Industrial Crops and Products 26 (2007) 324331

Atmospheric formic acid pulping and TCF bleaching of dhaincha

(Sesbania aculeata), kash (Saccharum spontaneum)
and banana stem (Musa Cavendish)
M. Sarwar Jahan , D.A. Nasima Chowdhury, M. Khalidul Islam
Pulp and Paper Research Division, BCSIR Laboratories, Dhaka, Dr. Qudrat-E-Khuda Road, Dhaka 1205, Bangladesh
Received 8 March 2006; accepted 26 March 2007

Abstract
Fractionation of dhaincha (Sesbania aculeata), kash (Saccharum spontaneum) and banana stem (Musa Cavendish) was investigated by atmospheric formic acid pulping. Pulping of dhaincha, banana stem and kash was not satisfactorily delignified when the
formic acid concentration was limited to 70%; even longer cooking time (120 min) at this concentration did not produce pulp of
lower lignin content. The marked effect of delignification was observed in case of 90% formic acid concentration. Peroxyformic
acid effectively reduced the residual lignin of the formic acid pulp. In alkaline peroxide bleaching, formic acid pulp was bleached to
7583% brightness depending on the nonwood. The strength properties were almost comparable to conventional pulp. The dhaincha
pulp was stronger than the banana stem and kash pulp. The bleaching improved the strength properties of the pulp. Isolated lignin
from formic acid spent liquor had higher syringyl unit than guaiacyl unit. Its -O-4 bond was cleaved during formic acid pulping,
which increased phenolic hydroxyl group. The lignin was formylated during pulping. The major devolatilization of formic acid
lignin was occurred between 200 and 550 C as shown by TG graph. The xylose was the main sugar in water-soluble fractions of
formic acid spent liquor that represented 5060% of the content in original raw materials.
2007 Elsevier B.V. All rights reserved.
Keywords: Nonwood; Formic acid pulping; Peroxide bleaching; Lignin; Syringyl unit; -O-4 linkage

1. Introduction
The world paper consumption is continuously
increasing. Globally the forest resources are diminishing
while the demand of paper is increasing. Forest deficient
countries like Bangladesh are looking for alternative
fibrous resources especially nonwood. The production
of nonwood pulp mainly takes place in China and India,
where 90% of production occurs. Traditionally nonwood
material is cooked with alkali-based chemicals. In delig-

Corresponding author.
E-mail address: m sarwar@bdonline.com (M.S. Jahan).

0926-6690/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2007.03.012

nification, the relatively high amount of silicon present in

nonwood material is dissolved together with lignin into
cooking liquor, impeding efficient chemical recovery. On
the other hand, collection of nonwood material is very
difficult. Therefore, conventional pulping process is not
suitable for many nonwood raw materials. Thus the difficulties in technology, economy and environment have
adversely affected nonwood in utilizing pulp production.
With increasing importance on minimizing the use
of chlorine and sulfur based chemicals in pulping and
bleaching process attracts alternative pulping process
since last few decades. Acetic acid or formic acid process
is an effective alternative method to delignify lignocellulosic materials to produce pulp for paper (Poppius et

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

al., 1991; Jimenez et al., 1998; Lam et al., 2001; Kham

et al., 2005a,b). The pulping operation can be carried
out at atmospheric pressure. Acid used in pulping can
be easily recovered by distillation and reused in the process (Muurinen, 2000). The three dominant components
in lignocellulosics, cellulose, hemicellulose and lignin
can be effectively separated by degradation in aqueous
acetic acid or formic acid. Organic acid lignin is an optimal feedstock for many value added products due to its
lower molecular weight and higher reactivity (Kubo et
al., 1998; Cetin and Ozmen, 2002). The sugars from
hemicellulose are readily convertible to chemicals and
fuels. Another advantage of organic acid pulping is the
retention of silica on the pulp fiber that facilitates efficient recovery of cooking chemicals (Seisto and Poppius,
1997). Rousu et al. (2002) developed a process, which
was also based on formic acid. In that process delignification was carried out in one stage, at a low liquor-to-fiber
ratio at higher temperature and pressure.
To establish a novel zero-emission process in fully
utilizing kash (Saccharum spontaneum), dhaincha (Sesbania aculeata) and banana stem, an effort was exerted
to fractionate these nonwoods by formic acid at atmospheric pressure into pulp, lignin and hemicellulose
(sugars). The objective of the present paper was also to
investigate the characteristics of the obtained fractions.
The formic acid lignin was characterized by thermal
analysis and 1 H NMR and IR spectroscopy in order to
assess its suitability as value added products.

