose. After that the pulp was
ready for the sheet formation.
2.4. Determination of kappa number
The Kappa number was determined by the amount of a
0.1 M potassium permanganate solution consumed for
the oxidation of lignin contained in 1gram of absolutely
dry pulp at the standard conditions. Prepared amount of
dried unbleached pulp was dispersed in 370 mL of
water avoiding fiber cutting until pulp agglomerates
disappear. A mixture of 50 mL of a 0.1 M potassium
permanganate and 50 mL of a 4 M sulphuric acid
solution were added to the pulp suspension under
continuous stirring and diluted with water to the total
volume of 500 mL. After 10 minutes, potassium
Atnafu Guadie et al.,
permanganate consumption was estimated by
iodometrictitration method.
The Kappa number (Kn) or pulp stiffness was
calculated according to Equation:
--(2)
Where d-converting coefficient into 50% potassium
permanganate consumption determined based on the
value of v; m- the amount of dry pulp in gram; [1
+0.013(25T)]-Temperature correction term; T- average
temperature of the reaction mixture measured 5 minutes
after the reaction start, ; V-the volume of 0.1 M
solution of potassium permanganate required for
titration, mL.
The weight percent of the lignin can be calculated by
the formula:
(3)
2.5. Physical test parameters of pulp
A number of standard tests were carried out on the pre
pared sheets. The basic dimensional and structural tests
such as thickness, porosity, bulkiness and basic strength
tests of the pulp or paper such as tensile, bursting index
tear and compression tests were carried out.
2.6. Chemical Recovery Mechanism
The weak black liquor that was separated from the pulp
after a cooking process was evaporated by using
Kjeldhal instrument at a temperature of 200 oC. The
concentrated black liquor after evaporation was burnt in
an oven by 180 oC for 24 hrs, the smelt of Na2CO3 and
Na2S were formed. The smelt was dissolved with
deionized water which formed green liquor. The
solution of green liquor was recausticized by calcium
oxide-water slurry (Ca(OH)2). After the caustization the
liquid phase containing NaOH and Na2S (white liquor)
was separated from the solid lime mud by a slow
decantation. The presences of the inorganic salts in the
separated liquor were checked by reused the liquor for
digestion of the accepted chips. At last the lime mud
was heated to decompose by furnace at 1200 0C.
2.7. Lignin recovery
Kraft black liquors acquired from the end of each cook
and at other times during the cooks were isolated by
precipitating the lignin from solution by acidification.
The black liquors were first filtered through a whatman
# 4 filter paper on a Buchner funnel. Approximately 0.5
grams of EDTA-2Na+ was added for every 100 ml of
black liquor. The liquors were neutralized with 2 M
H2SO4 until pH 6. The solutions were then stirred
vigorously for one hour. The liquors were further
acidified to a pH of 3 and frozen at -20 C. After
thawing the solutions, the precipitates were collected on
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 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
a medium sintered glass funnel and washed twice with
cold water by suspending the precipitates in the water
and stirring vigorously at 0 C. The precipitates were
collected, air dried. Finally the recovered lignin was
tested and characterized by FTIR instrument.
3. Results and Discussion
3.1. Effect of pH
The effect of pH on the synthesis of pulp was
investigated for a wide range of the measured pH at
different process stages of pulp synthesis (Figure 1).
For a reacting mixtures a short hand designation
symbols were used; mixture of white liquor chips
before hydrolyzed (MBPH), mixture of mother liquor
with chips after prehydrolyzed (MAPH), mixture of
white liquor with prehydrolyzed chips before cooking
(MBC), mixture of mother liquor with pulp after
cooked (MAC), mixture of bleaching chemicals with
cooked pulp before bleaching (MBCPBB).
p H E ffe c t
15
14
13
12
pH
11
10
9 Fine amount
M
B
p
H
M
A
p
H
M
B
C
M
A
C
M
B
C
P
B
B
8 Kappa number
