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Synthesis and Characterization of Eucalyptus

Pulp by Kraft Process for Paper Sheet
Formation

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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: [email protected]
................................................................................................................................................
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

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

viz., chemical, mechanical, semi-chemical and recycle screened with 0.8 mm mesh and 1.5 mm mesh sieves to
among which chemical pulping is the most common eliminate over sized and fine chips. Then, the chips
process [8]. Chemical (i.e., Kraft, soda, and sulfite) were washed several times with distilled water to
pulping involves cooking of wood chips using aqueous remove dirties and dried with electric oven and stored
chemical solutions at elevated temperature and pressure in moisture free place until analysis.
to extract pulp fibers [9]. Generally, paper is made by 100 grams of accepted chips with 0.8 mm mesh sieve
pulping wood, bleaching this pulp and then spreading it size were fed in to the autoclave at a pressure of 6 bar.
out into sheets to formulate paper. At various stages of The extraction (prehydrolyzed) experiments were
the process, chemicals are used to give the paper performed with white liquor (21.948 grams of NaOH
particular properties such as the bleaching chemicals and 14.88 grams of Na2S) to wood ratio of 4:1 at 100
o
that make paper white (and which also enable it to C for 100 minutes. The wood chip was then washed
subsequently be colored). Kraft pulping is by far the with distilled water. Then, the washed pre-hydrolyzed
most common pulping process in the world for virgin chip heated in an oven drier at 105 oC for 180 minutes
fiber, accounting for more than 80 percent of the total to remove the moisture gained during prehydrolyzed
world pulp production [10]. process. The weight loss during digestion and washing
The major reason why there are no additional paper process was determined by subtracting the dried weight
mills with better capacity in Ethiopia is estimated to be from the weight of chips feed to autoclave with
the huge capital investment that paper mills normally moisture.
require and significantly high cost of raw material that The yield was calculated by the formula:
is imported from different countries of the world. These
make the local production of paper inefficient and less (1)
competitive when compared to other sectors in the 2.2. Digestion of extracted pulp
industry, which significantly affects the overall 100 gram of dried pre-extracted wood chips was
economic growth of the country. For this reason, the cooked with an autoclave at 131 oC for 140 minutes
country should produce the raw material for paper with 4:1 liquor to wood ratio. The cooked pulp was
making from the available wood products. Eucalyptus washed with deionized water to remove black liquor
wood produces quickly to meet societys needs, and composed of digested lignin, Na2SO4 and Na2CO3.
also helps preserve indigenous forests. Eucalyptus trees Then the pulp was dried in an open air and weighed to
are highly profitable and take a shorter period to reach know the losses during cooking and washing processes.
at the harvesting age and require little human action on Finally the yield was calculated using equation (1).
the land during this period [11]. 2.3. Bleaching Experiment and Pulp sheet formation
It is clear that in Ethiopia, pulp is imported from abroad processes
for paper factories. In order to overcome this problem it Bleaching of Kraft pulp were performed in two
seems promising to establish pulp factory at a national bleaching methods; single (temporary) bleached by
wide. If so, eucalyptus can met the problem of highly hydrogen peroxide and sequential (true or permanent)
increasing cost of paper as alternative source of raw bleached by a sequence HEHP which are a combination
material for paper synthesis [3]. In order to overcome the of three types of chemicals H(sodium hypochlorite,
challenges of the paper industry, a special attention used in two different stages to accomplish two quality
should be given facilitating the productions of the parameters: high brightness and high delignification
major raw material (pulp) locally and discouraging (residual lignin removal), E(sodium hydroxide) and
importation so that the local manufacturers will be P(hydrogen peroxide).
competent enough on the market. The main objective of In the first place, the dried pulp was bleached by using
this work is to synthesize and characterize eucalyptus hydrogen per oxide as bleaching agent in the ratio of 1:
pulp by chemical Kraft process with investigation of 100, hydrogen peroxide (mL) to pulp (g). The solution
the recovery mechanism of the consumed chemicals. was prepared from ingredients 2% sodium hydroxide,
2. Materials and Methods 1% sodium sulfide and distilled water. Then, 0.08 mL
2.1. Raw material preparation and Pulp extraction hydrogen peroxide and 8 grams of dry pulp was added
Seven up to nine year eucalyptus wood was collected to the solution and bleached for 60 minutes at 80 oC.
from Debark at around North Gondar, Ethiopia. The Then, the bleached pulp was washed with distilled
eucalyptus wood was debarked, chipped and grinded in water, filtered and dried in an open air until the
to the range of 0.2-2 mm. The ground chips were moisture content removed. Finally, the dried bleached