325

After desired reaction time, pulp was filtered in

a buckner funnel and washed with fresh formic acid
followed by distilled water. Then the pulp yield was
determined gravimetrically. The lignin content in pulp
was determined by Tappi Test Methods (T 222 om98).
2.3. Peroxyformic acid treatment
Formic acid treated pulp was further delignified with
peroxyformic acid (PFA) at 80 C. The reaction was
carried out in a thermostatic water bath. The peroxyformic was prepared by adding 90% formic acid with
varying proportion of H2 O2 (2, 4 and 6% of o.d.
banana stem, dhaincha and kash pulp). The time was
varied from 60 to 180 min in each peroxide concentration. After completion of the pulping, a pulp was
filtered off and washed with 80% fresh formic acid, and
finally with water. Pulp yield was determined gravimetrically on raw material. Klason lignin (T222 om-98)
in pulp was determined according to Tappi standard
methods.
2.4. Bleaching

2. Material and methods

Bleaching experiments of unbleached pulp (50 g)

were carried out at 10% pulp concentration. The pH was
adjusted to 11 by adding NaOH. The hydrogen peroxide
was varied to 1, 2 and 3% on o.d. pulp. The bleaching
temperature was 80 C for 1 h. Similar procedure was
followed in the second stage of peroxide bleaching.

2.1. Materials

2.5. Evaluation of formic acid pulp

Dhaincha, kash and banana stem were collected from

Narsingdi, Dhaka. The lignin, -cellulose and pentosan
in dhaincha were 27.4, 48.7 and 23.1% (Jahan et al.,
2004), respectively. Kash had 16.0% lignin, 75.4% holocellulose and 24% pentosan (Jahan et al., 2002) while
banana stem had 12.7% lignin, 65.2% holocellulose and
41.2% lignin (Cordeiro et al., 2004).

Formic acid pulp was beaten in a PFI mill to SR value

of about 50 and handsheets were prepared for tensile
(T 494 om-96), tear (T 414 om-98) and burst (T 403
om-97) and double fold number. All characteristics were
determined according to Tappi Standard Methods given
in the parenthesis.
2.6. Isolation of lignin and sugar

2.2. Formic acid (FA) treatment

The banana stem, dhaincha and kash were refluxed
with formic acid in a hotplate under the following different conditions:
- Formic acid concentration was 70, 80 and 90% (v/v).
- Reaction time: 60, 120, and 180 min at boiling temperature.
- Liquor ratio 10.

The lignin dissolved during the delignification with

formic acid was precipitated from the concentrated spent
liquor with five volumes of water. The residue was filtered in a buckner funnel, and washed with water and
vacuum dried over P2 O5 . The isolated lignin was purified by dissolving in dioxan (9:1) and precipitate in ether
followed by vacuum drying over P2 O5 . The filtrate and
washing were collected and concentrated using a rotary
evaporator. Three volume of ethanol was added to the

326

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

Table 1
Effect of cooking time and formic acid concentration on the formic acid pulping of nonwood
Time (min)

Formic acid
concentration

Dhaincha

Banana stem

Kash

Pulp yield (%)

Klason lignin

Pulp yield (%)

Klason lignin

Pulp yield (%)

