Industrial Crops and Products 91 (2016) 66–75

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Industrial Crops and Products

journal homepage: www.elsevier.com/locate/indcrop

Effect of alkaline pre-extraction of hemicelluloses and silica on kraft

pulping of bamboo (Neosinocalamus affinis Keng)
Zhaoyang Yuan a,∗ , Nuwan S. Kapu a , Rodger Beatson a,b , Xue Feng Chang b ,
D. Mark Martinez a
a
Department of Chemical & Biological Engineering, University of British Columbia, 2360 East Mall, Vancouver, BC V6T 1Z4, Canada
b
Chemical & Environmental Technology, British Columbia Institute of Technology, 3700 Willingdon Ave., Vancouver, BC V5G 3H2, Canada

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

Article history: Commercial bamboo chips were pre-treated with sodium hydroxide (NaOH) solutions to completely
Received 19 February 2016 extract silica and partially extract hemicelluloses prior to kraft pulping. Reaction temperatures of
Received in revised form 13 June 2016 80–100 ◦ C, times of 1–5 h, and NaOH charges of 6–18% were explored. With increasing pre-extraction
Accepted 19 June 2016
severity, all silica and up to 50% of hemicelluloses in raw chips could be extracted without degrading
Available online 15 July 2016
cellulose and lignin. The chips from select extractions were cooked using the kraft process with varying
effective alkali (EA) charges. Pre-extraction resulted in significant improvement in the delignification of
Keywords:
chips during subsequent kraft pulping, offering an option to reduce the EA charge or the H-factor. The
Alkaline pre-extraction
Bamboo
pulp yield was similar to the control while the drainage resistance of pulp from pre-extracted chips was
Hemicellulose slightly improved. Physical strength properties of pulps made from pre-extracted chips showed lower
Kraft pulping tensile index and higher tear index as compared with the control runs. Moreover, silica was no more a
Pulp strength problem for chemical recovery and production of high-grade pulp. Extracted silica and hemicelluloses in
Silica the alkaline extraction liquor (AEL) can be used as a potential raw material for value-added products.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Non-wood materials are attracting growing attention for use
in conventional pulp and paper making and as a feedstock for
the bio-based economy due to diminishing forest resources and
increasing consumption of lignocellulosic products (Farrell et al.,
2000; Machmud et al., 2013; Salmela et al., 2008). Of the non-
woods, bamboo, abundantly distributed in Asia and South America,
is considered to be among the most attractive feedstocks due to its
rapid growth and comparable chemical composition with woods
(Luo et al., 2013; Scurlock et al., 2000; Sixta, 2006). Moreover, unlike
cereal straw, the kraft based technologies, similar to those used
for woody raw materials, are generally used for the production of
pulp and paper products from bamboo (Vu Mân et al., 2004). How-
ever, compared to wood, bamboo contains a much higher level of
silica. The high silica level creates problem in the recovery cycle
of the kraft pulping process and high amounts of residual silica
in dissolving pulps, cause poor filterability and interfere with the
downstream conversion of dissolving pulps into other products
∗ Corresponding author.
E-mail address: yuanzy87@hotmail.com (Z. Yuan).
(Liese, 1987; Salmela et al., 2008; Tsuji et al., 1965). Considerable
efforts have been expended in trying to solve the silica issue. These
efforts have been mainly focused on preserving silica in the final
pulp and desilication of black liquor rather than removing silica
from the raw material entering the pulping process (Jahan et al.,
2006; Kopfmann and Hudeczek, 1988; Pan et al., 1999; Tsuji et al.,
1965). Unfortunately, until now, none of this work has led to a
commercial process.
Recently, the proposed integrated forest biorefinery (IFBR) con-
cept has been advanced as a means of addressing concerns over
energy security and climate change. According to the IFBR concept,
hemicelluloses are partially or completely pre-extracted under
acidic or alkaline conditions prior to the pulping stages for the
generation of value-added products such as bioethanol, furfural,
acetone, or to be used as papermaking additives (Bai et al., 2012;
Hamzeh et al., 2013; Liu et al., 2013; Mao et al., 2008). Moreover,
pre-extraction of lignocellulosic biomass has been shown to be
an efficient way of removing hemicelluloses while also improv-
ing the digestibility of the residual biomass and preserving pulp
quality (Van Heiningen, 2006). Thus, a novel way to solve the silica
problems encountered when pulping bamboo could involve pre-
extraction of silica along with hemicelluloses prior to the pulping
processes.