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

pulp was weighed to determine the amount of final permanganate consumption was estimated by
product and determine losses during bleaching and iodometrictitration method.
washing processes. The Kappa number (Kn) or pulp stiffness was
In sequential (true) bleaching method all tested pulps calculated according to Equation:
were bleached under equal conditions with a simple --(2)
four-stage process, without pre-bleaching. The
conditions applied (including time, temperature and Where d-converting coefficient into 50% potassium
chemical charge) were kept almost the same for each permanganate consumption determined based on the
stage in different sequences. The dried cooked pulp was value of v; m- the amount of dry pulp in gram; [1
bleached by a sequence HEHP. +0.013(25T)]-Temperature correction term; T- average
In the first stage (sodium hypochlorite, H) the pulp with temperature of the reaction mixture measured 5 minutes
10% consistency was treated with NaOCl solution after the reaction start, ; V-the volume of 0.1 M
(charge of 2.5% based on pulp weight) at a pH of 10 for solution of potassium permanganate required for
60 minutes at 60 C. The product was then filtered and titration, mL.
washed with distilled water until free of chlorine ions. The weight percent of the lignin can be calculated by
In the second stage (sodium hydroxide, E) the product the formula:
of the first stage were suspended in an aqueous (3)
solution with 10% consistency which contained NaOH 2.5. Physical test parameters of pulp
(5% based on pulp weight) the suspension was agitated A number of standard tests were carried out on the pre
for 90 minutes at 60 C , filtered and washed with pared sheets. The basic dimensional and structural tests
distilled water until reaching neutral condition. such as thickness, porosity, bulkiness and basic strength
In the third stage (sodium hypochlorite, H) the product tests of the pulp or paper such as tensile, bursting index
of the second stage with 10% consistency was mixed tear and compression tests were carried out.
with a NaOCl solution (5% based on pulp weight) pH 2.6. Chemical Recovery Mechanism
of 10, which contained the remaining 5% of the active The weak black liquor that was separated from the pulp
chlorine requirement for 70 minutes at 70 C and the after a cooking process was evaporated by using
product was filtered and washed with distilled water till Kjeldhal instrument at a temperature of 200 oC. The
free of chlorine ions. In the last stage (hydrogen concentrated black liquor after evaporation was burnt in
peroxide, P) the product of the third stage with 10% an oven by 180 oC for 24 hrs, the smelt of Na2CO3 and
consistency was filtered and treated for 60 minutes at Na2S were formed. The smelt was dissolved with
60 oC with H2O2 (2.2 % based on pulp weight) , at a deionized water which formed green liquor. The
pH range of 9-11. Then, it was filtered, washed with solution of green liquor was recausticized by calcium
distilled water until reaching neutral condition and oxide-water slurry (Ca(OH)2). After the caustization the
dried in air. liquid phase containing NaOH and Na2S (white liquor)
For pasting, 400 grams of oven-dry pulp which was a was separated from the solid lime mud by a slow
mixture of prehydrolyzed, cooked, single and double decantation. The presences of the inorganic salts in the
bleached pulps were mixed and beaten at a range of separated liquor were checked by reused the liquor for
3000-4000 rpm and squeezed and pounded digestion of the accepted chips. At last the lime mud
mechanically the cellulose. After that the pulp was was heated to decompose by furnace at 1200 0C.
ready for the sheet formation. 2.7. Lignin recovery
2.4. Determination of kappa number Kraft black liquors acquired from the end of each cook
The Kappa number was determined by the amount of a and at other times during the cooks were isolated by
0.1 M potassium permanganate solution consumed for precipitating the lignin from solution by acidification.
the oxidation of lignin contained in 1gram of absolutely The black liquors were first filtered through a whatman
dry pulp at the standard conditions. Prepared amount of # 4 filter paper on a Buchner funnel. Approximately 0.5
dried unbleached pulp was dispersed in 370 mL of grams of EDTA-2Na+ was added for every 100 ml of
water avoiding fiber cutting until pulp agglomerates black liquor. The liquors were neutralized with 2 M
disappear. A mixture of 50 mL of a 0.1 M potassium H2SO4 until pH 6. The solutions were then stirred
permanganate and 50 mL of a 4 M sulphuric acid vigorously for one hour. The liquors were further
solution were added to the pulp suspension under acidified to a pH of 3 and frozen at -20 C. After
continuous stirring and diluted with water to the total thawing the solutions, the precipitates were collected on
volume of 500 mL. After 10 minutes, potassium