Klason lignin

60

70
80
90

65.1
59.4
54.5

15.3
13.0
11.2

63.1
56.3
49.7

12.7
11.4
10.3

63.5
56.4
49.8

11.8
10.9
9.8

90

70
80
90

64.3
57.8
53.7

14.1
11.9
9.3

62.3
55.1
49.3

11.5
10.1
9.0

62.7
55.3
49.5

10.2
9.3
8.8

120

70
80
90

63.8
56.2
52.9

13.2
11.1
8.5

61.0
54.3
48.3

10.3
9.0
7.4

61.3
54.3
48.2

9.7
8.5
7.1

concentrate, which precipitates the degraded hemicellulosic fragments (sugars). The precipitate was dried by
vacuum drying over P2 O5 . The carbohydrate in the liquor
was analyzed by alditol-acetates method (T 249 cm 00).
2.7. Acetylation of lignin
Formic acid lignin 100 mg was added in 1.5 ml of
dry pyridineacetic anhydride (1:1) for 72 h. The solution was added to a 10-fold volume of ice-cold water
whereupon the acetylated sample was recovered as a
precipitate, which was purified by successive washing
with water and dried under vacuum over P2 O5 .
2.8. Thermal properties
Thermal gravimetrical analysis was performed with
about 5 mg of air-dried lignin using a Perkin-Elmer
TGA7 and a heating rate of 20 C/min under nitrogen
atmosphere.
2.9. Spectroscopy
2.9.1. FTIR
Infra red spectra were recorded by using a Shimadzu FTIR spectrometer model 8201PC. The dried
samples were embedded in KBr pellets in the concentration of about 1 mg/100 mg KBr. The spectra were
recorded in the absorption band mode in the range 4000
400 cm1 .
2.9.2. 1 H NMR
Spectra of lignin solution (100 mg of acetylated lignin
contained in 0.5 ml CDCl3 ) were recorded in a Bruker
400 spectrometer. Solvent was used as internal standard
(7.25 ppm).

3. Results and discussion

3.1. Formic acid treatment
The effects of variables such as cooking time and
formic acid concentration on pulp yield and Klason
lignin content were studied. The results are given in
Table 1 shows that the delignification of dhaincha,
banana stem and kash can be successfully performed
in formic acid. The pulp yield and residual lignin were
decreased, when cooking time and formic acid concentration increased. Pulping of dhaincha, banana stems and
kash was not sufficiently delignified when the formic
acid concentration was limited to 70%; even longer
cooking time (120 min) at this concentration did not
produce pulp of lower lignin content. The pronounced
effect of delignification was observed in case of formic
acid concentration. The residual lignin in dhaincha,
banana stems and kash pulps was decreased from 13.2
to 8.5%, 10.3 to 7.4% and 9.7 to 7.1%, respectively, with
increasing formic acid concentration from 70 to 90% in
120 min of cooking. The best values were obtained at
a 90% formic acid. This result complies with the result
obtained in formic acid pulping of rice straw (Lam et
al., 2001) but differ from result obtained by Deinko
and Kostyukevich (1989) during acetic acid pulping.
Mire et al. (2005) obtained pulp yield above 40% with
kappa number around 30 from banana stem by formic
acid/acetic acid/water system. But in the present investigation, we obtained higher pulp yield from banana stem,
the residual lignin was also higher.
3.2. Peroxyformic acid treatment
Pulp obtained using 80% formic acid in 120 min of
cooking was further treated with peroxyformic acid at

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

327

Table 2
Effect of peroxide charge on the peroxyformic acid treatment of nonwood
H2 O2
concentration

Time
(min)

Temperature
( C)

Dhaincha

Banana stem

Kash

Pulp
yield (%)

Klason
lignin

Pulp
yield (%)

Klason
lignin

Pulp
yield (%)