http://dx.doi.org/10.1016/j.indcrop.2016.06.019
0926-6690/© 2016 Elsevier B.V. All rights reserved.
 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75
Previous studies on the pre-treatment of bamboo chips prior
to pulping were mainly focused on the extraction of hemicellu-
loses/lignin for the production of kraft pulp, high-grade dissolving
pulp or fermentable sugar (Leenakul and Tippayawong, 2010; Luo
et al., 2013; Sathitsuksanoh et al., 2010; Xiao et al., 2014). Limited
investigation has been conducted in extracting and recovering sil-
ica from bamboo. Additionally, bamboo silica, like silica in cereal
straw or rice husks, could be an excellent resource for silica-based
products such as silica gel and silica nanoparticles, which could
be used in various high-value products such as thixotropic agents,
pharmaceuticals, film substrates, electric and thermal insulators
composite filler, etc. (Kalapathy et al., 2002; Zhang et al., 2013).
Within this context, the pre-extraction of silica prior to subsequent
commercial pulping may not only be able to solve the silica prob-
lems of using bamboo in kraft pulping but also would add value
and increase revenue to the mill. Therefore, the kraft-based bam-
boo pulping process could be improved by adding a pre-extraction
stage.
In addition, even though bamboo belongs to the grass fam-
ily, having a woody stem it is structurally quite different from
other lignocellulosic materials such as softwoods, hardwoods and
cereal straw. Bamboo stem is composed of three parts: epidermal
(outmost cell layer of the stem), mid-cortex (the region between
epidermal layer and inner cortex), and inner cortex (the portion
encircling the hollow center of the culm). Due to the unique location
in the bamboo stem and their functions, these three regions dif-
fer substantially in chemical composition including extractives, ash
and silica content (Chand et al., 2006). These differences will affect
the bamboo feedstock processing methods in kraft-based pulping
and biorefinery applications. It is thought that it may be beneficial
to remove one or two regions of the bamboo stem (bamboo epi-
dermal or inner cortex) before pulping. However, the removal of
bamboo parts as waste will reduce the useful biomass fraction and
cause environmental problems (Li et al., 2014). Accordingly, before
optimizing the pulping processes, the chemical composition and
silica mass distribution in the bamboo stem needs to be quantified.
In the work reported in this paper, the chemical composition and
silica mass distribution of the bamboo stem (Neosinocalamus affinis
Keng) were quantified to provide insights into promising bamboo
stem processing methods for the preparation of bamboo chips. Sub-
sequently, alkaline pre-treatment was carried out to completely
extract silica and partially separate hemicelluloses from bamboo
chips prior to kraft pulping. The objectives of the work described
here were to study the effects of pre-treatment conditions (NaOH
charge, temperature and time) on silica and hemicelluloses pre-
extraction and to investigate the effect of alkaline pre-extraction
on the properties of kraft pulps such as silica content, yield, free-
ness, and tensile and tear strength indices by comparing with the
properties of the non-extracted counterpart. A modified pulping
process was proposed and a mass balance of the main components
from pre-extraction to kraft pulping was established. Our results
suggest that the modified pulping scheme fits well with the IFBR
concept.
2. Materials and methods
2.1. Raw materials and chemicals
Fresh bamboo trees (5 years old) of Neosinocalamus affinis Keng
were collected in September, 2012 from a natural forest in Sichuan
Province, China. Each bamboo stem was evenly cut into three parts
along the length of the bamboo stem: top-middle-bottom. All sam-
ples were washed thoroughly with distilled water to remove the
dust and other impurities from the surface. This washing operation
was performed 10 times, and then samples were dried for 48 h at
67
room temperature. Subsequently, the samples were cut into small
strips with a razor blade and ground using a Wiley Mill. The sam-
ple powder that passed through a 40-mesh sieve yet retained on a
60-mesh sieve was collected in glass jars for further use.
For the analysis of chemical composition in different layers
along the radial direction, the stems were separated manually with
a plane block (Lee Valley Tools Ltd. Canada) to three layers: epi-
dermal layer (≈0.1 mm), mid-cortex (≈3 mm) and inner cortex
(≈0.2 mm). The three fractions of bamboo samples were ground,
screened and stored as previously described.
Bamboo chips prepared from 3 to 7 year old trees were provided
by the Lee & Man Paper Manufacturing Ltd. China. The obtained
chips were washed with distilled water at a liquid-to-wood ratio
of 20 L/kg using a laboratory mixer to remove impurities, such as
soil and sand. The washed chips were air dried for approximately
24 h and stored at 4 ◦ C until used for subsequent alkaline pre-
treatment and kraft cooking experiments. The chips were analyzed
with respect to lignin content, carbohydrate composition, extrac-
tives, ash and silica content. All chemicals used in this study were
