Technical Note

Received: 1 August 2011 Revised: 1 November 2011 Accepted: 1 November 2011 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.3695

Alkali pretreatment of softwood spruce and

hardwood birch by NaOH/thiourea, NaOH/urea,
NaOH/urea/thiourea, and NaOH/PEG to
improve ethanol and biogas production
Abas Mohsenzadeh,a Azam Jeihanipour,a,b∗ Keikhosro Karimia,c
and Mohammad J. Taherzadeha

Abstract
Alkali-dissolution pretreatment of softwood spruce and hardwood birch to improve ethanol and biogas production was
investigated. The pretreatments were carried out at different temperatures between 15 and 80 ◦C with NaOH/thiourea
−
(7/5.5 wt%), NaOH/urea (7/12 wt%), NaOH/urea/thiourea (7/8/6.5 wt%), and NaOH/PEG (7/1 wt%) aqueous solutions.
The pretreated materials were then subjected to enzymatic hydrolysis for 72 h. The pretreatments by NaOH/thiourea at 15
◦
C improved the hydrolysis yields of spruce from 11.7% to 57% of theoretical yield, and for birch from 23.1% to 83% − of
theoretical
yield. The enzymatic hydrolysis and fermentation of these pretreated materials by NaOH/thiourea with baker’s yeast
resulted in 54.0% of theoretical yield compared with 10.9% for untreated spruce and 80.9% of theoretical yield compared
with 12.9% for untreated birch. Furthermore, anaerobic digestion of pretreated materials resulted in 0.36 L g−1 VS methane
compared with
0.23 L g−1 VS for untreated birch, and 0.21 L g−1 VS compared with 0.03 L g−1 VS for untreated spruce.
Ⓧc 2012 Society of Chemical Industry

Keywords: alkaline pretreatment; spruce; birch; enzymatic hydrolysis; bioethanol; biogas

INTRODUCTION re-association of cellulose hydroxyl groups. Thus, it can positively

Production of biofuels such as ethanol and biogas from ligno-
celluloses demands a pretreatment to make the recalcitrant and
crystalline structure of lignocelluloses available to enzymatic or
bacterial attack.1 In addition, this structure is covered by lignin,
which contributes to reducing the access of enzymes. Differ- ent
physical, chemical and biological methods are used as the pretreatment
step such as milling, steam explosion, ammonia fiber explosion,
alkaline, dilute- and concentrated-acid processes. 2 Among these methods,
chemical methods are more efficient and economically feasible.
One of the most effective chemical pretreatment methods is
dissolution of lignocellulosic materials. Dissolution can efficiently
disintegrate the structure of lignocellulose and thus improve the
biological conversion of lignocelluloses. Sodium hydroxide is a simple
chemical that can swell or even dissolve cellulose at high
concentrations. The dissolution mechanism is that soda hydrates can
penetrate the amorphous area of cellulose, and destroy the
neighboring crystalline regions.1 Furthermore, addition of
chemicals such as thiourea, 3 urea,4 or a combination of urea and
thiourea5 have been shown to improve the dissolution behavior of
lignocelluloses in the NaOH solution. The proposed mechanism is
that these components trap the free water and prevent the
interaction between cellulose chains via hydrogen bonds.6
Polyethylene glycol (PEG)/NaOH 7 aqueous solution has recently been
used as a potential ‘green’ solvent for cellulose. 8 PEG molecules act as
hydrogen-bonding acceptors and prevent the
affect the dissolving process.7,9 Based on the cellulose dissolution
capability, these chemicals can be used for pretreatment of
lignocelluloses.10 Alkaline pretreatment by NaOH was previously used
successfully to improve ethanol and biogas production from wood
under mild operating conditions. 11 No investigation of hardwood
and softwood pretreatment prior to enzymatic or bacterial
hydrolysis for ethanol or biogas production by these solvents was
found in the literature.
The overall goal of this work was to investigate the effects of
different alkali dissolution systems including NaOH/thiourea,
NaOH/thiourea/urea, NaOH/urea, and NaOH/PEG aqueous solu- tions at
different temperatures on hard- and softwoods, to develop an efficient
pretreatment method for bioconversion of lignocel- luloses. Two
common wood species including a softwood spruce and a hardwood
birch were pretreated and then subjected to
∗
Correspondence to: Azam Jeihanipour, School of Engineering, University of
Borås, Borås, Sweden. E-mail: Azam.Jeihanipour@hb.se
a School of Engineering, University of Borås, Borås, Sweden
b Faculty of Advanced Sciences and Technologies, University of Isfahan, Isfahan,
81746-73441, Iran
c Department of Chemical Engineering, Isfahan University of Technology,
Isfahan, 84156-83111, Iran