Klason
lignin

2
4
6

60
60
60

80
80
80

51.2
51.0
50.9

6.0
5.4
5.1

48.2
47.4
46.7

5.1
4.4
3.9

48.5
47.2
46.5

4.3
3.6
3.0

2
4
6

120
120
120

80
80
80

50.8
50.4
49.9

5.4
4.8
3.5

47.5
46.8
46.1

4.3
3.4
2.7

47.1
46.7
46.2

3.7
3.0
2.5

2
4
6

180
180
180

80
80
80

50.1
49.7
49.2

4.0
3.9
3.0

47.0
46.1
45.4

3.5
2.8
2.2

46.6
46.1
45.4

3.1
2.3
2.0

varying concentration and different time at 80 C. The

peroxyformic acid was prepared by adding H2 O2 to 90%
formic acid. Such a mixture of FA, H2 O2 and peroxyacid
proved to be an efficient in delignification of unbleached
pulp through the combined action of the peroxyacids as
oxidizing agent and formic acid as solvent for the lignin
(Kham et al., 2005a,b). The test results of nonwood pulp
obtained in formic acid cooking showed that this oxidizing medium decreased residual lignin significantly. The
pulp yield and residual lignin in pulp were decreased
with increasing H2 O2 concentration and reaction time
(Table 2). The pulp yield and residual lignin of dhaincha, banana stem and kash were 49.9 and 3.5; 46.1 and
2.7; 46.2 and 2.5%, respectively, at 6% H2 O2 in 120 min
of cooking (Table 2). The pulp yields were higher than
the corresponding soda-AQ pulps (Cordeiro et al., 2004;
Jahan et al., 2002). If reaction time was increased to
180 min residual lignin of dhaincha, banana stem and
kash pulp decreased to 4.0, 3.5 and 3.1%, respectively,
at only 2% peroxide. The residual lignin in dhaincha
pulp was higher than banana stem and kash. This is may
be due to higher lignin in dhaincha. The delignification
of PFA can be explained by the action of the hydroxonium ion OH+ formed during peroxyacid stage in acidic
medium:
RCOOOH + H+ RCOOH + OH+
In fact, OH+ ion is a strong electrophilic agent, which
can react with lignin (Gierer, 1982). It is worthwhile to
point out that peroxyacid under acidic condition act as
delignifying and activating agent and not as bleaching
agent. Peroxide is an expensive chemical, which makes
the process nonviable. This high expense can be compensated by recovering value added lignin and sugar
(hemicellulose) from the spent liquor. Also peroxide

charge could be reduced to 2% by increasing peroxyacid treatment time or reducing residual lignin in the first
formic acid stage through proper equipment (agitation).
3.3. Bleaching
The bleaching of peroxyformic acid treated dhaincha,
banana stem and kash pulp was done by an alkaline peroxide treatment. Kash pulp responded well as compared
to banana stem and dhaincha pulp in the same bleaching treatment. It is clearly seen from Fig. 1 that the kash
pulp reached to 83% brightness at 4% peroxide charge,
while banana stem and dhaincha pulps were 79 and 75%,
respectively, at the same peroxide charge. Since increase
of peroxide from 4 to 6% charge decreased viscosity
(Fig. 1), but slightly increased the brightness. These
results show that the bleaching on nonwood formic acid
pulp using TCF sequence is an efficient one.
3.4. Strength properties
Pulp strength properties in the unbleached state and
after bleaching with alkaline peroxide were determined.
The pulps were beaten in a PFI mill for 1000 revolutions.
The results showed that dhaincha pulp was stronger than
banana stem or kash pulp (Table 3). The results given in
Table 3 show that the bleaching improved the strength
properties of the pulp. This can be explained by a better
hydration of pulp on alkaline peroxide bleaching. The
fibrillation can take place more easily during the beating. This result is in good agreement with carboxylic
acid and peroxyacid pulping of wheat straw (Lam et al.,
2001). The breaking length of dhaincha pulp increased
to 6420 m from 5371 m on bleaching, while kash and
banana stem pulp increased to 5712 and 5361 m from

328

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

Fig. 1. Effect of peroxide charge on the brightness and viscosity on different nonwood pulps.
Table 3
Physical properties of unbleached and bleached formic acid pulping from nonwood
Properties

Freeness ( SR)
Breaking length (m)
Burst index (mPa m2 /g)
Tear index (mN m2 /g)

Dhaincha

Banana stem

Kash

UB

UB

UB

44
5371
3.8
7.4

49
6420
4.7
7.7

47
4845
3.7
6.1

53
5361
4.5
6.6

50
4374
3.4
5.7

53
5712
4.3
5.9

4374 and 4845 m, respectively. Formic acid/acetic acid

pulp of banana stem had breaking length of 3889 m in the
unbleached state (Mire et al., 2005). The maximum tear
index (7.7 mN m2 /g) was obtained in case of dhainchableached pulp. All strength properties were inferior to
conventional soda-AQ or kraft pulp (Jahan et al., 2002,
2007). Similar result was found in acetic acid pulping of
wheat straw (Pan and Sano, 2005). Ash rich epidermal
cells remaining in formic acid pulp can be considered as
one reason of lower strength. These nonfiber cells were
short and stiff. They had no contribution to the strength
of the pulp, but obstructing bonding between fibers. The
second reason may be the damage of the fibers caused
by acidic pulping. The hydroxyl group of cellulose was
formylated, which inhibits fiber bonding. During bleaching, formyl group was hydrolysed to hydroxyl group,
thus increased fiber bonding. This may be another reason of better strength after bleaching of organic acid pulp
(Kham et al., 2005b).