P u lp S a m p le s w ith liq u o r
Figure 1 Effect of pH on pulping processes at different
stages
The pH of the reacting mixtures of pulp samples are
decreasing from MBPH-MAPH, MBC-MAC, and
MAC-MBCPBB and sharply increasing from MAPH-
MBC (Figure 1). The results showed that during the
Kraft process as a result of large amount of NaOH used,
the pH at the start of the prehydrolyzed and cooking
processes recorded were high due to the alkaline
pulping process. It decreases continuously during the
course of cooking since organic acids were liberated
from lignin and carbohydrates (hemicelluloses) during
the pulping reaction as a result of hydrolysis and
dissolution processes. This indicates the alkaline Kraft
process hydrolyzes and dissolves the lignin and the
amorphous hemicelluloses at higher pH, and prevents
the hydrolysis of cellulose which is favorable in acidic
conditions at a lower pH value. At acidic condition
cellulose fibers were degraded up on decreasing of its
pH when lignin is dissolved [12].
The sharp decrease from MAC-MBCPBB
indicates large amount of lignin dissolution at the time
of cooking at higher pH and the residual lignin content
Atnafu Guadie et al.,
decreased due to the bleaching chemicals. During
bleaching adjustment of pH is necessary at strong
alkaline range due to the decrease in alkalinity up on
addition of bleaching chemicals otherwise cellulose
degradation takes place at lower pH value which
decreases pulp yield. Generally these results give
higher alkaline process (Kraft) process is suitable for
high pulp yield product and adjustment of pH is
necessarily up on cooking and bleaching processes to
adjust the decrease in pH due to the lignin acidic
groups are dissolved [13].
3.2. Pulp extraction
In basic Prehydrolysis 100 g of eucalyptus chips were
suspended in a solution of sodium hydroxide (21.948 g)
and sodium sulfide (14.88 g) white liquor and heated
for 100 minutes in autoclave which gives 70.9 g of
prehydrolyzed pulp.
Table 1 The result of the recovered mass and
qualitative observation obtained after pre hydrolysis
process
Parameter Quantitative Qualitative
Initial weight 100 g -
Final Weight 70.9 g -
Color - Light brown
Medium -
20.8 -
Lignin content High -
After Prehydrolysis only 70.9 g of pulp was obtained
per 100 g of input chips. In other studies, the yield of
pulp for acid and alkaline pre-hydrolyzed pulp is 65%
and 74% respectively [14]. In this study, after
Prehydrolysis with base 70.9% yield of pulp was
achieved. On the other hand, 29.1% of cellulose during
pre-base Prehydrolysis stage was obtained. In the
Prehydrolysis of the eucalyptus chips, alkaline
hydroslysis provided a higher yield than acid hydrolysis
with higher kappa number (more lignin content pulp)
and light brown in color. At prehydrolyzed step only
some amount of lignin is removed so that the produced
pulp has high kappa number which is 20.8. Besides,
medium fine amount of fibers were obtained in this step
due to incomplete digestion process.
The low yield in the acid pulping could be
related to acid hydrolysis of cellulose to sugar
monomer. Acid hydrolysis proceeds in three steps. The
reaction starts with a protonation of the glycosidic
oxygen linking in to two sugar units, forming
protonated cellulose (conjugate acid). Then, water
makes a nucleophilic attack on the protonated cellulose
which breakdown to the cyclic carbonium ion [14]. This
Page No. 30
 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
indicates Kraft alkaline process is suitable for high
yield of pulp synthesis.
3.3. Cooking or Digestion of Eucalyptus Wood
In this study, after digestion only 46.4 g of
pulp was obtained per 100 grams of input
prehydrolyzed chips (Table 2) at cooking conditions of
6 bars, 131 oC for 140 minutes, liquor to wood ratio of
4:1 and effective alkali of 87.8g per liter with a
sulphidity of 24.4 %.
Table 2. The result obtained after cooking process
Parameter Quantitative Qualitative
Initial weight 100 gm - Lignin content
Final weight 46.4 gm - The single bleached eucalyptus pulp has a
Color - Dispersed white