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 www.soci.org
enzymatic hydrolysis for 72 h, and the best results were applied for
ethanol and biogas production.
MATERIALS AND METHODS
Raw materials and their analyses Spruce
(Picea abies) and birch (Betula pendula) wood species were collected
from the forests around the city of Borås in Sweden. They
were debarked and milled to particle size between 75 and 500 m, and
their dry weights were determined by drying at 105 ◦C for 24 h.
The carbohydrate and lignin fractions were analyzed according to
NREL procedure.12 In this method, acid hydrolysis of cellulose and
hemicelluloses is carried out to depolymerize them to sugars, and the
lignin is measured as acid-insoluble and acid-soluble lignins. The acid-
soluble lignin was measured by UV– vis spectroscopy at 205 nm with
absorptivity of 30 (L g−1 cm−1).
Pretreatments
Aqueous alkali solutions were prepared by mixing 7 wt% NaOH with
12 wt% urea, 5.5 wt% thiourea, 1 wt% PEG, or 8 wt% urea/6.5 wt%
thiourea in deionized water. For the pretreatments, 7 g of wood species
was added to 93 g alkaline solution and stirred for 30 min at room
temperature. The mixtures were stored at 15, 0, 22, and 80 ◦C for 16
−h
then, 100 mL of deionized water was added to each solution and stirred
for 1 h at ambient temperature. The pretreated wood samples were
then filtered and washed with deionized water to remove the
chemicals, and neutralize to pH 7. These pretreated materials were
then freeze-dried to maintain the water swelling state and to prevent
structural collapse before further use.13
Enzymatic hydrolysis
The pretreated and untreated lignocelluloses were enzymatically
hydrolyzed using 5% w/v dry matter in 50 mmol L−1 sodium citrate
buffer at pH 4.8. The suspensions were autoclaved, and then supplemented
with 20 FPU cellulase (celluclast 1.5L, Novozyme, Denmark) and 50 IU
β-glucosidase (Novozyme 188, Novozyme, Denmark) per gram of dry
wood. The enzymatic hydrolyses were carried out at 45 ◦C in 100 mL
flasks in a water bath shaker (OLS 200, Grant Instruments, UK) at 120
rpm for 72 h. The activities of the cellulase and β-glucosidase were 80
FPU mL−1 and 240 IU mL−1 measured according to Adney and Baker14 and
Ximenes et al.,15 respectively.
Fermentation
Fermentations were performed in 118 mL anaerobic bottles. The
fermenting microorganism was a flocculation strain of Saccha-
romyces cerevisiae (CCUG 53 310, Culture Collection, University of
Gothenburg, Sweden). The strain was preserved on agar plates
containing (g L−1): yeast extract, 10; soy peptone, 10; glucose, 20; agar,
20. It was grown at 30 ◦C and maintained at 4 ◦C. A volume of 20 mL of
each hydrolyzate was supplemented with 5 mL of all other nutrients16
and were inoculated with 1.0 0.1g L−1 yeast and were
± incubated at 30
◦
C in a shaking bath for 30 h anaero- bically. Samples were analyzed for
ethanol and sugar by HPLC. All experiments were performed in
duplicate and average values were reported. The inocula were prepared
by aerobic cultivation of the yeast in 1 L cotton-plugged Erlenmeyer
flasks in a water-bath shaker at 120 rpm and 30 ◦C for 24 h. A 500 mL
growth medium was prepared as previously reported.17 The yeast was
separated after 5 min settlement followed by 5000 rpm
centrifugation for 10 min under aseptic conditions.
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A Mohsenzadeh et al.