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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 decreased due to the bleaching chemicals. During
cold water by suspending the precipitates in the water bleaching adjustment of pH is necessary at strong
and stirring vigorously at 0 C. The precipitates were alkaline range due to the decrease in alkalinity up on
collected, air dried. Finally the recovered lignin was addition of bleaching chemicals otherwise cellulose
tested and characterized by FTIR instrument. degradation takes place at lower pH value which
3. Results and Discussion decreases pulp yield. Generally these results give
3.1. Effect of pH higher alkaline process (Kraft) process is suitable for
The effect of pH on the synthesis of pulp was high pulp yield product and adjustment of pH is
investigated for a wide range of the measured pH at necessarily up on cooking and bleaching processes to
different process stages of pulp synthesis (Figure 1). adjust the decrease in pH due to the lignin acidic
For a reacting mixtures a short hand designation groups are dissolved [13].
symbols were used; mixture of white liquor chips 3.2. Pulp extraction
before hydrolyzed (MBPH), mixture of mother liquor In basic Prehydrolysis 100 g of eucalyptus chips were
with chips after prehydrolyzed (MAPH), mixture of suspended in a solution of sodium hydroxide (21.948 g)
white liquor with prehydrolyzed chips before cooking and sodium sulfide (14.88 g) white liquor and heated
(MBC), mixture of mother liquor with pulp after for 100 minutes in autoclave which gives 70.9 g of
cooked (MAC), mixture of bleaching chemicals with prehydrolyzed pulp.
cooked pulp before bleaching (MBCPBB). Table 1 The result of the recovered mass and
qualitative observation obtained after pre hydrolysis
p H E ffe c t
15
process
14
Parameter Quantitative Qualitative
13
Initial weight 100 g -
12
Final Weight 70.9 g -
pH