Kappa number 9.834
Fine amount small - residual lignin content almost removed up on bleaching
After cooked with white liquor, a yield of
46.4 % pulp was achieved which is nearer value of
yield to the expected one which is 53-56 % [4] for
eucalyptus Kraft pulp. The eucalyptus cooked pulp has
a kappa number of 9.834 (Table 2) which is less than
from the kappa number of prehydrolyzed pulp which
has a (kappa number of 20.8) (Table 1). This suggested
that much of the lignin was dissolved and entered into
the liquid phase during cooking step. 7-10 % cellulose
loss of fiber pulp is less than that of the expected value
due to unfavorable conditions for digestion like the
non-selectivity of the chemicals (white liquor) used to
degrade lignin, time, temperature and the decrease in
pH. In the cooking stage of this process in a pressurized
autoclave with a specific pressure of 6 bar, the cooking
chemicals (white liquor) used in pulping process alter
the structure of lignin in such a way that soluble
fragments of polymer was produced by different
possible mechanisms.
3.4. Pulp Bleaching Sequence
Pulping process alone is not enough to produce
cellulose of eucalyptus suitable for Pulp synthesis
applications. After pulping, cellulose must be subjected
to further purification. The goal of bleaching is to
reduce the kappa number without drastically decreasing
the degree of polymerization of the cellulose. In single
bleaching step, 20 grams of cooked dried pulp was
bleached with bleaching agent of 0.2 mL of hydrogen
per oxide for 60 minute at 80 oC operating temperature.
At the end of operation, the bleached pulp was washed,
dried and weighed.
After bleached by H2O2 18.22 g of white
bleached pulp was obtained from 20 g of dried cooked
Atnafu Guadie et al.,
pulp input which corresponds to 8.9 % loss and 91.1%
yield (Table 3).
Table 3 Yield and quality of pulp obtained by single
bleaching process
Parameter Quantitative Qualitative
Initial weight 20 gm -
Final weight 18.22 gm -
Color - white
Kappa number 7.7 -
Fine content Very small -
Low -
kappa number of 7.7 which is less than the kappa
number 9.834 of cooked pulp (Table 2) signifies the
with hydrogen peroxide. The fine content of the fibers
also increased very well due to removal of a residual
lignin that can compact the fibers by holding together.
The 91.1 % yield from the single bleached pulp reveals
that hydrogen peroxide has a high selectivity power to
degrade the residual lignin without interfering to the
degradation of carbohydrates specially cellulose fiber
which is the main constituent of pulp yield and gives
achievable brightness of the pulp product.
It was reported that lignin removal rates is as
high as 95 % during bleaching pulp which leads high
levels of brightness (whiteness) without pulp
degradation [15]. In that case, the result obtained in this
experiment has comparable pulp yield of 91.1%. Thus,
hydrogen peroxide can remove the residual lignin
attached to the cellulose after cooking and cleavage aryl
ether linkage of the attached cellulose that increases the
dissolution of lignin. But, it only gives temporarily
brightness which is not suitable for manufacturing of
many types of paper grades.
In the sequentially bleached pulp, after each
bleaching stage, the pulps were thoroughly washed with
deionized water and analyzed for yield and residual
lignin contents (Kappa number).The progress of the
digestion was monitored by measuring the pH. The
resulted sequentially bleached pulp has 5.9 of kappa
number which indicates almost the total removal of
lignin from pulp which gives brightest permanent
whiteness colored pulp. The weight of pulp at the first
bleaching stage was 20 g at one step whereas the
weight of the bleached pulp after the sequential
bleaching was 15.4 g. This shows that a weight loss of
6.6 g pulp and a decrease in pulp yield to 77 % which is
less than single bleached pulp yield of 91.1 %. It may
be due to the unselectively degradation of cellulose by
Page No. 31
 International Journal of Environmental Science and Technology, 2015, 1(2),20-26