Digestion
Using thermophilic bacteria at 55 ◦C, anaerobic digestion was performed
in serum glass bottles which were closed with butyl rubber seals
and aluminum caps.18 The working volume of the bottles was 118
mL. The inoculum was delivered from a 3000 m 3 municipal solid waste
digester operating at thermophilic (55 ◦C) conditions (Borås Energi
och Miljo¨ AB, Borås, Sweden). Pretreated or untreated wood (0.25 g),
20 mL inoculum, and 5 mL deionized water were added to each flask.
In order to estimate the amount of biogas produced by just the
inoculum, deionized water and inoculum were used as blank.
Furthermore, each flask was flushed with a mixture of 80% nitrogen and
20% carbon dioxide to achieve anaerobic conditions. In order to
calculate the amount of methane produced during digestion, samples of
gas were taken from the headspace of flasks on a regular basis and
analyzed by a gas chromatograph (GC).
Analytical methods
The methane and carbon dioxide in biogas were analyzed using a
GC (Auto System Perkin Elmer, Waltham, MA) supplied with a
packed column (Perkin Elmer, 6 r 1.8rr OD, 80/100, Mesh) and a
×
thermal conductivity detector (Perkin Elmer) with inject
◦
temperature of 150 C. The carrier gas used was nitrogen with a flow
rate of 23 mL min−1 at 60 ◦C. Sugars and fermentation products were
analyzed by HPLC (Waters, Milford, MA) supplied with RI detector
(Waters 2414) and an ion-exchange column (Aminex HPX-87H, Bio-Rad,
Hercules, CA) at 60 ◦C using 5 mmol L−1 H2SO4 as eluent at flow rate
0.6 mL min−1.
The crystallinity of pretreated lignocelluloses was measured by a
Fourier transform infrared (FTIR) spectrometer (Impact 410, Nicolet
Instrument Corp., Madison, WI). The spectra were acquired with an
average of 64 scans and a resolution of 4 cm −1, in the range from 600
to 4000 cm−119 monitored by ‘Nicolet OMNIC 4.1’ software.
All experiments and analyses were performed in duplicate,
except the digestions, which were performed in triplicate, and
results are presented as mean values. The average standard deviation
was 4.3%.
RESULTS
Spruce and birch wood species were pretreated by four different
alkaline solutions including [7 wt% NaOH, 5.5 wt% thiourea], [7
wt% NaOH, 8 wt% urea, 6.5 wt% thiourea], [7 wt% NaOH, 12 wt% urea],
or [7 wt% NaOH, 1 wt% PEG] at 15, 0, −22 and 80 ◦C for 16 h. The
effects of all pretreatments on the composition and enzymatic
hydrolysis of the wood species were investigated. Then, the best
pretreatment conditions were applied to further study of the
crystallinity changes of the lignocelluloses, and yields of ethanol and
biogas in fermentation and anaerobic digestion, respectively.
Effects of the pretreatments on the composition of birch
and spruce
The effects of pretreatments of birch and spruce on their cellulose and
lignin compositions are summarized in Table 1. Acid-insoluble lignin
(AIL) was dominant in these wood species. The AIL content of birch
was 21.9%, which was increased to 23.1 – 27.3% after various
pretreatments, while the AIL in spruce which was 28.3% was not
significantly changed (Table 1). On the other hand, the effect of
alkaline pretreatment on the acid-soluble lignin (ASL) content was
more significant. By decreasing the temperature of
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Table 1. Cellulose and lignin content of treated and untreated birch and spruce