reagent grade and were purchased from Fisher Scientific, Canada.
2.2. Alkaline pre-treatments
Alkaline pre-extraction experiments were carried out in 4 sil-
icate glass bottles of 2 L capacity immersed in a laboratory-scale
heated oil bath. A series of alkaline pre-extraction experiments
were conducted over two temperatures (80 and 100 ◦ C), sodium
hydroxide (NaOH) charges (6–18%) and reaction times (1–5 h). In
all alkaline pre-extraction experiments, the liquid-to-wood ratio
was kept constant at 8 L/kg. For an alkaline pre-treatment run, bam-
boo chips of 100 g oven dried (o.d.) and the calculated volume of
distilled water and NaOH solution (stock concentration of 100 g/L)
were mixed and placed in a reactor. Subsequently, the reactor was
placed in the oil bath pre-heated to the target temperature. After
the pre-treatment, the vessels were rapidly cooled down in an
ice/water bath. The pre-treated bamboo chips were separated from
the liquor through vacuum filtration. The liquor was collected and
stored at 4 ◦ C for the composition analysis. The treated chips were
washed thoroughly with distilled water and stored at 4 ◦ C for com-
ponent analysis and kraft cooking. All experiments were performed
in triplicate.
2.3. Kraft pulping
Pulping of pre-extracted and untreated (without pre-extraction)
bamboo chips by the kraft process was conducted in four 300 mL
stainless steel reactors in an oil bath under conditions covering the
range of practical interest. For all cooks, the temperature was raised
to 165 ◦ C in 85 min and held at 165 ◦ C for 75 min. The liquid-to-
wood ratio and sulfidity were fixed at 4 L/kg and 25% (percentage
of Na2 S, expressed as Na2 O), respectively. The effective alkali (EA)
(expressed as Na2 O) was varied in the range of 13–19% (based on
oven dried wood mass). For each kraft cook, 45 g o.d. extracted or
non-extracted bamboo chips and the calculated volume of cook-
ing chemicals and distilled water were placed in the reactor and
mixed for 10 min. Afterwards, the cooking process was carried out
according to the conditions being investigated. Upon completion
of a cook, the reactor was rapidly cooled and kraft pulp was recov-
ered using vacuum filtration. The kraft pulp was thoroughly washed
with distilled water until the pH of the filtrate reached neutral.
Then, the pulp was disintegrated, screened, and filtered to mea-
sure total yield, screened yield, and rejects of the kraft cooking. All
experiments were performed in triplicate.
68 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75
2.4. Analytical methods
The moisture content of solid samples was measured by dry-
ing at 105 ± 2 ◦ C to constant weight. The contents of water and
solvent extractives of bamboo culm samples and bamboo chips
were determined using a Soxhlet extractor according to TAPPI T
204 cm-97.
Carbohydrates and lignin content of the solids was determined
after air drying. Lignin content was calculated as the sum of Kla-
son lignin and acid soluble lignin. Klason lignin content of bamboo
chips and pulp was determined using National Renewable Energy
Laboratory (NREL) standard protocols (Sluiter et al., 2012). Briefly,
40–60 mesh samples were subjected to a two-step sulfuric acid
(H2 SO4 ) hydrolysis protocol to digest the polysaccharides into
monomeric sugars. After hydrolysis, Klason lignin was separated
through filtration and weighed after drying at 105 ± 2 ◦ C. Acid sol-
uble lignin in the hydrolysate (after removing Klason lignin) was
measured at wavelength 205 nm using a UV–vis spectrophotome-
ter (Dence, 1992). Monomeric sugars were determined using a
Dionex ICS 5000+ HPLC (high performance liquid chromatography)
system equipped with an AS-AP autosampler and an electrochemi-
cal detector (Thermo Fisher Scientific, MA, USA) following the NREL
methods (Sluiter et al., 2012). The monomeric sugars were sepa-
rated on a Dionex Carbopac SA10 analytical column (Thermo Fisher
Scientific, MA, USA) at 45 ◦ C using 1 mM NaOH as the mobile phase.
Fucose was used an internal standard.
The ash content of bamboo chips and pulp was determined
according to TAPPI T211 om-02. Silica content of bamboo chips and
pulp was measured gravimetrically, using a method modified from
Ding et al. (2008). Briefly, about 5 g of dried and powdered bam-
boo sample was completely ashed at 550 ◦ C. After cooling, 10 mL of
dilute HCl (6 mol/L) was added to the ash to precipitate silica and
dissolve acid-soluble ash. The resultant solution was gently boiled
to near dryness in a boiling water bath. HCl treatment was repeated
three times in about 30 min, after which another 15 mL of dilute HCl
(6 mol/L) was added to the solution. After 2 more min, the solution
was filtered off through No. 42 ashless filter paper (Fisher Scien-
tific, Canada). The precipitate was rinsed 5–6 times with 1 mol/L
HCl solution and 5–6 times with hot distilled water (≈50 ◦ C). Both
the filter paper with the precipitate was ashed at 700 ◦ C and cal-
cined at 1000 ◦ C in a muffle furnace to reach a constant weight. The
resultant silica residue was weighed to determine silica and ash
content. All measurements were run in triplicate.
Before measuring the properties of the extracts and black
