Bioresource Technology 159 (2014) 373–379

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

A combined adsorption and flocculation process for producing

lignocellulosic complexes from spent liquors of neutral sulfite
semichemical pulping process
Mehdi Dashtban a,b, Allan Gilbert b, Pedram Fatehi b,⇑
a
Biology Department, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1, Canada
b
Chemical Engineering Department, Lakehead University, 955 Oliver Road, Thunder Bay, Ontario P7E 5E1, Canada

h i g h l i g h t s

 Lignocelluloses of NSSC pulping process was removed by adsorption and flocculation.

 Maximum turbidity and COD reductions of SL were 39% and 79%.
 Lignin and hemicellulose adsorptions reached 2.5 and 0.5 g/g for PDADMAC/SL/AC.
 MW of PDADMAC affected the properties of complexes and SL significantly.

a r t i c l e i n f o a b s t r a c t

Article history: The spent liquor (SL) of a neutral sulfite semichemical pulping process contains lignocelluloses that are
Received 8 January 2014 currently treated in a waste water system. In this work, an adsorption process using activated carbon (AC)
Received in revised form 27 February 2014 was considered for isolating the lignin and hemicelluloses from SL. The maximum adsorptions of 0.9 g/g
Accepted 1 March 2014
lignin and 0.43 g/g of hemicelluloses on AC were achieved under the conditions of 30 °C, pH 7 and 3 h
Available online 12 March 2014
with SL/AC weight ratio of 90. The addition of polydiallyldimethylammonium chloride (PDADMAC) to
the SL/AC system significantly improved the adsorption of lignin to 2.5 g/g on AC. The molecular weight
Keywords:
of PDADMAC considerably affected the results in that the higher MW PDADMAC led to less lignin, but
Lignin
Hemicellulose
more hemicelluloses, turbidity and chemical oxygen demand removals from the SL. The thermal analysis
NSSC also revealed that the higher MW PDADMAC generated precipitates with a lower incineration tempera-
Biorefinery ture and heating value.
Adsorption Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction hemicelluloses is separated from wood chips in a pretreatment

The rising cost of energy, environmental concerns and tight
competitions have led pulping processes to seek for process alter-
natives in order to reduce their production costs and/or produce
materials with considerable profits (Dashtban et al., 2012; Saeed
et al., 2011). In this context, many processes are under develop-
ment to convert pulping operations to forest biorefineries (Fatehi
et al., 2013a; van Heiningen, 2006).
In a neutral sulfite semichemical (NSSC) pulping process, wood
chips are pretreated with sodium sulfite and carbonate to soften
the structure of wood chips. Subsequently, the pretreated wood
chips are disintegrated by mechanical refining (Benjamin et al.,
1969; Dashtban et al., 2012). In this process, a part of lignin and
⇑ Corresponding author. Tel.: +1 807 343 8697; fax: +1 807 346 7943.
E-mail address: pfatehi@lakeheadu.ca (P. Fatehi).
process and dissolved in the spent liquor (SL), which is treated in
the waste water system of the mill (Area et al., 2000a,b). Alterna-
tively, these separated lignin and hemicelluloses of SL can be used
as the feedstock for the production of value-added products, which
will ultimately increase the revenue of this pulping process
(Dashtban et al., 2012; van Heiningen, 2006). However, the SL is
very dilute and contains cooking chemicals (i.e. inorganics) that
hinder the direct use of SL for producing value-added chemicals
in downstream processes (Fatehi et al., 2013a). To facilitate the
application of these components, they should be first extracted
from the SL. In the past, solvent extraction and ultrafiltration have
been proposed for the extraction of hemicelluloses from the spent
liquors of different pulping processes (Chen and Liu, 2007; Jonsson
et al., 2008). However, these processes face some difficulties such
as high operational costs and challenging solvent recovery, which
make them industrially unattractive (Wallberg et al., 2003). On

http://dx.doi.org/10.1016/j.biortech.2014.03.006
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
374 M. Dashtban et al. / Bioresource Technology 159 (2014) 373–379
the other hand, an adsorption process showed promising results in
isolating lignin and hemicelluloses from spent liquors of kraft-
based dissolving pulp process (Fatehi et al., 2013a; Liu et al.,
2011, 2012).