bleaching chemicals and loosing of the pulp during higher lignin content. Consequently, low Kappa
open air dried. numbers should be targeted if the pulp is to be bleached
[14]
3.5. Determination of kappa number .
The amount of lignin remains in cellulose after In this experiment, the mass, blend temperature
pulping and bleaching usually estimated by Kappa and volumes were measured for cooked pulp, single
number. The Kappa number is an indicator of the bleached pulp and sequential bleached pulp during each
residual lignin content of the pulp and is an important of the experiment separately.
quality parameter. The higher Kappa number gives
Table 4. the measured parameters and the calculated kappa number of bleached & unbleached pulps
Parameters
Sample name m (g) C b (ml) V2(ml) C(M) V(ml) d Kappa number
Cooked pulp 3 20 12 6.8 0.2 27.4 1.011 9.834
Single bleached 3 23 12 10.8 0.2 22.8 0.991 7.7
Sequential bleached 3 23.8 12 13.1 0.2 18 0.970 5.9

The kappa number decrease as bleaching stage
increase. The result indicated that residual lignin
content of cooked pulp is highest whereas due to
effective bleaching, it decreases when the pulp was
bleached. Lignin content would not be completely
removed during the digestion step which has a higher
amount of residual lignin content whereas up on
bleached with single chemical it decreases a lesser
extent and bleaching with a combination of chemicals
as HEHP sequence resulted almost pure pulp.
Generally, the result indicates that sequential bleaching
sequence was an achievable and efficient method for
complete removal of the residual lignin which gives a
lower kappa number of 5.9.
3.6. Characterizations of the synthesized pulp
3.6.1 FTIR data of single and sequential bleached
pulps
FTIR spectra of single and sequential bleached
pulps were recorded for further investigation of the
structures of constituents and the chemical changes of
eucalyptus pulps during Kraft pulping and bleaching.
Thus, the IR spectra of the two types of bleached pulps
have almost the same number of peak absorption bands
(Figure 2). However, the amount of absorption bands
sharpness of the peaks, their intensities, their
broadening and overlapping are different. An intense,
very broad absorbance peak at around 3444.9 cm-1
indicates the OH- bond stretching vibration of alpha
cellulose. The signals at around 2894 cm-1 is due to C-
H stretching vibrations in methyl and methylene groups
of the polysaccharide (lingo cellulosic components).
The peaks observed at around 1639 cm-1 is due to the
OH- vibration of the adsorbed water. The short
branched peak at around 1423 cm-1 is attributed to
skeletal vibration of the aromatic ring combined with
C-H in plane deforming and stretching and the OH- in
plane bending of cellulose of bleached pulp. The
medium sharp tiny peak at around 1374 cm-1 indicates
bending vibration of aliphatic C-H stretching in methyl
and C-O groups of the aromatic ring in polysaccharides
(cellulose). The absorbance short branched peak at
around 1311 cm-1 assigned to C-H in plane bending of
cellulose I and cellulose II and used to characterize
polymorphs of crystalline cellulose.
The medium branched peak at around 1157 cm-
1
is due to C-O-C ring vibrational stretching of B(1,4)-
glycosidic linkage for cellulose I and cellulose II and C-
O anti-symmetric bridge stretching of cellulose. The
broad long peak at around 1060 cm-1 indicates the C-
OH stretching vibration of the cellulose and
hemicelluloses.The very short tiny absorption band at
around 893 cm-1 assigned to C-O-C -glycosidic
linkages between the glucose units of cellulose. The
peaks at around 677 cm-1 and 607 cm-1 can be attributed
to C-OH out of plane bending of cellulose. The result of
the FTIR spectrum in this study is the same as reported
in previous studies [16-22].
Similarly, the spectra of sequential bleached
pulps shows a bands at 1423, 1374,1157,1060,893 and
677 cm-1 are assigned to O-H in-plane bending of
cellulose and C-H asymmetric deformation, bending
vibration of aliphatic C-H stretching in methyl and C-
O groups of the aromatic ring, C-O-C ring vibrational
stretching of B(1,4)-glycosidic linkage for cellulose I
and cellulose II and C-O anti symmetric bridge
stretching of cellulose.
The C-OH stretching vibration of the cellulose
and hemicelluloses-O-C B-glycosidic linkages between
the glucose units of cellulose and C-OH out of plane
bending of cellulose, which are associated with typical
absorption of cellulose. This indicates the evidence of
lignins removed from the bleached pulp effectively.In