Acid insoluble lignin (AIL) Birch (wt%) Acid insoluble lignin (AIL) Spruce (wt%)
◦
Reagent Temp.( C) −15 0 22 80 −15 0 22 80

NaOH/Thiourea 27.3 25.1 24.6 23.1 28.4 27.9 28.1 27.4

NaOH/Thiourea/Urea 26.8 25.3 24.6 22.1 28.5 28.4 28.2 27.3
NaOH/Urea 26.1 24.7 24.6 25.3 28.2 27.9 28.1 29.4
NaOH/PEG 26.1 24.3 24.3 25.5 28.0 27.4 28.1 30.3
Untreated 21.9 21.9 21.9 21.9 28.3 28.3 28.3 28.3

Acid soluble lignin (ASL) Birch (wt%) Acid soluble lignin (ASL) Spruce (wt%)

NaOH/Thiourea 5.8 3.8 4.9 4.4 0.63 0.63 0.68 0.68

NaOH/Thiourea/Urea 5.6 5.6 4.6 4.4 0.60 0.60 0.69 0.69
NaOH/Urea 5.7 3.8 4.6 4.6 0.61 0.60 0.60 0.53
NaOH/PEG 5.8 5.8 4.6 4.4 0.48 0.48 0.57 0.49
Untreated 2.7 2.7 2.7 2.7 0.50 0.50 0.50 0.50

Cellulose Birch (wt%) Cellulose Spruce (wt%)

NaOH/Thiourea 37.5 53.4 56.1 58.4 32.3 45.8 45.7 48.5

NaOH/Thiourea/Urea 38.8 55.8 57.3 58.1 33.5 46.8 46.3 48.7
NaOH/Urea 38.8 55.7 56.8 57.8 32.8 45.7 45.3 48.6
NaOH/PEG 37.6 53.6 55.7 58.4 32.2 44.6 45.9 48.3
Untreated 40.0 40.0 40.0 40.0 43.0 43.0 43.0 43.0

the pretreatment, the ASL content of birch increased between 41 and
115% compared with an untreated sample. However, it did not change
more than 38% for spruce (Table 1).
Although it seems that the pretreatment has increased the lignin
content, the calculated lignin removal of pretreatments showed
dissimilar results (Table 2). A considerable part of lignin, i.e. 11.1 –
38.9%, was removed by the pretreatments. The lignin removal by
NaOH/thiourea and NaOH/thiourea/urea was more successful at
higher temperatures, for both hard-
and softwoods – whereas at 80 ◦C, the NaOH/thiourea solution
removed 34.2 and 18.7%, and NaOH/thiourea/urea removed 38.9 and
19.4% of the lignin of birch and spruce, respectively. However, the best
temperatures for lignin removal by NaOH/urea and NaOH/PEG from
both hard- and softwoods were 0 and 22 ◦C, respectively (Table 2).
The cellulose contents of the pretreated and untreated
lignocellulosesarepresentedin Table 1. Forallreagents, increasing the
temperature of pretreatment generally resulted in higher cellulose
content of the pretreated materials (Table 1). The effect of the
pretreatments on the cellulose is clearer when calculating the cellulose
recovery (Table 2). The recoveries of cellulose were defined as the ratio
of the difference between the amount of cellulose before and after
the pretreatments to the amount of cellulose in untreated
lignocellulose. Cellulose recovery for spruce was more than that for
the birch species, and in both cases it increased with the
temperature due to better solubility of cellulose at the lower
temperature (Table 2). It is apparent from the data in Table 2 that the
cellulose recovery is more dependent on the temperature than on the
type of mixed reagent with NaOH. However, for all the temperatures,
the recovery of cellulose

Table 2. Lignin removal and cellulose recovery after alkali pretreatment of birch and spruce species under different conditions

Birch Spruce

Reagent Temp.( ◦C) −15 0 22 80 −15 0 22 80

Lignin removal (wt%)