Activated carbons possess a porous structure and large surface
area, and thus are suitable candidates for adsorption at industrial
scales (Lashaki et al., 2012; Moreno-Castilla, 2004). In the past,
activated carbons were used for removing different organic mate-
rials (i.e. phenols and hydrocarbons) from aqueous solutions (e.g.
drinking water and/or wastewater) (Lashaki et al., 2012; Moreno-
Castilla, 2004). In one study, activated carbon adsorbed 231, 204
and 245 mg/g of hemicelluloses, lignin and furfural on an activated
carbon from a model pre-hydrolysis liquor (Fatehi et al., 2013a).
These results, however, cannot be practically applied for simulat-
ing the adsorption performance of lignocelluloses of SL on acti-
vated carbon since the chemistry and compositions of PHL and
SL are different. The first objective of this work was to evaluate
the performance of an adsorption process in isolating the lignin
and hemicelluloses from the spent liquor of an NSSC process. In
fact, this is the first attempt to systematically isolate the lignocel-
luloses of SL using adsorption concept.
Alternatively, to improve the adsorption of lignocelluloses on
activated carbons, a combination of adsorption (using activate car-
bon) and flocculation (using polydiallyldimethylammonium chlo-
ride (PDADMAC)) were employed in the past (Liu et al., 2012),
and the results showed 83.3% lignin, 32.7% hemicelluloses and
100% furfural removals from PHL, respectively. In this context,
the application of PDADMAC as a flocculant for the lignocelluloses
of SL was investigated (Sitter et al., 2014). The second objective of
this study was to systematically assess the performance of a com-
bined adsorption and flocculation process in isolating the lignin
and hemicelluloses from SL. However, this process cannot accom-
modate the separate adsorption of lignin or hemicelluloses on acti-
vated carbon.
In this work, the lignin and hemicelluloses were systematically
isolated from SL by means of adsorption or a combined system of
adsorption/flocculation. In fact, this system is introduced for the
first time ever to isolate the lignin and hemicelluloses from NSSC
spent liquors. The isolated materials can be considered as fuel of
the NSSC process or filler for use in the corrugated medium papers.
In other words, the product of this process (i.e. precipitates of
adsorption process) can be directly used as a value-added material
in the NSSC process. More importantly, the reduction in the ligno-
cellulose content of SL will lead to a lower load in the waste water
system of the mill, which will help reduce the production costs of
the NSSC process.
2. Methods
2.1. Materials
The analytical grades of furfural (>99%), acetic acid (>99%), glu-
cose (>99%), activated carbon (catalog number#AC404045000),
polydiallyldimethylammonium chloride (PDADMAC) with two
molecular weights of 100–200 and 400–500 kDa, and poly vinyl-
sulfate potassium salt (PVSK with the molecular weight of
170 kDa) were purchased from Sigma Aldrich. The spent liquor
(SL) was received from an NSSC pulping process located in eastern
Canada. In the NSSC process, wood chips are pretreated with so-
dium sulfite and carbonate with liquid to wood ratio of 5 (kg/kg)
for 15–18 min at 180 °C prior to mechanical refining the treated
wood chips. The SL is the supernatant of the pretreatment stage
that was collected via filtering the pretreated wood chips prior to
refining.
2.2. BET and charge density analyses
The BET surface area of AC was determined according to the
previously described method (Fatehi et al., 2013a). Briefly, the AC
surface area was determined via nitrogen adsorption/desorption
isotherms using a Quantachrome Instrument, Nova 2200e, Florida,
USA, using 0.1 g (o.d.) of AC. The AC was pretreated at 120 °C and
10 7 Torr overnight for contamination removal. The charge density
analysis of AC was carried out using a particle charge detector,
Mütek PCD-04 titrator (Herrsching, Germany) with a PDADMAC
or PVSK solution (5 mM) as previously described (Liu et al., 2011).