Atnafu Guadie et al., Page No. 32

 International Journal of Environmental Science and Technology, 2015, 1(2),20-26

general band intensity changes in the spectra reflects changes (degradation and condensation) taking place
the sequential bleached pulps have an intense and during bleaching and lignin extraction as a result their
sharper peaks than single bleached once which peaks are differ in band intensity.
indicates the effectiveness of the former system. The

Figure 2. FTIR Spectra of single and sequential eucalyptus pulp by alkaline H2O2

3.6.2. FTIR Spectra of the recovered lignin O stretching vibration of H2SO4 added at lignin
In order to elucidate the structure of Kraft lignin recovery acidification step [18, 23]. 467 cm-1, and 426 cm-
1
isolated from the eucalyptus pulp from black liquor by is due to the Na metallic absorption of sodium metal
acid precipitation were analyzed by FTIR (Figure 3). that came from digestion step.
The wide absorption band at around 3410 cm-1 is R e c o v e r e d L ig n in
45

assigned to aromatic and aliphatic OH- vibrations of 40 1311

872

Kraft lignin. The band at around 3020 cm-1 is reflected 35

30
1214
Transmittance: %

to the C-H vibration of methyl and methylene groups of 25 426

467
Kraft lignin. The band at around 1694.8 cm-1 20

15
3020 7 8 1 .8 558

corresponding to conjugated carbonyl stretching (C=O) 10 1416 586

5 3410 1 6 9 4 .8 963

of ketones and carboxyl groups of lignins [23].The band 0

1095 1046
4000 3500 3000 2500 2000 1500 1000 500

at around 1416 cm-1 indicates skeletal vibration of W ave num ber / C m

-1

aromatic ring (C-C) vibration of the lignin. The band at

Figure 3. IR Spectra of recovered kraft lignin from the
around 1311 cm-1 is due to syringyl ring vibration with
black liquor
valence vibration of CO-group which indicates syringyl
In the IR spectrum of recovered kraft lignin,
aromatic structure of the lignin. The absorbance peak
absorption band of valence vibrations of alcohol and
around 1214 cm-1 reflects the C-O vibration of ring
phenol O-H bonds is surely identified with maximum
guaiacyl structure of lignin and the skeletal vibration of
absorption at about 3410 cm-1. Moreover, an intense
syringyl ring. The peak appeared at around 1095 cm-1
vibration band of carbonyl group (C=O) is observed at
comes from the ArC-H in-plane deformation in
1694.8 cm-1 that can be explained by either carbonyl
guaiacyl ring and the plane deformation vibration of
groups presence in lignin structure or acetylated alcohol
ArC-H bond in syringyl ring structure of the recovered
fragments or ester linkage of carboxylic group in the
lignin [23].
ferulic and p-coumeric acids of lignin or hemicellulose
The band at 1046 cm-1 comes from plane [18]
.
deformation vibrations of C-H bond in guaiacyl ring
The absence of this peak in the above bleached
and deformation vibrations of C-OH bond in primary
pulp spectra indicates the removal of lignin and
alcohols and C-O-C vibrations in ethers of the kraft
hemicellulose during the chemical treatments of
lignin [16]. The peak appeared at around 963 cm-1 arises
beaching process. Absorption band at 1416 cm-1 may be
from the C-H out-of plane bending in guaiacyl units of
assigned to skeletal vibrations of aromatic ring. Peaks
lignin. The peak at around at around 873 cm-1 indicates
at 1311 cm-1 corresponds to skeletal vibrations of
out of plane bending of C-H in syringyl units of lignin
syringyl ring and at 1214 cm-1 that corresponds to
and syringyl ring vibration of the recovered lignin [17].
skeletal vibrations of syringyl ring with guaiacyl ring
The band at around 781.8 cm-1 arises due to C-OH out
vibration super position. The absence of this peaks in
of plane bending of the dissolved cellulose and ArC-H
bleached pulp spectra (Figure 2) believed to be due to
vibrations of the guaiacyl units of lignin [23]. The peaks
the removal of lignin after chemical treatments.
arise at 586 cm-1 and 558 cm-1 is associated with the S-