liquors, the liquors were filtered to remove potential fines material.
Total solid content of the extracts and black liquors was deter-
mined by vacuum drying at 45 ◦ C for 48 h. Silica content of liquors
was measured by using the silicon molybdenum blue photomet-
ric method (Tong et al., 2005). For the determination of lignin
and carbohydrates content of the extracts, the filtered AELs were
neutralized using dilute sulfuric acid. Then the samples were auto-
claved with 4% (w/w) H2 SO4 for 60 min. The analysis was continued
as described for the analysis of the solid samples. Lignin content of
the black liquors was determined gravimetrically by acid precipita-
tion and centrifugation (Rocha et al., 2012). The chemical contents
in extracts were determined in mg/ml and then converted into per-
centage of original oven dry wood weight by multiplying with the
value of the liquid-to-wood ratio divided by 10.
2.5. Evaluation of pulps
The kappa number of screened pulps was determined according
to TAPPI T236 om-99. The fines content of the pulps was measured
with a Fibre Quality Analyzer (Op Test Equipment Inc., ON, Canada)
based on TAPPI T271 om-07. The pre-extracted and untreated bam-
boo pulps were beaten in a laboratory disc refiner (PFI mill) at
different revolutions according to TAPPI T248 sp-00. The freeness
(drainability) of the pulps was determined according to TAPPI T227
om-99 (Canadian Standard Method). Standard handsheets of about
60 g/m2 were made by TAPPI T 205 sp-02. The handsheets were
tested for tensile and tear strength properties using TAPPI T 220
sp-01.
3. Results and discussion
3.1. Characterization of the raw material
Table 1 shows the results of the analysis of chemical composi-
tion of different fractions along the length (top, middle, bottom) of
the bamboo stem and layers (epidermal, mid-cortex, inner cortex)
across the cross section of the original bamboo stem. The composi-
tion of each component analyzed (glucan, xylan, galactan, arabinan,
lignin, extractives, ash, silica), is expressed as the average mass
percentage of this component in the oven dry solids, determined
from at least three tests. With regards to the composition along
the length of the bamboo stem, the cellulose and lignin content of
the three fractions along the length of the stem (top, middle, bot-
tom) were similar at around 46.5% and 23.5%, respectively, while
the hemicellulose (mainly xylan) content of the bamboo at the top
of the stem (24.8%) was the highest, followed by that in the middle
(23.4%). Hemicellulose content was the lowest at the bottom of the
stem (21.4%). Arabinan and galactan content in all three parts were
less than 1% while mannan was undetectable by the HPLC method-
ology used. The main difference in chemical composition among
the three parts along the stem was found in the silica content. At
the top of the stem the silica content was 0.91% which decreased
by almost 50% to a value of 0.47% at the bottom of the stem. This is
in agreement with previous studies that reported decreasing silica
levels from the apical to basal portions of the stem (Collin et al.,
2012). The most important observation was that the ratio of silica
mass in the three parts was about 1:1:1 due to the difference in the
weight fraction of bamboo biomass in each region.
The chemical composition and silica mass distribution of differ-
ent layers (epidermal, mid-cortex, inner cortex) along the radial
direction of the stem are shown in Table 1. It was found that
the glucan content of the bamboo mid-cortex (49.4%) was much
higher than that of the epidermal layer (44.3%) and the inner cor-
tex (43.3%). Lignin content was found to be highest in the bamboo
epidermal portion (28.5%), followed by the inner cortex (24.1%)
and mid-cortex (23.2%). The hemicellulose (xylan, arabinan and
galactan) content in the epidermal region, mid-cortex, and inner
cortex were comparable at 22.3%, 23.5% and 24.4%, respectively.
The highest extractives content was in the bamboo inner cortex
(8.4%), followed by the mid-cortex (5.2%) and the epidermal layer
(4.8%). The ash and silica contents of the bamboo epidermal part
were higher than those of the bamboo mid-cortex and inner cor-
tex. The difference in silica content (1.3%) was especially high with
that in the epidermal region being about seven-times higher than
in the mid-cortex or the bamboo inner cortex. However, the major-
ity of silica mass in the bamboo was located in bamboo mid-cortex
(63%) because this region accounts for about 88% of the biomass
while the epidermal portion and the inner cortex account for only
6% each. According to the composition analysis results, the removal
of bamboo epidermal layer or inner cortex does not result in a sig-
nificant decrease of silica amount input into the pulping processes;
in contrast, it would increase the capital cost and cause environ-
mental problems by the increasing industrial wastes. Moreover,
compared with bamboo mid-cortex, bamboo epidermal part and
inner cortex have comparable concentrations of hemicelluloses,
which can be pre-extracted for bioconversion. Consequently, rather
than removing biomass of epidermal region and inner cortex the
 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75 69