11
10 Color - Light brown
9 Fine amount Medium -
M
B
p
H

M
A
p
H

M
B
C

M
A
C
M
B
C
P
B
B

8 Kappa number 20.8 -

P u lp S a m p le s w ith liq u o r Lignin content High -

Figure 1 Effect of pH on pulping processes at different After Prehydrolysis only 70.9 g of pulp was obtained
stages per 100 g of input chips. In other studies, the yield of
pulp for acid and alkaline pre-hydrolyzed pulp is 65%
The pH of the reacting mixtures of pulp samples are and 74% respectively [14]. In this study, after
decreasing from MBPH-MAPH, MBC-MAC, and Prehydrolysis with base 70.9% yield of pulp was
MAC-MBCPBB and sharply increasing from MAPH- achieved. On the other hand, 29.1% of cellulose during
MBC (Figure 1). The results showed that during the pre-base Prehydrolysis stage was obtained. In the
Kraft process as a result of large amount of NaOH used, Prehydrolysis of the eucalyptus chips, alkaline
the pH at the start of the prehydrolyzed and cooking hydroslysis provided a higher yield than acid hydrolysis
processes recorded were high due to the alkaline with higher kappa number (more lignin content pulp)
pulping process. It decreases continuously during the and light brown in color. At prehydrolyzed step only
course of cooking since organic acids were liberated some amount of lignin is removed so that the produced
from lignin and carbohydrates (hemicelluloses) during pulp has high kappa number which is 20.8. Besides,
the pulping reaction as a result of hydrolysis and medium fine amount of fibers were obtained in this step
dissolution processes. This indicates the alkaline Kraft due to incomplete digestion process.
process hydrolyzes and dissolves the lignin and the The low yield in the acid pulping could be
amorphous hemicelluloses at higher pH, and prevents related to acid hydrolysis of cellulose to sugar
the hydrolysis of cellulose which is favorable in acidic monomer. Acid hydrolysis proceeds in three steps. The
conditions at a lower pH value. At acidic condition reaction starts with a protonation of the glycosidic
cellulose fibers were degraded up on decreasing of its oxygen linking in to two sugar units, forming
pH when lignin is dissolved [12]. protonated cellulose (conjugate acid). Then, water
The sharp decrease from MAC-MBCPBB makes a nucleophilic attack on the protonated cellulose
indicates large amount of lignin dissolution at the time which breakdown to the cyclic carbonium ion [14]. This
of cooking at higher pH and the residual lignin content

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

indicates Kraft alkaline process is suitable for high pulp input which corresponds to 8.9 % loss and 91.1%
yield of pulp synthesis. yield (Table 3).
3.3. Cooking or Digestion of Eucalyptus Wood Table 3 Yield and quality of pulp obtained by single
In this study, after digestion only 46.4 g of bleaching process
pulp was obtained per 100 grams of input
prehydrolyzed chips (Table 2) at cooking conditions of Parameter Quantitative Qualitative
Initial weight 20 gm -
6 bars, 131 oC for 140 minutes, liquor to wood ratio of
Final weight 18.22 gm -
4:1 and effective alkali of 87.8g per liter with a
Color - white
sulphidity of 24.4 %. Kappa number 7.7 -
Table 2. The result obtained after cooking process Fine content Very small -
Parameter Quantitative Qualitative
Initial weight 100 gm - Lignin content Low -
Final weight 46.4 gm - The single bleached eucalyptus pulp has a
Color - Dispersed white kappa number of 7.7 which is less than the kappa
Kappa number 9.834 number 9.834 of cooked pulp (Table 2) signifies the
Fine amount small - residual lignin content almost removed up on bleaching
with hydrogen peroxide. The fine content of the fibers
After cooked with white liquor, a yield of also increased very well due to removal of a residual
46.4 % pulp was achieved which is nearer value of lignin that can compact the fibers by holding together.
yield to the expected one which is 53-56 % [4] for The 91.1 % yield from the single bleached pulp reveals
eucalyptus Kraft pulp. The eucalyptus cooked pulp has that hydrogen peroxide has a high selectivity power to
a kappa number of 9.834 (Table 2) which is less than degrade the residual lignin without interfering to the
from the kappa number of prehydrolyzed pulp which degradation of carbohydrates specially cellulose fiber
has a (kappa number of 20.8) (Table 1). This suggested which is the main constituent of pulp yield and gives
that much of the lignin was dissolved and entered into achievable brightness of the pulp product.
the liquid phase during cooking step. 7-10 % cellulose It was reported that lignin removal rates is as
loss of fiber pulp is less than that of the expected value high as 95 % during bleaching pulp which leads high
due to unfavorable conditions for digestion like the levels of brightness (whiteness) without pulp
non-selectivity of the chemicals (white liquor) used to degradation [15]. In that case, the result obtained in this
degrade lignin, time, temperature and the decrease in experiment has comparable pulp yield of 91.1%. Thus,
pH. In the cooking stage of this process in a pressurized hydrogen peroxide can remove the residual lignin
autoclave with a specific pressure of 6 bar, the cooking attached to the cellulose after cooking and cleavage aryl
chemicals (white liquor) used in pulping process alter ether linkage of the attached cellulose that increases the
the structure of lignin in such a way that soluble dissolution of lignin. But, it only gives temporarily
fragments of polymer was produced by different brightness which is not suitable for manufacturing of
possible mechanisms. many types of paper grades.
3.4. Pulp Bleaching Sequence In the sequentially bleached pulp, after each
Pulping process alone is not enough to produce bleaching stage, the pulps were thoroughly washed with
cellulose of eucalyptus suitable for Pulp synthesis deionized water and analyzed for yield and residual
applications. After pulping, cellulose must be subjected lignin contents (Kappa number).The progress of the
to further purification. The goal of bleaching is to digestion was monitored by measuring the pH. The
reduce the kappa number without drastically decreasing resulted sequentially bleached pulp has 5.9 of kappa
the degree of polymerization of the cellulose. In single number which indicates almost the total removal of
bleaching step, 20 grams of cooked dried pulp was lignin from pulp which gives brightest permanent
bleached with bleaching agent of 0.2 mL of hydrogen whiteness colored pulp. The weight of pulp at the first
per oxide for 60 minute at 80 oC operating temperature. bleaching stage was 20 g at one step whereas the
At the end of operation, the bleached pulp was washed, weight of the bleached pulp after the sequential
dried and weighed. bleaching was 15.4 g. This shows that a weight loss of
After bleached by H2O2 18.22 g of white 6.6 g pulp and a decrease in pulp yield to 77 % which is
bleached pulp was obtained from 20 g of dried cooked less than single bleached pulp yield of 91.1 %. It may
be due to the unselectively degradation of cellulose by