Atnafu Guadie et al., Page No. 33

 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
The absorption bands at 1694.8, 1214, 1095, 1046, 963
and 872 cm-1 in this spectra attributed to the functional
groups present in the lignin before delignification but
they are absent in the bleached pulps spectra (Figure 2).
Thus, the spectra show that the recovered lignin is
composed of guaiacyl and syringyl structures, which
are typical for lignin of hard wood pulp [19].
3.6.3. UV-Visible diffuse absorption spectrum of
bleached pulps for brightness studies
UV-Vis reflectance spectroscopy is an efficient
method for brightness stability studies. The absorbance
of UV spectra is directly proportional to the purity level
of lignin. Visible spectral region and reflectance spectra
are sensitive to the changes in colored pulp components
determining pulp brightness. UV-active structures (like
HexA, carbonyl groups and some lignin units) are
known precursors to the colored structures formed
during yellowing [24]. Single and sequentially bleached
pulps were recorded by UV-visible diffuse reflectance
spectrometer (Figure 4).
Figure 4. The UV-visible spectra of single and
sequential bleached eucalyptus pulp The spectra near
370 and 320 nm are bands probably arise from strongly
Table 5. Results of physical testers of pulp after sheet formation
Parameters
Bursting strength (kg/cm2)
Porosity (sec/100m)
Tear strength (MN)
Smoothness (mL/sec)
Tensile strength (kg)
Thickness (mm)
Bulkiness (cm3/gm)
The prepared sheet has a value of porosity
11.02 sec/100m which is greater than the standard value
(10 sec/100m) which indicates the sheet prepared from
eucalyptus pulp is highly air permeable and porous due
to increased amount of beating which gives a denser
smooth paper [4, 24]. The air permeability of high kappa
pulp is lower than low kappa pulp so that the prepared
strength. The resulted eucalyptus Kraft pulp that was
prepared in this experiment has enough strength.
Smoothness (mL/sec) refers to the absence of surface
Atnafu Guadie et al.,
conjugated C=O and C=C systems such as occur in o-
Quinones and in aromatic aldehyde, acids and ketones.
The main functional group contributing to the
oxidation of hard wood Kraft residual lignin is syringyl,
C5 non condensed guaiacyl units and stilbene phenolic
structures. The inability to oxidize the phenyl propane
side chain of lignin and/or C5 condensed guaiacyl
phenolics detrimentally impacts bleachability [24]. The
UV-vis difference spectrum had no absorption band at
max 370 nm suggesting the absence of phenolic
stilbene-like structures which are the main components
of residual lignin.
The UV-vis spectrum of the bleached pulps
shows that both spectrum of pulps are visible
transparent which indicates enough brightness of the
pulps so that the lignin chromospheres were removed
by chemical treatments with bleaching agents.
3.6.4. Physical test parameters of pulp after sheet
formation
The basic dimensional and structural tests such as
thickness, porosity, bulkineness and basic strength tests
of the pulp or paper such as tensile, bursting and tear
tests were carried out. The maximum pressure that the
prepared sheet can resist when applied perpendicularly
to the surface of the sample was 1 kg/m2 which is less
than the standard (1.2 kg/m2). This may happen due to
short fibers of the eucalyptus pulp and the effect of
beating. Bursting strength increases with increasing
beating energy.
Test result Standard
1.00 1.2
11.02 10
63.04 65
388.42 365-424
5.6 6
0.16 0.1
1.78 1.67
sheet of eucalyptus pulp is low kappa pulp than the
standard once due to its high porosity.
The tear Strength (MN) measures the ability of the
sheet to resist the propagation of a tear and the amount
of energy to fracture a sample [24]. The prepared sheet
had a value of tear strength 63.04 MN which is nearer
to the standard ones which has value of 65 MN tear
rregularities under either usual or unusual conditions.
Smoothness is higher for denser, smaller and more
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 International Journal of Environmental Science and Technology, 2015, 1(2),20-26