NaOH/Thiourea 17.4 30.8 29.9 34.2 15.1 17.4 17.6 18.7

NaOH/Thiourea/Urea 19.8 28.8 33.2 38.9 14.8 16.4 18.1 19.4
NaOH/Urea 22.2 32.8 28.8 29.5 16.6 17.9 16.9 13.8
NaOH/PEG 13.6 28.1 28.5 28.1 16.8 19.4 23.4 11.1

Cellulose recovery (wt%)

NaOH/Thiourea 63.8 80.7 83.9 88.3 63.3 89.0 87.7 94.1

NaOH/Thiourea/Urea 62.2 81.1 82.8 85.6 65.8 90.3 88.0 94.2
NaOH/Urea 61.6 82.8 87.3 86.1 63.6 88.3 88.0 94.2
NaOH/PEG 64.2 81.3 84.0 83.4 62.9 86.3 82.3 93.6

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 www.soci.org A Mohsenzadeh et al.

when treating spruce with NaOH/thiourea/urea was a little higher

Table 3. Yield of ethanol production of untreated spruce and birch
compared with the treatment with other solutions (Table 2). and samples pretreated by NaOH/thiourea aqueous solution at −15 ◦C
Spruce (% Birch (%
Sample theoretical yield∗) theoretical yield∗)
Enzymatic hydrolysis
Pretreated and untreated lignocelluloses were subjected to Untreated 10.9 12.9
enzymatic hydrolysis in order to investigate the effect of the Pretreated with 54.9 80.9
pretreatment. The results are presented in Figs 1 and 2. The enzymatic NaOH/thiourea
hydrolysis of untreated birch and spruce for 72 h resulted in 23.1% ∗
Percentage of theoretical ethanol yield = [ethanol produced (g
and 11.7% hydrolysis compared with the theoretical yield. A large L−1)]/[0.51×1.111×initial weight of biomass (g L−1) × F]×100, where F is
improvement was observed after pretreatment of hardwood birch, cellulose fraction in biomass.
and the hydrolysis yields were improved to 48 – 83% of the theoretical
yield (Fig. 1). The effect of temperature on the improvement of the
saccharification of birch is more significant for NaOH/thiourea The materials pretreated by NaOH/thiourea at 15 ◦C were−selected for
than for the other reagents (Fig. 1). In other words, the final cellulose more investigation of fermentation, crystallinity and biogas
conversion of birch, at 72 h, pretreated with NaOH/urea/thiourea, production.
NaOH/urea, or NaOH/PEG was not significantly changed by
changing the temperature (Fig. 1(B), 1(C), 1(D)). The best
Fermentation
saccharification yield of birch, i.e. 83% of theoretical yield, was
The fermentation experiments with S. cerevisiae for 30 h were carried
obtained using NaOH/thiourea at 15 ◦C.
out for untreated birch and spruce species and samples pretreated with
The pretreatment of− spruce improved its hydrolysis yields from 11% NaOH/thiourea at 15 ◦C, which had − the best yield of enzymatic
to 27 – 57% of the theoretical yield (Fig. 2). The effect of temperature
on the yield of enzymatic hydrolysis of pretreated spruce with hydrolysis after 72 h for both lignocelluloses. A significant
NaOH/urea was not significantly affected by the pretreatment improvement in ethanol yield was obtained, from 10.9% of theoretical
yield for untreated spruce to 54.9% for the pretreated one, and also
temperature (Fig. 2(C)). However, temperatures of 15 and 0 ◦C were the
from 12.9% of theoretical yield for untreated birch to 80.9% for the
most effective ones in pretreating spruce with NaOH/thioureaand
− NaOH/PEG(Fig. 2(A) and 2(D)). Incontrast, the efficiency of pretreated one (Table 3). Hence, NaOH/thiourea pretreatment at 15 ◦C of
hardwood birch for ethanol production was more efficient than that of
pretreatment of spruce with NaOH/urea/thiourea at 80 ◦C on the yield −
the softwood spruce.
of enzymatic hydrolysis was as effective as pretreatment at 15 ◦C
(Fig. 2(B)). The highest saccharification
− Biogas production
yield of spruce after 72 h, which was 57% of the theoretical yield,
was obtained by pretreatment with NaOH/thiourea at Selected pretreated and untreated birch and spruce species were also
−15 ◦C. subjected to anaerobic digestion for 30 days under thermophilic
conditions (55 ◦C). The pretreatment greatly affected