2.3. Adsorption
To study the impact of pH on the adsorption performance of AC,
the pH of original SL (5.7) was adjusted to 3.0 by adding 4 wt.%
H2SO4 or to 7.0, 9.0 or 11.0 by adding 1 M NaOH solution. Then,
the SLs were centrifuged at 2000 rpm (448 g) for 10 min to remove
any precipitates due to the pH change. Subsequently, 1 g of AC was
added to 30 g of these SLs in 250 mL Erlenmeyer flasks and incu-
bated at 30 °C for 3 h at 100 rpm in a Boekel water bath shaker.
To study the adsorption isotherm, various masses (15, 30, 45, 90,
120 and 180 g) of SL (with optimal pH of 7) was mixed with 1 g
of AC at 30 °C and shaken for 180 min in the water bath shaker.
To study the adsorption kinetics, 1 g of AC was mixed with 90 g
of SL (having pH of 7) and incubated at 30 °C for various time inter-
vals (10, 20, 30, 45, 60, 180, 360 and 1440 min) in the water bath
shaker. Alternatively, the control of each sample was prepared
(i.e. SL having the same pH, but without mixing with AC) and incu-
bated under the same experimental conditions. After incubating,
the SL samples were centrifuged at 2000 rpm (448 g) for 10 min
so that the treated AC could be easily separated. The supernatants
were kept for hemicelluloses, lignin, turbidity and chemical oxygen
demand (COD) analyses. All of the above adsorption experiments
were repeated three times and the average values were reported
in this work. Also, the precipitates of the experiments conducted
with 90 g of the SL (having pH of 7) and 1 g of AC at 30 °C for 3 h
and 100 rpm was collected for TGA, calorimetric and CHNS analy-
ses. As there is no method to determine the lignin and hemicellu-
loses of SL together, the lignin and hemicellulose concentrations
were determined separately, and discussed in this work separately
(Figs. 1–4).
2.4. Combined adsorption/flocculation
To improve the adsorption of lignin and hemicelluloses on AC, a
combined adsorption and flocculation experiment was considered.
Fig. 1. Effect of pH on the adsorption performance of lignin and hemicelluloses of
SL on AC (conducted at 30 °C, SL/AC wt. ratio of 30 at 100 rpm for 24 h).
 M. Dashtban et al. / Bioresource Technology 159 (2014) 373–379
Fig. 2. Adsorption isotherms of lignin (top) and hemicellulose (bottom) of SL on AC
conducted at 30 °C, pH 7 and 100 rpm for 180 min.
Fig. 3. Adsorption of lignin and hemicelluloses of SL on AC as a function of time
(conducted at 30 °C, pH 7, SL/AC wt. ratio of 90 at 100 rpm).
In this set of experiments, the adsorption experiment was con-
ducted under the conditions of pH 7.0, SL/AC weight ratio of
90 g/g, 3 h of incubation and 30 °C. Subsequently, various dosages
(ranging from 1 to 20 mg/g) of low or high MW PDADMAC were
added to the SL/AC mixture and shaken at 100 rpm and 30 °C for
24 h in the water bath shaker. Afterwards, the samples were cen-
trifuged at 2000 rpm (448 g) for 10 min to separated supernatants
from precipitates. All of the supernatants were collected for lignin
and hemicellulose analyses. The precipitates formed via adding
20 mg/g of low or 15 mg/g of high MW PDADMAC/SL in the SL/
AC system were collected for TGA and CHNS analyses.