Table 1
Chemical composition of original bamboo stem (Neosinocalamus Affinis Keng).

Location Glucan (%) Xylan (%) Galactan (%) Arabinan (%) Lignin (%) Extractives (%) Ash (%) Silica (%) Silica mass
fraction

Length Top 46.57 ± 1.52 24.82 ± 1.02 0.58 ± 0.12 0.63 ± 0.05 23.14 ± 0.21 5.64 ± 0.72 1.35 ± 0.10 0.91 ± 0.05 0.36
direction Middle 46.71 ± 1.85 23.43 ± 0.87 0.44 ± 0.25 0.52 ± 0.11 23.75 ± 0.32 4.12 ± 0.64 1.31 ± 0.12 0.60 ± 0.02 0.34
Bottom 46.89 ± 1.94 21.41 ± 0.98 0.35 ± 0.14 0.41 ± 0.13 23.56 ± 0.20 3.83 ± 0.81 1.28 ± 0.13 0.47 ± 0.04 0.30
Cross Epidermal 44.32 ± 1.56 21.53 ± 1.12 0.18 ± 0.04 0.62 ± 0.13 28.52 ± 0.22 4.78 ± 0.44 2.12 ± 0.08 1.32 ± 0.03 0.32
section Mid-cortex 49.44 ± 2.12 22.61 ± 1.26 0.20 ± 0.04 0.77 ± 0.14 23.21 ± 0.31 5.24 ± 0.36 0.93 ± 0.04 0.17 ± 0.02 0.63
Inner cortex 43.35 ± 1.85 23.37 ± 1.55 0.20 ± 0.02 0.91 ± 0.14 24.08 ± 0.26 8.41 ± 0.29 1.26 ± 0.04 0.20 ± 0.05 0.05

Table 2 bamboo chips while minimizing the loss of cellulose and lignin.
Chemical characteristics of commercial bamboo chips (Neosinocalamus Affinis Keng).
The presence of lignin in the spent pre-treament liquor hampers
Property Bamboo Moso Aspen (Jun Loblolly Pine its utilization in bioethanol or xylitol production because lignin
Bamboo (Li et al., 2012) (Huang and Ragauskas, degradation products inhibit the growth and metabolic activity
et al., 2012) 2013)
of micro-organisms used in bioconversion processes. Moreover,
Glucan, % 47.30 44.4 44.10 45.50 silica recovery through lowering the pH of spent liquor is nega-
Xylan, % 20.30 22.9 19.60 7.30 tively affected due to co-precipitation of lignin (Minu et al., 2012;
Galactan, % 0.52 – 1.80 2.10
Shi et al., 2011). Since high temperature low alkali charge pre-
Arabinan, % 0.84 0.2 0.80 1.40
Mannan, % – – 2.00 9.80 extraction processes have several drawbacks such as high capital
Klason lignin, % 24.40 22.0 21.2 27.70 investment cost and the low molecular-mass of the hemicelluloses
Acid soluble 0.91 – 3.02 – extracted-which renders the hemicelluloses difficult to concen-
lignin, %
trate and separate (Jun et al., 2012; Yoon et al., 2011), high alkali
Extractives, % 4.60 7.10 – 3.20
Ash, % 2.11 2.40 0.60 – charge (6–18%) and relatively lower reaction temperatures were
Silica, % 1.12 – – – investigated in this study. Table 3 shows the results of extrac-
tions in terms of chemical composition of pre-treated chips prior
to pulping. Results indicated that the yield depended on all three
whole bamboo stem should be used as the raw material in pulping factors, extraction temperature, NaOH charge and time. For exam-
or biorefinery processes. ple, the use of 6% NaOH resulted in chip yields between 92%
According to above results, bamboo chips were prepared from and 97% at 80 ◦ C while the yield decreased to 88–94% at 100 ◦ C.
the bamboo stem. Table 2 compares the chemical composition of With regards to the composition changes, as expected, alkaline
the commercial bamboo chips used in this work to that reported extraction at low temperatures (<100 ◦ C) resulted in little loss of
in the literature for other cellulosic biomasses such as different cellulose and lignin while significantly reducing the hemicellu-
bamboo species, softwood and hardwood. As shown in Table 2, glu- loses (xylan) and silica contents. On the basis of the chip yield
can content of the commercial chips was 47.3%, which was a little and composition analysis, the actual loss of the different bamboo
higher than the reported data for Moso bamboo and the woods components during the alkaline extraction was calculated (cal-
(Huang and Ragauskas, 2013; Jun et al., 2012; Li et al., 2012). The culation not shown). By increasing the alkali charge up to 18%
higher glucan content should translate into a higher chemical pulp- (based on the original chips), the calculated cellulose mass frac-
ing yield. In terms of the hemicelluloses in bamboo isxylan rich with tion loss was 0.1–1.2% (based on the o.d. original chip mass),
a similar xylan content (20%) to that of the hardwood, aspen. The which would not significantly affect the pulping yield. Its high
Klason lignin content in the studied bamboo was 24.4%, which was crystallinity and limited accessibility towards chemicals make cel-
slightly higher than other reported results for Moso bamboo and lulose very recalcitrant towards degradation under mild conditions
aspen, but lower than that of softwood (Loblolly Pine) (Table 2). such as those utilized in this study (Engström et al., 2006). The
Lower lignin content means easier delignification in kraft pulping mass fraction loss of lignin, calculated from the data presented
process. Water and solvent extractives were 4.6%, lower than the in Table 3, was 0.2–1.3% (based on the original o.d. chip mass).
7.1% found for Moso bamboo (Li et al., 2012). The ash and silica con- The results show that the treatment time and temperature used
tent of bamboo chips (2.11% and 1.12%, respectively) were much in this study did not significantly degrade the lignin in bamboo
higher than those of woods in which the silica content is less than chips, which means the lignin co-precipitation can be avoided dur-
0.01% while the ash content is 0.3–1.0% (Torelli and Čufar, 1995). ing the silica recovery from the AEL, resulting in high purity silica
These data illustrate both the advantage and challenge of using particles.
bamboo as an alternative feedstock for pulping applications. In The loss of galactan and arabinan, did not contribute much to
terms of the challenge, for example, on a daily basis, approximately yield loss as the content in the starting material was low (total
34 tons/day of soluble silicates will be generated from a 1500 ton mass fraction less than 1.5% in raw chips); the majority of the
chips/day bamboo kraft pulp mill and 70% of these silicates will extracted hemicelluloses was xylan. According to the data shown
be introduced into the chemical recovery circuit of a typical kraft in Tables 2 and 3, it can be concluded that up to 50% of the original
mill using bamboo (Salmela et al., 2008). In addition to the chal- xylan in raw chips was extracted during alkaline pre-treatment and
lenges posed by silica, high overall ash content will interfere with that the amount of extracted xylan increased with increasing NaOH
other process steps; for example high ash levels can lead to acid charge, reaction temperature and reaction time. For example, about
neutralization reactions during pre-hydrolysis with dilute acid or 30% of original xylan mass was extracted by treating bamboo chips
water/steam used to remove hemicellulose in dissolving pulp and at 80 ◦ C with 18% NaOH charge for 5 h. In contrast, at 100 ◦ C with
biofuels production (Kapu and Trajano, 2014). the same NaOH charge (18%), about 50% of xylan was extracted in
5 h (Table 3).
3.2. Alkaline extraction of bamboo chips With alkaline extraction, the amount of silica removal from
bamboo chips increased with increasing NaOH charge and tem-
In this study, the goal of alkaline pre-treatment prior to pulping perature. For example, treating bamboo chips for 5 h with 6% NaOH
is to extract maximum silica and hemicelluloses from commercial
70 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75