60 60
(A) NaOH/thiourea (B) NaOH/thiourea/urea
50 50
(% of theoretical

(% of theoretical

40 40
Glucose yield

Glucose yield

30 30

20 20

10 10

0 0
0 24 48 72 0 24 48 72

60 60
(C) NaOH/urea (D) NaOH/PEG
50 50
(% of theoretical

(% of theoretical

40 40
Glucose yield

Glucose yield

30 30

20 20

10 10

0 0
0 24 48 72 0 24 48 72
Time (h) Time (h)

Figure 1. Enzymatic hydrolysis of untreated and pretreated birch by aqueous solutions of NaOH/thiourea, NaOH/thiourea/urea, NaOH/urea, and NaOH/PEG at different
temperatures: ( ) untreated wood, and pretreatment at (◆) −15 ◦C, (□)0 ◦C, (▲) 22 ◦C, and (×) 80 ◦C. The glucose yield is calculated as the percentage of theoretical
yield [glucose produced (g L−1) (1.111× biomass (g L−1) ×F), where F is the cellulose fraction in biomass].
•

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100 100
90 (A) NaOH/thiourea (B) NaOH/thiourea/urea
90
80 80

(% of theoretical
70

(% of theoretical
70

Glucose yield

Glucose yield
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 24 48 72 0 24 48 72
100 100
90 (C) NaOH/urea (D) NaOH/PEG
90
80 80
(% of theoretical

70

(% of theoretical
70
Glucose yield

Glucose yield
60 60
50 50
40 40
30 30
20 20
10 10
0 0
0 24 48 72 0 24 48 72
Time (hr) Time (hr)

Figure 2. Enzymatic hydrolysis of untreated and pretreated spruce by aqueous solutions of NaOH/thiourea, NaOH/thiourea/urea, NaOH/urea, and NaOH/PEG at different
temperatures: ( ) untreated wood, and pretreatment at (◆) −15 ◦C, (□)0 ◦C, (▲) 22 ◦C, and (×) 80 ◦C. The glucose yield is calculated as the percentage of theoretical
−1 • −1
yield [glucose produced (g L ) (1.111× biomass (g L ) ×F), where F is the cellulose fraction in biomass].

0.4 0.8
Untreated Treated

0.3
Methane yield (l/g

0.2
0.7
Crystallinity

0.1

0
0 5 10 15 20 25 30 35 0.6
Time (days)

Figure 3. Effect of pretreatment of spruce and birch by NaOH/thiourea

aqueous solution at 15 ◦C on the yield of methane in biogas production:
−
(Q) untreated birch, (□) treated birch, (o) untreated spruce, and (▲) treated
spruce. 0.5
Birch Spruce