2.5. Hemicellulose analysis
The concentration of hemicellulose in the SL was determined by
using an established procedure via applying 3,5-dinitrosalicylic
acid (DNS reagent) (Dashtban et al., 2011). To measure the total
sugars, the SL samples were first treated with 4 wt.% sulfuric acid
and then incubated at 121 °C for 1 h in an oil bath. This acid treat-
ment converts oligomeric sugars to monomeric sugars, which can
ultimately be determined by the DNS method. In this set of
375
Fig. 4. Adsorption of lignin (top) and hemicelluloses (bottom) of SL on AC via
adding various dosages of low and high MW PDADMAC in the SL/AC system (SL/AC
system was conducted under the conditions of SL/AC wt. ratio 90, 30 °C and 3 h,
then PDADMAC was added to SL/AC system at 100 rpm and shaken for another
24 h).
experiments, all of the SL samples before and after treating with
AC and PDADMAC were treated with acid so that all of their oligo-
meric sugars could be converted to monomeric sugars. Subse-
quently, the sugar concentrations of acid-treated samples were
determined using the DNS method. In other words, this analysis re-
flected the change in the total sugar of SLs before and after treating
with AC and PDADMAC, which could directly show the adsorption
amounts of hemicelluloses on the AC.
2.6. Ash and lignin analyses of SL
The ash content of the SL was determined according to TAPPI
T412, while the lignin content of SLs was determined according
to TAPPI UM 250 using UV spectrophotometry, Genesys 10S UV–
Vis at 205 nm (Liu et al., 2011).
2.7. Furfural and acetic acid analyses of SL
A Varian Unity Inova 500 MHz 1H NMR spectrometer was used
for determining the concentrations of furfural and acetic acid in SLs
according to the previously described method (Saeed et al., 2012).
Furfural and acetic acid standard solutions were prepared to estab-
lish calibration curves for determining furfural and acetic acid con-
centrations in SLs.
2.8. COD and turbidity analyses
To identify the impact of adsorption process on the SL proper-
ties, the turbidity and chemical oxygen demand (COD) of the trea-
ted SLs obtained under the optimal adsorption conditions of SL/AC
weight ratio of 90, pH 7.0 at 30 °C for 180 min, and the optimal
adsorption/flocculation conditions using 20 mg/g of low or
15 mg/g high MW PDADMAC were investigated.
The COD analysis of the selected SL samples was carried out
using a COD kit (0–1500 mg/l) obtained from CHEMetrics Inc.,
376 M. Dashtban et al. / Bioresource Technology 159 (2014) 373–379
USA according to ASTM D1252. In this analysis, the SLs were mixed
with the COD chemicals as received from the company, and then
incubated in a block digester at 150 °C for 2 h. Afterwards, the
absorbency of the samples was measured at 620 nm (Saeed et al.,
2011). The turbidity of the SL samples before and after the treat-
ments with ACs were conducted by using a turbidimeter,
2100AN, Hach Co., CO, USA at room temperature.
2.9. Precipitate analyses
A thermo-gravimetric analysis (TGA) was considered for assess-
ing the thermal performance of the selected precipitates. At first,
the samples were dried at 105 °C and then heated with a ther-
mo-gravimetric analyzer (TGA)-i1000 series (instrument Specialist
Inc.) using N2 (30 ml/min) with an increment rate of 10 °C/min in
the temperature range of 25 and 700 °C (Zhang et al., 2011).
The calorific value analysis of the precipitates was also investi-
gated. In this set of experiments, approximately 0.8–1.2 g of the
selected precipitates was ground to 2 mm using a Wiley mill and
then pelletized using a Parr Pellet press. Gross calorific values of
theses samples were measured according to ASTM E711-87 using
a Parr 6200 oxygen bomb calorimeter.
Elemental analysis of the selected precipitates was conducted
using Vario EL Cube Instrument (Germany) according to the proce-
dure illustrated in the literature (Fadeeva et al., 2008). In this
method, the AC samples were weighed and loaded in an integrated
carousel. First, the AC samples were flushed with a carrier gas (He).
Subsequently, the combustion of ACs was carried out, which was
followed by the reduction of the combusted gases so that the pro-
duced gases could be identified with the instrument and eventu-
ally elemental balance of the ACs could be developed (Fadeeva
et al., 2008).