stage (Tf ). Both banana stem and dhaincha lignin decomposed in a single thermo gravimetric step with inflexion.
But kash lignin showed a different pattern of thermo
gravimetric curve. The decomposition takes place in a
wide temperature range; the major devolatilization step
occurring between 200 and 550 C. The initial weight
loss was caused by the moisture. Till 200 C no clear
weight loss occurred, indicating that these lignins are
thermally stable till this temperature. The char residues
at 590 C were 42.9% for kash, 39.4% for dhaincha and

3.5. Lignin characterization

3.5.1. Thermo gravimetric analysis
Fig. 2 shows the mass loss (TG) curve of kash, dhaincha and banana stem lignin. For each thermo gravimetric
curve the following thermal characteristics have been
determined: onset temperature (Ti ), temperature corresponding to maximum mass loss (Tm ), and to the end

Fig. 2. Thermogravemetric analysis of formic acid lignin from nonwood.

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

Table 4
Thermo gravimetric results of nonwood formic acid lignin
Sample

Kash
Dhaincha
Banana stem

Temperature ( C)

Char at 590 C (%)

Ti

Tm

Tf

250.2
293.8
271.9

344.2
352.3
354.7

405.2
384.3
376.6

42.9
39.4
45.8

45.8% for banana stem (Table 4). The lignin of low

methoxyl group content produce higher char than lignin
of high methoxyl content (Jakab et al., 1997).
3.5.2. FTIR spectra
Formic acid lignin from kash, banana and dhaincha
display important formate ester absorption at 1716 cm1
(Table 5 and Fig. 3). This band shows the esterification of the phenol and alcohol of the propane chain (C
and C ) occurred during formic acid pulping. This is in
accordance with the studies performed on lignin models by Ede et al. (1988). Similar band was observed
during peroxyformic acid pulping of nonwood (Seisto
and Poppius, 1997). The intensity of dhaincha lignin at

329

band 1716 cm1 was stronger than that of banana and

kash lignin, indicating the easier formylation of dhaincha during formic acid pulping. All spectra are in keeping
with the botanical origin of the corresponding lignin.
The two bands at 1600 and 1500 cm1 are characteristics of aromatic compounds and are due to the vibration
of aromatic skeleton. The bands at 1330 (syringyl) and
1270 cm1 (guaiacyl) in all lignin indicated the presence
of both syringyl and guaiacyl unit. Further evidence of
syringyl unit in these lignins was confirmed by band near
835 cm1 . The band at 1160 cm1 in kash lignin is typical of HGS lignin, indicating the presence of carbonyl
groups in conjugated ester structure.
3.5.3. 1 H NMR
The acetylated formic acid lignin from kash, dhaincha
and banana stem was studied by 1 H NMR spectroscopy.
The spectra are reported in Fig. 4. The presence of
formate ester at 8.2 ppm (weak signal) is seen in all
lignins. Aromatic signal demonstrated that all formic
acid lignin had higher intensity in syringyl (6.6) region
than guaiacyl region (6.9). The intensity ratio of syringyl
to guaiacyl was 1.4 for kash, 1.6 for banana and 2.0

Table 5
Assignment of FTIR spectra of formic acid lignin from nonwood
Peak location range (cm1 )

Assignment

Dhaincha

Kash

Banana stem

34123460
30002842
17381709

OH stretching
CH stretch in methyl and methylene group
C O stretch in unconjugated ketone, carbonyl and ester
groups
C O stretching in comjugated p-subst. Aryl ketones
Aromatic skeleton vibrations plus C O stretching; S > G:
Gcondensed > Getherified
Aromatic skeleton vibrations (G > S)
CH deformations (asym in CH3 and CH2 )
Aromatic skeleton vibrations combined with CH in plane
deformations
Aliphitic CH stretching in CH3 and phen. OH
Condensed S and G ring (G ring bound via position 5)
G ring plus C + O stretching
CC + CO + C O stretching (Gcondensed > Getherified )
Typical for HGS lignins; C O in ester groups (conj.)
Aromatic CH in-plane deformation (typical of G unit;
Gcondensed > Getherified )
Typical of S unit; also secondary alcohol and C O strt.
CO deformation in sec. alcohol and aliphatic ether
Aromatic CH in-plane deformation (G > S) plus CO
deform. in primary alcohols plus CH stretching
(unconjugated)
HC CH out of plane deformation. (trans)
CH out of plane (aromatic ring)
CH out of plane in positions 2, 5 and 6 (G units)
CH out of plane in positions 2 and 6 of S units
CH out of plane in positions 2, 5 and 6 of G units