the methane production for both birch and spruce species (Fig. 3). The
biogas yields of untreated birch and spruce were 0.23 and
0.03 L g−1 VS, respectively, which were improved by 56% and
600% after pretreatment.
Change in structure of the wood by pretreatment
Using FTIR spectroscopy, changes in the crystallinity of the treated
and untreated birch and spruce were studied. The 1427 and 898
cm−1 absorption bands assigned to the crystalline cellulose I and
cellulose II, respectively, were used to investigate the crystallinity
changes. The crystallinity index, which is the absorbance ratio
A1427/A898 is presented in Fig. 4. The spruce was more crystalline than the
birch species. However, the pretreatment reduced the crystallinity of
both materials. The crystallinity index was decreased by pretreatment
from 0.56 for untreated birch to
0.54 for pretreated birch, and from 0.71 for untreated spruce to
0.68 for pretreated spruce.
Figure 4. Total crystallinity index of untreated spruce and birch and pretreated
by NaOH/thiourea aqueous solution at −15 ◦C.
DISCUSSION
The hydrolyses of both hard- and softwood species was signifi- cantly
improved by the selected pretreatments under all condi- tions tested.
Dissolving in NaOH/thiourea, NaOH/thiourea/urea, NaOH/urea, and
NaOH/PEG aqueous solutions significantly mod- ified the structure of
wood and increased the yield of its biodegradation products.
The hydrolysis of softwoods is usu- ally more difficult than that of
hardwoods,20,21 and the presence of lignin is an important factor for
the hydrolysis.22 This claim is in line with our results in which the
lignin content of hardwood birch was less than that of softwood
spruce, and consequently, the pretreatment process was more efficient
for birch. However, lignin removal is not at the highest level for
pretreatment by NaOH/thiourea at −15 ◦C, which gave the best yield
of enzymatic

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 www.soci.org
hydrolysis. Therefore, the parity of lignin removal with improving
enzymatic hydrolysis might not be the only important factor, at
least for some lignocelluloses. The crystallinity of pretreated and
untreated materials was also investigated. FTIR analyses showed that the
alkali pretreatment was able to reduce the crystallinity of both birch
and spruce species. Decreasing the crystallinity index can also result in
improving the hydrolysis yield, but more investi- gation is necessary to
find the most important reason. Using these dissolution systems is
more efficient than NaOH pretreatment alone, particularly on the
softwood spruce. In another study using the same wood species,
enzymes and method, Mirahmadi et al.11 showed that NaOH
pretreatment could improve the yield of enzy- matic hydrolysis of
spruce from 14.1% to 35.7%, while dissolution with NaOH/thiourea at
15 ◦C in the current work improved
− the hydrolysis yield from 11.7% to
57%.
The ethanol yield in this work was increased from 12.9% of
theoretical yield for untreated birch to 80.9% for pretreated birch, and
also from 10.9% of theoretical yield for untreated spruce to 54.9% for
pretreated spruce. The pretreatment with dissolution systems
significantly enhanced the yield of ethanol production, particularly for
the hardwood birch. In addition, the pretreatment greatly affected the
methane production for both wood species. The biogas yields of
untreated birch and spruce were improved by 56% and 600% after
pretreatment. However, the pretreatment was more efficient for the
hardwood than for the softwood used.
The analyses of lignin removal and cellulose recovery before and
after pretreatments showed that a higher temperature is more
effective for lignin removal. A lower temperature resulted in lower
recovery of cellulose for all combinations of tested reagents, implying
that the dissolution of cellulose in NaOH is increased by decreasing
the temperature.9 It has previously been reported that the addition of
urea and thiourea increases cellulose dissolution.5,9 However, these
components do not interact with cellulose directly; they trap the free
water and prevent interaction between cellulose chains via hydrogen
bonds.6 PEG molecules also act as hydrogen- bonding acceptors and
prevent the reassociation of cellulose hydroxyl groups.7 Therefore,
these compounds can affect the dissolution process positively, while
increasing the temperature decreases the quality of the solvent. 9
According to the results obtained in this study, the temperature is
an important factor in this process, which affects the composition of
wood.
CONCLUSION
Among the different alkali dissolution systems, pretreatment by
NaOH/thiourea aqueous solution at 15 ◦C −and atmospheric pres- sure is an
effective alternative for pretreating hard- and softwoods to enhance
biogas and bioethanol production. However, the pro- cess is more
effective for hardwood birch than for softwood spruce.
ACKNOWLEDGEMENT
This work was supported financially by Sparbanken Sjuha¨ rad (Sweden).
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