3. Results and discussion
3.1. SL properties
The SL (pH 5.7) contained 60.22 g/l lignin, 22.13 g/l hemicellu-
loses (17.12 g/l poly-sugars and 5.01 g/l mono-sugars), 26.5 g/l
acetic acid and a trace of furfural (0.52 g/l). The ash content of SL
was approximately 63.8 g/l, which was most probably originated
from the chemicals used in the pretreatment stage of wood chips
conducted in the NSSC pulping process. In one study, the SL of
NSSC spent liquor contained 59–69% lignin, 2–24% hemicelluloses
and 12–29% acetic acid on ash free basis (Area et al., 2000a,b).
3.2. Effect of pH on adsorption
The AC had a 27.2 leq/g charge density. A similar result was
reported using different activated carbons, for which a charge den-
sity of 28.0 meq/g was obtained (Newcombe, 1999; Takahashi
et al., 2012). The surface area of the AC was 2753 m2/g. In the past,
it was reported that acetic acid had a limited adsorption affinity on
activated carbon (Liu et al., 2011). The concentration of furfural
was also very limited in the SL. Therefore, the adsorption analysis
of acetic acid and furfural on AC was excluded from this study.
Previous studies indicated that the pH of spent liquors was a
crucial factor on the adsorption of lignocelluloses on adsorbents
(Garcia-Araya et al., 2003; Moreno-Castilla, 2004; Myers, 1981).
Fig. 1 presents the adsorption performance of lignin and hemicel-
luloses of SL on AC at different pHs. As can be seen, approximately
0.58 g/g of lignin and 0.4 g/g of hemicelluloses were adsorbed on
AC at pH 7 (i.e. optimum pH of the system). The extra OH or H ions
in solutions help ionize or neutralize the dissolved compounds
and/or the charged groups on the surface of the adsorbents (i.e.
activated carbons) under acidic or basic conditions (Garcia-Araya
et al., 2003; Moreno-Castilla, 2004; Myers, 1981). We selected
pH 7 as optimal pH of our experiments, as our results showed
the highest adsorption at pH 7 (especially for hemicelluloses).
3.3. Adsorption isotherms
Fig 2 depicts the adsorption isotherms of lignin and hemicellu-
loses of SL on AC. In this figures, the adsorption amount was drawn
versus the remaining amount of hemicelluloses or lignin in SL after
the adsorption experiment. In this figure, the points from left to
right corresponded to the SL/AC ratio of 15, 30, 45, 90, 120 and
180 g/g. Evidently, 0.93 g/g of lignin (top figure) and 0.47 g/g of
hemicelluloses (bottom figure) were adsorbed on AC after 3 h of
experiments at 30 °C (pH 7), which corresponded to the lignin
and hemicellulose removals of 7% and 14% from the SL, respec-
tively. These results also showed that the highest adsorption of lig-
nin and hemicelluloses on AC was obtained at SL/AC wt. ratio of 90.
In another study, a maximum of 170 mg/g phenol was adsorbed on
activated carbon at 25 °C after 10 h, when the concentration of
phenol in suspension was 100 mg/l (Fierro et al., 2008). Generally,
the lignin and hemicelluloses of spent liquors usually contain anio-
nic charges due to the existence of carboxylic or sulphonated
groups on their structures (Fatehi et al., 2013a,b; Takahashi et al.,
2012). These groups could develop hydrogen bonding with the car-
boxylic, hydroxyl and/or carbonyl groups of AC, which facilitate the
adsorption of lignin and hemicelluloses (Chinn and King, 1999;
Hubbe and Lucia, 2007; Fatehi et al., 2013a; Sulaymon and Ahmed,
2008; Uraki et al., 2007). Lignin has hydrophobic properties due to
its aromatic ring structure, which promote its adsorption on AC.