flexible fiber made papers but lower for bulky papers
[1]
. The prepared sheet has a value of smoothness
388.42 mL/sec which is a comparable value to the
standard indicates a smooth paper made with no
irregularities.
Tensile strength (KN/m2) is the maximum force
per unit weight that a paper can tolerate without
breaking with the load applied in the direction of
parallel to the length of the sample. The stress is
expressed as force per unit width of a test specimen.
Tensile index relates the value of tensile strength to the
basis weight of the material. Tensile index is mainly
used for pulp strength whereas tensile strength is
preferable for paper strength [4]. The prepared sheet has
tensile strength value of 5.6 Kg nearer to the standard
sheet which has a value of tensile strength 6 kg.
The thickness of the paper (mm) was measured
between two parallel plates applying certain pressure.
The prepared eucalyptus pulp sheet has thickness value
of 0.16 mm higher than the standard. This may be due
to the less compact of fibers. The actual physical
thickness of a piece of paper usually expressed in
thousands of an inch is the bulk of the paper. Bulk
affects the flexibility of the paper. In general, bulk
decreased continuously with increased amount of
beating. The sheets made from high lignin containing
pulp had lower bulk whereas the sheet made from lower
lignin containing pulp had higher bulk [24]. The prepared
sheet had a bulk value of 1.78 cm3/g which is higher
than the standard so that the sheet was formed from
lower lignin containing pulp.
3.6.5. Recovery of Inorganic Chemicals
The chemicals used were recycled for
profitability and environmental reasons. Firstly the
weak black liquor was evaporated by Kjeldhal
instrument. The result of this evaporation was
concentrated black liquor. After concentration of the
black liquor it was burned by using an oven so that due
to the reduced sodium sulfur compounds Na2S
containing smelt with NaCO3 was formed. The smelt
was dissolved with water that was given a green liquor
product. The solution of green liquor was reacted with
calcium oxide-water slurry for caustization process.
After caustization two phase solution were
obtained which indicates the formation of the solid lime
mud due to calcium carbonate formation and a white
liquor mixture of a liquid phase containing NaOH and
Na2S. This white liquor was separated from the solid
lime mud by slow decantation and once again used for
digesting of eucalyptus chips. At last the lime mud was
heated by furnace at 1200 C so that CO2 was evolved
from the mud that indicates the regeneration of calcium
oxide of calcium oxide slurry.
3.7. Material Balance
The material (mass) balance calculation of
this document is based on experimental results obtained
during laboratory analysis and can be scaled up into
industrial level considering the annual pulp demand of
about 10,000 tons of pulp for Ethiopia Paper Factory
(Wonji). The main purpose of performing material and
energy balance is to know raw material and energy
demand as well as the size of equipments for the
proposed production capacity.
As indicated in the Table 6, it is clear that mass
of output product (unwashed prehydrolyzed pulp) is
equal to that of the sum of individual input.

Table 6. Combined experimental result for the purpose of mass balance

Process step Pre Digestion Single Bleaching Sequentially
hydrolysis bleaching
Initial weight (gram) 100 100 20 20
Final weight (gram) 70.9 46.4 18.22 15.4
NaOH + Na2S (gram) 36.828 99.9 0.96
Water to make liquor 400 400 80 320
(mL)
Washing water(ml) 2000 1600 1000 1200
H2O2 (gram) ------- -------- 0.12 0.022
NaOCl (gram) . 1.5
NaOH(gram) 1