Table 3
Chemical composition of bamboo chips after pre-treatments with NaOH under varying conditions.

Tmax (◦ C) NaOH Time at Tmax (h) Yield (%) Glucan (%) Xylan (%) Galactan (%) Arabinan (%) Lignin (%) Silica (%)
charge (%)

80 6 1 96.5 48.85 ± 0.65 20.65 ± 0.41 0.52 ± 0.05 0.81 ± 0.04 26.18 ± 0.24 0.58 ± 0.03
2 95.2 49.26 ± 0.44 20.17 ± 0.33 0.54 ± 0.06 0.76 ± 0.08 26.11 ± 0.36 0.36 ± 0.02
3 94.3 49.82 ± 0.59 19.62 ± 0.42 0.51 ± 0.06 0.71 ± 0.07 26.20 ± 0.25 0.23 ± 0.01
4 93.1 50.38 ± 0.28 19.33 ± 0.51 0.59 ± 0.05 0.72 ± 0.1 26.38 ± 0.33 0.21 ± 0.02
5 92.0 50.94 ± 0.45 19.13 ± 0.44 0.50 ± 0.08 0.71 ± 0.06 26.53 ± 0.42 0.18 ± 0.01

12 1 93.5 50.25 ± 0.84 20.86 ± 0.43 0.49 ± 0.07 0.73 ± 0.06 26.75 ± 0.26 0.42 ± 0.02
2 92.2 51.78 ± 0.56 19.85 ± 0.55 0.56 ± 0.04 0.70 ± 0.05 26.85 ± 0.37 0.23 ± 0.01
3 90.7 51.65 ± 0.47 18.74 ± 0.67 0.58 ± 0.05 0.65 ± 0.07 27.13 ± 0.22 0.14 ± 0.02
4 89.1 52.61 ± 0.65 17.73 ± 0.49 0.60 ± 0.08 0.61 ± 0.08 27.45 ± 0.56 0.08 ± 0.01
5 88.4 52.93 ± 0.42 17.26 ± 0.51 0.41 ± 0.04 0.64 ± 0.04 27.50 ± 0.89 0.01 ± 0.01