Therefore, the higher adsorption of lignin than hemicelluloses
may be ascribed to (1) higher lignin content of SL and/or (2) higher
hydrophobic nature and tendency of lignin for adsorption on AC.
3.4. Adsorption kinetics
Fig. 3 presents the adsorption of lignin and hemicelluloses on
AC as a function of time. The results show that the adsorption of
lignin reached plateau at 0.93 g/g on AC after 90 min, while hemi-
celluloses reached the saturation of 0.44 g/g after 360 min. The fas-
ter adsorption of lignin may indicate that the size (and thus the
MW) of lignin was smaller than those of hemicelluloses. Therefore,
it diffused into the pores of AC more quickly than hemicelluloses
did (Fatehi and Xiao, 2008; Lashaki et al., 2012). These results are
well in harmony with previously reported results on the adsorp-
tion of lignin and hemicelluloses of pre-hydrolysis liquor (PHL)
on activated carbon and precipitated calcium carbonates (Liu
et al., 2011; Fatehi et al., 2013a). In another study, 160 mg/g of
phenol was adsorbed on activated carbon after 90 min of treat-
ment at 25 °C (Fierro et al., 2008). Alternatively, 210 mg of lignin
and 175 mg of tannin were adsorbed on activated carbon in
60 min of treatment at 29 °C (Mohan and Karthikeyan, 1997).
3.5. Addition of PDADMAC to SL/AC system
In the second stage of this study, PDADMAC was added to SL/AC
system in order to improve the adsorption of lignocelluloses on AC.
In one report, it was suggested that PDADMAC interacted with
lignocelluloses and formed complexes through charge interaction
and hydrogen bonding (Liu et al., 2011, 2012). By adding PDAD-
MAC to the SL/AC system, a part of PDADMAC will interact with
unadsorbed lignocelluloses of SL and form complexes that can de-
posit on the surface of AC. Another part of the added PDADMAC
will adsorb on the surface of AC that is already covered by lignin
and hemicelluloses. This will promote the adsorption of unad-
sorbed lignocelluloses of SL on AC through charge interaction.
 M. Dashtban et al. / Bioresource Technology 159 (2014) 373–379
Therefore, the adsorption of complexes made of lignocelluloses and
PDADMAC and layer-by-layer assembly of lignocelluloses and
PDADMAC on the AC could be the possible mechanisms for the ex-
tra adsorption of lignocelluloses on AC in PDADMAC/SL/AC system
(Fatehi et al., 2013a,b; Liu et al., 2012). Fig. 4 shows the adsorption
of lignin and hemicelluloses of SL on the AC via adding PDADMAC
with two different MWs. Interestingly, the adsorption of lignin was
increased from 933 to 2573 mg/g by adding 20 mg/g of low MW
PDADMAC and to 2320 mg/g by adding 15 mg/g of high MW
PDADMAC to the system (top figure), which corresponded to 47%
and 43% lignin removals from the SL, respectively. However, the
adsorption of hemicelluloses was increased from 400 to 500 mg/
g by adding up to 15 mg/g of high MW PDADMAC and insignifi-
cantly changed by adding up to 15 mg/g low MW PDADMAC (bot-
tom figure), which corresponded to 27% hemicellulose removal
from SL. Apparently, the increase in the dosage of PDADMAC signif-
icantly improved the adsorption of lignin on AC, whereas it mar-
ginally affected the adsorption of hemicelluloses. These results
suggest that there was a stronger interaction between lignin and
PDADMAC rather than between hemicelluloses and PDADMAC.