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

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 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-

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

The absorption bands at 1694.8, 1214, 1095, 1046, 963 conjugated C=O and C=C systems such as occur in o-
and 872 cm-1 in this spectra attributed to the functional Quinones and in aromatic aldehyde, acids and ketones.
groups present in the lignin before delignification but The main functional group contributing to the
they are absent in the bleached pulps spectra (Figure 2). oxidation of hard wood Kraft residual lignin is syringyl,
Thus, the spectra show that the recovered lignin is C5 non condensed guaiacyl units and stilbene phenolic
composed of guaiacyl and syringyl structures, which structures. The inability to oxidize the phenyl propane
are typical for lignin of hard wood pulp [19]. side chain of lignin and/or C5 condensed guaiacyl
3.6.3. UV-Visible diffuse absorption spectrum of phenolics detrimentally impacts bleachability [24]. The
bleached pulps for brightness studies UV-vis difference spectrum had no absorption band at
UV-Vis reflectance spectroscopy is an efficient max 370 nm suggesting the absence of phenolic
method for brightness stability studies. The absorbance stilbene-like structures which are the main components
of UV spectra is directly proportional to the purity level of residual lignin.
of lignin. Visible spectral region and reflectance spectra The UV-vis spectrum of the bleached pulps
are sensitive to the changes in colored pulp components shows that both spectrum of pulps are visible
determining pulp brightness. UV-active structures (like transparent which indicates enough brightness of the
HexA, carbonyl groups and some lignin units) are pulps so that the lignin chromospheres were removed
known precursors to the colored structures formed by chemical treatments with bleaching agents.
during yellowing [24]. Single and sequentially bleached 3.6.4. Physical test parameters of pulp after sheet
pulps were recorded by UV-visible diffuse reflectance formation
spectrometer (Figure 4). 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
Figure 4. The UV-visible spectra of single and
beating energy.
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 Test result Standard