3.8. Cost Effectiveness and Selected Equipment
Design of the Process
The supply of paper in Ethiopia is dominated
by imported products. The only paper producing
factory in Ethiopia is Ethiopian Pulp and Paper Share
Company which is located at Wonji. This factory has a
production capacity of 8,000-10,000 tones, annually.
Due to the limited production capacity of the country's
sole producer of paper, the country imports a large
quantity of paper from oversees. The information (data

Atnafu Guadie et al., Page No. 35

 International Journal of Environmental Science and Technology, 2015, 1(2),20-26
of 2005 E.C) gathered from Ethiopia Pulp Factory
shows that the raw material (pulp) demand of the
factory is about 10,000 -15,000 tons per year. This
limited production of the country is due to lack of raw
material (pulp) in the country national wide. The supply
of kraft paper in Ethiopia is through import. The
information obtained from external trade in (2000 E.C)
statistics gives that the present effective demand for
kraft paper is estimated to be 5,504 tones. Design
(sizing) of major equipments that are used in eucalyptus
pulp production is performed based on experimental
result and the equipment capacity should be scaled up
Table 7 Annual materials requirement in tones and cost
Description Quantity
Wood chip 18,750
NaOH 2010
Na2S 13.7688
H 2O 2 14.2
NaOCl 15
CaO 101.25
Electricity 10,500,000 (KWh)
Water 750000 (m3)
Chemicals are also required in the pulp making process.
These include caustic soda, Sodium sulfide, sodium
hypochlorite, starch, hydrogen peroxide and lime. The
process is economically effective.
4. Conclusions
The Kraft pulp is lignin free and can be used in
making high quality writing and printing papers that are
both coated and uncoated. The result obtained after
bleaching process was close to the expected result
which has less lignin content pulp with a kappa number
of 20.8, 9.834, 7.7 and 5.9 for prehydrolyzed, cooked,
single bleached and sequentially bleached eucalyptus
pulp respectively. The sequential bleaching process
produces a brightest pulp which is an efficient method
than the single bleaching ones. The FTIR spectrum of
single and sequentially bleached pulps showed that the
chemical treatments could successfully be used to
remove lignin and hemicelluloses. An increase in the
cellulose content in each chemical treatment observed
at the major peaks in the spectrum indicating cellulose
functional groups. Band intensity changes in the spectra
reflect the sequential bleached pulps have an intense
and sharper peaks than single bleached once which
indicates the increase of cellulose content up on
sequentially bleached eucalyptus pulp.
The FTIR spectrum of recovered lignin agrees
closely with certain values for functional groups of hard
wood pulp lignin. IR spectrum indicates that the
Atnafu Guadie et al.,
considering the annual pulp demand of existing paper
factory of the country.
The digester which is suitable to the reaction is
mixed flow reactor. The production design is to have
eight batches per day with three hours resident time in
the cooker (reactor). From annual production of 10,000
tons of pulp, we can have the amount produced
28,571.4 kg/day (3,571.4 kg per batch) of pulp. To
obtain 3,571.4 kg per batch of pulp we have to use
11916.68 kg of eucalyptus wood chip for single bleach
process and 14116.32 kg of eucalyptus wood chip for
sequentially bleach process.
Unit price Total cost (birr)
200 3750
4360 8763.6
1200 121500
0.335
1.5
recovered lignin is composed of guaiacyl and syringyl
structures, typical for lignin of hard wood pulp. Peak
intensity changes in the spectra of recovered lignin,
single and sequentially bleached pulps point out
degradation and condensation processes during
bleaching and lignin extraction. The UV-Visible
spectrums of single and sequential bleached pulps
indicate the lignin purity of the pulps based on the
value of absorbance. The UV-Visible graph of the
bleached pulps, transparent at visible region indicates
the brightness of the pulps. The physical test parameters
such as tensile strength, tear strength, porosity, bursting
strength, bulkiness and thickness obtained from the
instrumental readings were closer with the standards of
the pulp and paper factories. In this study, the Kraft
process in manufacturing pulp from eucalyptus is
generally a suitable process with cost effective due to
the cheapest raw material used and the recovery of the
used chemicals.
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