18 1 92.4 50.57 ± 0.53 20.67 ± 0.42 0.42 ± 0.05 0.68 ± 0.07 26.96 ± 0.48 0.25 ± 0.03
2 90.3 51.79 ± 0.78 19.58 ± 0.68 0.47 ± 0.05 0.67 ± 0.04 27.36 ± 0.75 0.10 ± 0.02
3 88.5 52.87 ± 0.82 18.34 ± 0.79 0.36 ± 0.05 0.72 ± 0.05 27.75 ± 0.64 0.05 ± 0.02
4 85.7 54.66 ± 0.43 17.59 ± 0.46 0.38 ± 0.04 0.76 ± 0.06 28.48 ± 0.87 0.02 ± 0.01
5 84.3 55.54 ± 0.65 16.48 ± 0.54 0.43 ± 0.06 0.73 ± 0.05 28.78 ± 0.92 ND

100 6 1 93.7 49.95 ± 0.55 20.76 ± 0.53 0.37 ± 0.08 0.79 ± 0.03 26.80 ± 0.55 0.34 ± 0.02
2 92.1 50.84 ± 0.68 20.04 ± 0.51 0.39 ± 0.09 0.74 ± 0.07 27.10 ± 0.46 0.27 ± 0.01
3 90.4 51.79 ± 0.58 19.26 ± 0.42 0.33 ± 0.07 0.71 ± 0.1 27.33 ± 0.72 0.19 ± 0.01
4 88.7 52.76 ± 0.66 18.49 ± 0.65 0.52 ± 0.05 0.65 ± 0.06 27.63 ± 0.65 0.14 ± 0.01
5 87.7 53.37 ± 0.44 17.45 ± 0.37 0.43 ± 0.06 0.70 ± 0.08 27.72 ± 0.26 0.11 ± 0.03

12 1 91.6 51.13 ± 0.67 20.56 ± 0.59 0.48 ± 0.04 0.77 ± 0.06 27.30 ± 0.25 0.23 ± 0.02
2 90.3 51.79 ± 0.62 19.08 ± 0.48 0.43 ± 0.07 0.71 ± 0.04 27.48 ± 0.42 0.16 ± 0.02
3 88.5 52.98 ± 0.73 17.74 ± 0.55 0.58 ± 0.1 0.64 ± 0.04 27.81 ± 0.81 0.08 ± 0.01
4 86.1 54.22 ± 0.53 16.58 ± 0.44 0.62 ± 0.04 0.60 ± 0.03 28.35 ± 0.53 0.02 ± 0.005
5 84.2 55.47 ± 0.42 15.31 ± 0.46 0.51 ± 0.06 0.55 ± 0.05 28.75 ± 0.46 ND

18 1 89.4 52.32 ± 0.34 20.51 ± 0.53 0.39 ± 0.05 0.70 ± 0.10 27.98 ± 0.25 0.05 ± 0.02
2 87.2 53.58 ± 0.21 18.68 ± 0.52 0.37 ± 0.07 0.64 ± 0.09 28.34 ± 0.38 0.01 ± 0.004
3 85.8 54.39 ± 0.41 16.66 ± 0.61 0.44 ± 0.08 0.60 ± 0.07 28.57 ± 0.59 ND
4 84.5 54.16 ± 0.54 14.62 ± 0.45 0.43 ± 0.06 0.57 ± 0.03 28.77 ± 0.57 ND
5 82.3 55.07 ± 0.64 12.06 ± 0.38 0.55 ± 0.07 0.59 ± 0.06 29.10 ± 0.64 ND

Note: ND-not detected. Yield-weight percentage of recovered mass after pre-treatment to non pre-extracted biomass, both in dry matter.