Furthermore, the adsorption of lignin reached the maximum via
adding 15 mg/g of high MW PDADMAC, while it gradually in-
creased via increasing the dosage of PDADMAC in the SL. It is well
known that low MW polymers can adsorb more than high MW
ones on adsorbents (Fatehi and Xiao, 2008). On the other hand,
the smaller the polymers, the smaller the complexes can be made
from these polymers. This is due to the fact that large polymers
tend to bridge complexes. Similarly, small complexes can adsorb
more than large ones on the surfaces of an adsorbent. Therefore,
by adding more of low MW PDADMAC, (1) more of low MW PDAD-
MAC might have adsorbed on the surface of AC, thus facilitating the
adsorption of lignin on AC and/or (2) more of small complexes of
low MW PDADMAC and lignin could be formed and adsorbed on
AC. As also seen in Fig. 4, the amount of hemicellulose adsorption
was reduced when PDADMAC dosage was increased from 15 to
20 mg/g. As lignin-PDADMAC and hemicellulose-PDADMAC com-
plexes competed for the adsorption on AC, the increase in the
adsorption of lignin-PDADMAC complexes led to space constrains
and thus reduced the available surface area for the adsorption of
hemicellulose-PDADMAC complexes on AC. However, further anal-
ysis is required to prove this hypothesis.
3.6. COD and turbidity analyses
Table 1 shows the characterization of SL after various stages. As
can be seen, the COD of SL before and after AC treatment was sim-
ilar, which is due to the insignificant reduction of lignin and hemi-
celluloses of SL via AC treatment. However, the COD dropped by
30% or 39% for the systems of low MW PDADMAC/SL/AC or high
MW PDADMAC/SL/AC, respectively. The turbidity of SL was re-
duced by 33% via treating SL with AC, and by 60% or 79% via treat-
ing SL with low MW PDADMAC/SL/AC or high MW PDADMAC/SL/
AC, respectively.
Table 1
Turbidity and COD analyses of SL, as well as elemental analysis of AC before and after treatment.
Sample N wt.% C wt.% H wt.% S wt.%
SL 0.17 33.97 4.02 4.0
AC 0.73 75.05 2.48 0.08
SL/AC 0.48 59.67 4.61 3.72
Low MW PDADMAC/SL/AC 2.03 51.81 6.367 3.114
High MW PDADMAC/SL/AC 1.65 52.23 6.063 3.152
377
3.7. Elemental and heating value analyses
The elemental analysis of precipitates is also included in Table 1.
As seen, the SL contained 33% carbon, 8% hydrogen and sulfur, and
58 wt.% of other components (i.e. inorganics and oxygen). The AC
had 75% carbon and 2.5% hydrogen and sulfur, and 21.2% of other
constituents. The SL-treated AC contained 59% carbon, 7.3% hydro-
gen and sulfur and 31.5 wt.% other components. The PDADMAC/SL
treated ACs contained 51–52 wt.% carbon, 9% hydrogen and sulfur
and 36–37% remaining components. Consequently, the addition of
PDADMAC to the SL/AC system caused the precipitates to contain
less carbon (compared to SL/AC precipitates), which may indicate
that more inorganics were adsorbed on the AC via adding
PDADMAC. The increase in the nitrogen content of AC for the
PDADMAC/SL treated AC (compared to SL treated AC) is due to
the presence of PDADMAC on the AC. The heating value analysis
also revealed that the heating value of SL treated AC was
24.8 MJ/kg, which is slightly lower than that of AC. The heating va-
lue was slightly lower for the precipitates of low MW PDADMAC/
SL/AC and was the lowest for that of high MW PDADMAC/SL/AC.
Generally, the decrease in the heating value of AC is due to the in-
crease in the lignin, hemicellulose and inorganic content of AC.
However, these results are interesting as the precipitates contained
approximately 25 wt.% AC and 75 wt.% lignin and hemicelluloses as
observed in Fig. 3.
3.8. TGA analysis
Fig. 5 (top) shows the weight loss of ACs, which were treated
with SL under altered scenarios. It is observable that the major
weight loss of AC occurred at a temperature that was higher than
500 °C. However, the SL-treated AC had two major weight losses
at the temperatures of 250 and 500 °C. Additionally, approximately
80% of the SL-treated AC was incinerated during the TGA analysis,
which could be attributed to lignin and hemicelluloses incineration
in the TGA analysis (Shi et al., 2012; Yang et al., 2004). In the liter-
ature, the initial weight loss (below 300 °C) is attributed to the
removal of easily oxidizable amorphous carbonaceous species
(Koo et al., 2008; Zhang et al., 2011). However, the oxidation of
char occurs at higher temperatures (>500 °C) (Zhang et al., 2011).