3417.6
2933.5
1716.5

3421.5
2918.1
1720.4

3415.5
2937.4
1720.4

1608.5

1607.8

1604.7

1506.3
1456.2
1423.4

1508.2
1458.1
1421.5

1508.2
1458.1
1421.5

1328.9

1325.3

1328.1

1224.7

1224.5

1163

1118.6

1031.8

1118.6

1031.8

1118.6

1031.8

16751655
15931605
15051515
14601470
14221430
13651370
13251330
12661270
12211230
1166
1140
11251128
1086
10301035

966990
915925
853858
834835
817832

833.2

330

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

Fig. 4. 1 H NMR spectra of formic acid lignin from nonwood.

7.3 and 7.6 ppm is assigned to aromatic protons of pcoumaric acid and ferulic acid, usually found in nonwood
such as grass lignins.

Fig. 3. FTIR spectra of formic acid lignin from nonwood.

for dhaincha. The contents of alcoholic and phenolic

hydroxyl group were determined as acetoxyl groups.
Generally, the content of alcoholic hydroxyl group is
higher than phenolic hydroxyl group in MWL. The
spectra showed almost similar or higher intensity in phenolic hydroxyl groups (2.2 ppm) than aliphatic hydroxyl
(2.0 ppm), which indicated the cleavage of -O-4 bond
during formic acid pulping. Davis et al. (1987) showed
that acetic acid cleaved the -O-4 ether containing free
phenolic unit. Methoxyl protons (OCH3 ) give a sharp
signal at 3.63.8 ppm. Protons in aliphatic groups exhibit
signals between 1.5 and 0.8 ppm. A clear signal between

3.5.4. Analysis of sugars

The analytical results of the water solubles in the
formic acid spent liquor are shown in Table 6. The glucose was present only 46% of original raw materials
in the water-soluble fractions of spent liquor, which
indicates the preservation of cellulose during formic
acid pulping. But xylose was the main sugar in watersoluble fractions that represented 5060% of the content
in original raw materials, which indicated a preferenTable 6
Sugar composition of formic acid lignin from nonwood

Glucose
Xylose
Mannose
Galactose
Arabinose

Dhaincha

Banana stem

Kash

1.9
12.3
0.3
0.3
0.2

2.1
11.9
0.2
0.6
0.3

2.2
12.6
0.5
0.5
0.3

M.S. Jahan et al. / Industrial Crops and Products 26 (2007) 324331

tial dissolution of xylan during formic acid pulping. The

similar result was observed during acetic acid pulping of
rice straw (Pan and Sano, 2005).
4. Conclusions
The following conclusions may be drawn from the
present investigation:
- The formic acid concentration had a remarkable effect
on the delignification of kash, dhaincha and banana
stem. The residual lignin of formic acid treated pulp
was higher even at longer cooking time (120 min) and
higher formic acid concentration (90%).
- Peroxyformic acid treatment reduced the residual
lignin remarkably. Pulp yield after peroxyformic acid
treatment was better than the conventional pulp.
- Alkaline peroxide bleaching of peroxyformic acid
treated pulp responded very well. The kash pulp
showed maximum brightness of 83%.
- Acceptable physical properties were obtained in
formic acid pulp. Dhaincha pulp had better physical
properties as compared to kash and banana stem pulp.
The physical properties were improved on bleaching.
- Formic acid lignin was thermally stable till 200 C.
The char of formic acid lignin at 590 C was 3946%
depending on raw materials as observed by TG analysis. The maximum char was obtained for banana stem
lignin.
- 1 H NMR study showed that the formic acid lignin contain more phenolic hydroxyl group. The -O-4 bond
was broken during formic acid pulping. Formic acid
lignin was formylated during pulping as evidenced by
FT-IR and 1 H NMR.
References
Cetin, N.S., Ozmen, N., 2002. Use of organosolv lignin in phenolformaldehyde resins for particleboard production I. Organosolv
lignin modified resins. Int. J. Adhes. Adhes. 22, 477480.
Cordeiro, N., Belgacem, M.N., Tores, I.C., Moura, J.C.V.P., 2004.
Chemical composition and pulping of banana pseudo-stems. Ind.
Crops Prod. 19 (2), 147154.