Bursting strength (kg/cm2) 1.00 1.2
Porosity (sec/100m) 11.02 10
Tear strength (MN) 63.04 65
Smoothness (mL/sec) 388.42 365-424
Tensile strength (kg) 5.6 6
Thickness (mm) 0.16 0.1
Bulkiness (cm3/gm) 1.78 1.67
The prepared sheet has a value of porosity sheet of eucalyptus pulp is low kappa pulp than the
11.02 sec/100m which is greater than the standard value standard once due to its high porosity.
(10 sec/100m) which indicates the sheet prepared from The tear Strength (MN) measures the ability of the
eucalyptus pulp is highly air permeable and porous due sheet to resist the propagation of a tear and the amount
to increased amount of beating which gives a denser of energy to fracture a sample [24]. The prepared sheet
smooth paper [4, 24]. The air permeability of high kappa had a value of tear strength 63.04 MN which is nearer
pulp is lower than low kappa pulp so that the prepared to the standard ones which has value of 65 MN tear
strength. The resulted eucalyptus Kraft pulp that was rregularities under either usual or unusual conditions.
prepared in this experiment has enough strength. Smoothness is higher for denser, smaller and more
Smoothness (mL/sec) refers to the absence of surface

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

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

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

of 2005 E.C) gathered from Ethiopia Pulp Factory considering the annual pulp demand of existing paper
shows that the raw material (pulp) demand of the factory of the country.
factory is about 10,000 -15,000 tons per year. This The digester which is suitable to the reaction is
limited production of the country is due to lack of raw mixed flow reactor. The production design is to have
material (pulp) in the country national wide. The supply eight batches per day with three hours resident time in
of kraft paper in Ethiopia is through import. The the cooker (reactor). From annual production of 10,000
information obtained from external trade in (2000 E.C) tons of pulp, we can have the amount produced
statistics gives that the present effective demand for 28,571.4 kg/day (3,571.4 kg per batch) of pulp. To
kraft paper is estimated to be 5,504 tones. Design obtain 3,571.4 kg per batch of pulp we have to use
(sizing) of major equipments that are used in eucalyptus 11916.68 kg of eucalyptus wood chip for single bleach
pulp production is performed based on experimental process and 14116.32 kg of eucalyptus wood chip for
result and the equipment capacity should be scaled up sequentially bleach process.

Table 7 Annual materials requirement in tones and cost

Description Quantity Unit price Total cost (birr)
Wood chip 18,750 200 3750
NaOH 2010 4360 8763.6
Na2S 13.7688
H 2O 2 14.2
NaOCl 15
CaO 101.25 1200 121500
Electricity 10,500,000 (KWh) 0.335
Water 750000 (m3) 1.5
Chemicals are also required in the pulp making process. recovered lignin is composed of guaiacyl and syringyl
These include caustic soda, Sodium sulfide, sodium structures, typical for lignin of hard wood pulp. Peak
hypochlorite, starch, hydrogen peroxide and lime. The intensity changes in the spectra of recovered lignin,
process is economically effective. single and sequentially bleached pulps point out
4. Conclusions degradation and condensation processes during
The Kraft pulp is lignin free and can be used in bleaching and lignin extraction. The UV-Visible
making high quality writing and printing papers that are spectrums of single and sequential bleached pulps
both coated and uncoated. The result obtained after indicate the lignin purity of the pulps based on the
bleaching process was close to the expected result value of absorbance. The UV-Visible graph of the
which has less lignin content pulp with a kappa number bleached pulps, transparent at visible region indicates
of 20.8, 9.834, 7.7 and 5.9 for prehydrolyzed, cooked, the brightness of the pulps. The physical test parameters
single bleached and sequentially bleached eucalyptus such as tensile strength, tear strength, porosity, bursting
pulp respectively. The sequential bleaching process strength, bulkiness and thickness obtained from the
produces a brightest pulp which is an efficient method instrumental readings were closer with the standards of
than the single bleaching ones. The FTIR spectrum of the pulp and paper factories. In this study, the Kraft
single and sequentially bleached pulps showed that the process in manufacturing pulp from eucalyptus is
chemical treatments could successfully be used to generally a suitable process with cost effective due to
remove lignin and hemicelluloses. An increase in the the cheapest raw material used and the recovery of the
cellulose content in each chemical treatment observed used chemicals.
at the major peaks in the spectrum indicating cellulose 5. References
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