The ACs that were treated with PDADMAC and SL contained
20 wt.% ash at 700 °C, while original AC and the one treated with
SL had marginal ash. These results indirectly confirm that some
inorganics might have also been adsorbed on the AC, which led
to ash formation in the system of PDADMAC/SL/AC (Fig. 5, top).
The weight loss rates of the AC samples were depicted in Fig. 5
(bottom). It is apparent that the weight loss of AC occurred at
645 °C, whereas the SL and ACs treated with SLs showed two main
peaks at 230 and 530 °C. These results are in agreement with pre-
vious reports on the combustion of hemicelluloses and lignin at
220–300 and 380–530 °C, respectively (Lv et al., 2010; Shi et al.,
2012; Yang et al., 2004). The AC that was treated with PDAD-
MAC/SL had a larger peak at 230 °C, but a smaller peak at the tem-
perature range of 500–650 °C, compared to the treated AC with SL.
It is inferred from these results that the addition of PDADMAC to
Remaining element, wt.% Turbidity, NTU COD, mg/l Heating value, MJ/kg
57.84 4815 ± 4.24 1.2  105 ± 325 14.14
21.26 – – 27.24
31.51 3243 ± 21 0.99  105 ± 1138 24.77
36.68 1923 ± 29.3 0.83  105 ± 478 25.03
36.91 998.6 ± 9.01 0.73  105 ± 702 22.4
378 M. Dashtban et al. / Bioresource Technology 159 (2014) 373–379
Fig. 5. Weight loss (top), weight loss rate (bottom) of AC samples after treating
with SL under different scenarios (conducted in N2 at 30 ml/min heated at 10 °C/
min).
the system created complexes with more easily oxidizable at
230 °C rather than at 650 °C. This is very interesting since the
addition of PDADMAC reduced the incineration temperature of
the precipitates (SL treated AC).
3.9. Performance of low vs. high MW PDADMAC
The results in Fig. 1 depicted that the adsorption performance of
low MW PDADMAC was slightly better than that of high MW
PDADMAC in adsorbing lignin (rather than hemicelluloses) on
AC. It is observable in Table 1 that high MW PDADMAC was more
efficient in reducing turbidity and COD levels of the SL. These re-
sults indicate that lignin contributed less than hemicelluloses
and other components of SL in the turbidity and COD of SL as since
the high MW PDADMAC removed less lignin, but more hemicellu-
loses (Fig. 4). It is also observable in Fig. 5 that the rate of weight
loss for the precipitates of high MW PDADMAC occurred at a rela-
tively lower temperature than that of low MW PDADMAC. The
lower rate of weight loss and heating value results are attributed
to the lower lignin and higher hemicellulose contents of high
MW PDADMAC/SL/AC precipitates than those of low MW PDAD-
MAC/SL/AC precipitates, also it may imply that a lower MW poly-
mers or more easily oxidizable materials contained in the
precipitates of high MW PDADMAC.
4. Conclusions
AC could remove a part of lignin and hemicelluloses from SL and
the optimal conditions were 30 °C, pH 7 and 3 h of treatment.
Interestingly, the addition of PDADMAC significantly improved
the adsorption of lignin and hemicelluloses on AC, implying that
the addition of a polymer could be crucial in obtaining the maxi-
mum performance. The MW of PDADMAC played an important role
on the SL and precipitate properties since the higher MW PDAD-
MAC led to lower lignin but higher hemicelluloses, turbidity and
COD removals, as well as to precipitates with a lower heating value
and thermal decomposition properties.
Acknowledgements
The authors would like to acknowledge NSERC Discovery grant
for supporting this research.
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