331

Davis, J.L., Nakatsubu, F., Murakami, K., Umezawa, T., 1987. Organic
acid pulpig of wood IV. Reaction of arylglycerol-beta-guaiacyl
ethers. Mokuzai Gakkaishi 33 (6), 478486.
Deinko, I.P., Kostyukevich, N.G., 1989. Khim. Driv. 5, 115 (in Russian).
Ede, R., Brunow, G., Poppius, K., Sundquist, J., Hortling, B., 1988.
Formic acid/peroxyformic acid pulping. I. Reactions of -aryl ether
model compounds with formic acid. Nordic Pulp Pap. Res. J. 3,
119123.
Gierer, J., 1982. The Chemistry of delignificationa general concept
Part II. Holzforschung 36 (1), 55.
Jakab, E., Faix, O., Till, F., 1997. Thermal decomposition of milled
wood lignins studied by thermogravimetry/mass spectrometry. J.
Anal. Appl. Pyrol. 4041, 171186.
Jahan, M.S., Moynul Hasan, A.J.M., Islam, M.K., Nasima Chowdhury, D.A., 2002. Investigation on Soda and soda-AQ pulping of
Saccharum spontaneum. TAPPSA J. (May), 2125.
Jahan, M.S., Mun, S.P., Rashid, M., 2004. Fiber dimensions and chemical properties of various nonwood materials and their suitability
for paper production. Ktappi J. 36 (5), 2935.
Jahan, M.S., Nasima Chowdhury, D.A., Islam, M.K., 2007. Pulping of
dhaincha. Cellulose Chem. Technol., in press.
Jimenez, L., Torre, M., Maestre, J., Ferrer, Perez, F., 1998. Delignification of wheat straw by use of low molecular weight organic acid.
Holzforschung 52 (2), 191196.
Kham, L., Bigot, Y.E., Delmas, M., Avignon, G., 2005a. Delignification of wheat straw using a mixture of carboxylic acids and
peroxoacids. Ind. Crops Prod. 21, 915.
Kham, L., Bigot, Y.L., Mlayah, B.B., Delmas, M., 2005b. Bleaching
of solvent delignified wheat straw pulp. Appita J. 58 (2), 135137.
Kubo, S., Uraki, Y., Sano, Y., 1998. Preparation of carbon fibers from
softwood lignin by atmosperic acetic acid pulping. Carbon 36
(78), 11191124.
Lam, H.Q., Bigot, Y.L., Delmas, M., Avignon, G., 2001. Formic acid
pulping of rice straw. Ind. Crops Prod. 14, 6571.
Mire, M., Mlayah, B.B., Delmas, M., Bravo, R., 2005. Formic
acid/acetic acid pulping of banana stem (Musa Cavendish). Appita
J. 58 (5), 393396.
Muurinen, E., ORGANOSOLV PULPING, 2000. A review and distillation study related to peroxyacid pulping. Ph.D. Thesis. Faculty
of Technology, University of Oulu, Finland.
Pan, X., Sano, Y., 2005. Fractionation of wheat straw by atmospheric
acetic acid process. Bioresour. Technol. 96, 12561263.
Poppius, K., Mustonen, R., Huovila, T., Sundquist, J., 1991. Milox
pulping with acetic acid/peroxy acid. Paperi ja Puu 73 (2), 154158.
Rousu, P., Rousu, P., Anttila, J., 2002. Sustainable pulp production
from agricultural waste. Resour. Conserv. Recycl. 35, 85103.
Seisto, A., Poppius, L., 1997. Peroxyformic acid pulping of nonwood
plants by MILOX methodsPart-1 Pulping and Bleaching. Tappi
J. 80 (9), 215221.