charge at 80 ◦ C and 100 ◦ C, about 85% and 90% of initial silica in bam-
boo chips could be removed, respectively. In contrast, at 80 ◦ C using
12% and 18% NaOH charge, up to 95% of silica could be removed
within 3 h. When treating bamboo chips at 100 ◦ C with 18% NaOH
charge, nearly 96% of silica was removed in 1 h. As shown in Table 3,
after the removal of more than 96% of silica mass, the silica content
of treated chips was about 0.04% or even less (based on treated
o.d. chip mass), which means that even the silica impact on high
purity dissolving-grade pulp can be eliminated (Sixta, 2006). With
such low amount of silica (≤0.04%) in treated bamboo chips, the
adverse effect of silica on the chemical recovery process of kraft
pulping can be significantly resolved. Therefore, treated bamboo
chips with more than 96% of silica removal could be readily used
for subsequent production of kraft pulp or dissolving-grade pulp.
3.3. Analysis of the AEL
To further assess the effects of alkaline pre-treatment on the
dissolution of bamboo components, the sugars, soluble lignin and
silica in the extract liquors were analyzed (Table 4). An interest-
ing observation is that the sum of chip yield (Table 3) and solid
contents of the AEL (Table 4) was larger than 100% in all experi-
mental runs. The excess values of the mass balance might be partly
due to the sodium ions bound to dissolved components such as
acetic or uronic acid. On the other hand, the dissolved sodium com-
pounds determined as residual alkali (data not shown) in the AEL
also contributed to the total solid content. As shown in Table 4,
varying the severity of the pre-treatment had little effect on the
extraction of glucan and lignin from bamboo chips into the AEL.
The low glucan (0.1–0.9%) and lignin (0.1–1.2%) content (based on
original o.d. chip mass) in the AEL also confirmed that the cellulose
and lignin are resistant to the studied alkaline pre-extraction con-
ditions. The low lignin content in the AEL not only preserves the
heating value of black liquor obtained from kraft pulping but also
avoids the lignin co-precipitation during silica recovery process.
Thus, the precipitated silica could be easily separated and purified
for further applications such as production of silica nanoparticles
or silica gel. Clearly, this alkaline pre-treatment favored the silica
removal and recovery during kraft pulping of bamboo chips.
The other goal of the alkaline pre-treatment was to extract
hemicelluloses prior to pulping. Even at extraction conditions that
resulted in larger than 96% silica removal, the contents of galactan
and arabinan in the AEL were less than 0.6% of the original o.d. chip
mass; in contrast, depending on the alkaline pre-treatment condi-
tions employed, the xylan content in the AEL increased significantly
from 4.7% to 9.2% (based on the original o.d. chip mass), which cor-
responded to 23–45% of initial xylan in bamboo chips. Moreover,
the data in Tables 3 and 4 show that the hemicellulose content in
both biomass residuals and AELs was 94.2–98.6% of initial hemicel-
luloses in raw chips for all experimental runs, showing a reasonable
agreement of mass balance. The 2–6% xylan not accounted for might
be lost during chip washing after the pre-treatment or through
xylan degradation into products undetected by the methodology
used.
In the alkaline pre-extraction process, the ester linkages
between polysaccharides and lignin were hydrolyzed (Lehto and
Alén, 2013), resulting in the release of hemicelluloses. Moreover, it
has been reported that the hemicelluloses extracted with alkaline
pre-treatment were mostly in the oligomeric or polymeric form
due to the stopping of alkaline peeling reactions at the branches in
the molecular chains (Taherzadeh and Karimi, 2008; Yoon and Van
Heiningen, 2010). Compared to hemicelluloses in the monomeric
form, hemicelluloses in the oligomeric or polymeric form have
potential higher economic applications such as barrier films, hydro-
 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75 71

Table 4
Sugars, soluble lignin and silica in alkaline pre-extraction liquors (% of original oven dried chip mass).

Tmax (◦ C) NaOH charge (%) Time at Tmax (h) Glucan (%) Xylan (%) Galactan (%) Arabinan (%) Lignin (%) Silica (%) TS (%)

80 6 1 0.18 ± 0.11 0.34 ± 0.12 0.01 ± 0.01 0.05 ± 0.01 ND 0.52 ± 0.04 8.44
2 0.40 ± 0.09 0.79 ± 0.25 ND 0.11 ± 0.02 0.40 ± 0.05 0.75 ± 0.02 9.76
3 0.36 ± 0.18 1.48 ± 0.23 0.02 ± 0.01 0.15 ± 0.02 0.50 ± 0.10 0.88 ± 0.02 10.66
4 0.41 ± 0.08 2.05 ± 0.20 0.02 ± 0.01 0.15 ± 0.02 0.65 ± 0.10 0.90 ± 0.02 11.82
5 0.45 ± 0.12 2.40 ± 0.18 0.05 ± 0.01 0.15 ± 0.03 0.85 ± 0.05 0.92 ± 0.03 12.68

12 1 0.35 ± 0.21 0.50 ± 0.10 ND 0.12 ± 0.03 0.25 ± 0.05 0.70 ± 0.02 17.24
2 0.51 ± 0.17 1.80 ± 0.20 ND 0.17 ± 0.02 0.45 ± 0.11 0.88 ± 0.02 18.75
3 0.52 ± 0.12 3.10 ± 0.21 ND 0.24 ± 0.01 0.65 ± 0.05 0.96 ± 0.03 20.21
4 0.53 ± 0.07 4.24 ± 0.10 ND 0.25 ± 0.04 0.78 ± 0.08 1.02 ± 0.03 21.82
5 0.60 ± 0.18 4.66 ± 0.05 0.12 ± 0.03 0.25 ± 0.02 0.92 ± 0.12 1.08 ± 0.02 22.13

18 1 0.55 ± 0.09 1.04 ± 0.08 0.11 ± 0.02 0.18 ± 0.03 0.36 ± 0.03 0.86 ± 0.03 24.49
2 0.60 ± 0.13 2.46 ± 0.16 0.07 ± 0.03 0.20 ± 0.03 0.58 ± 0.02 1.01 ± 0.02 25.68
3 0.60 ± 0.05 4.01 ± 0.07 0.15 ± 0.04 0.18 ± 0.02 0.70 ± 0.05 1.02 ± 0.04 27.39
4 0.58 ± 0.04 5.06 ± 0.14 0.17 ± 0.02 0.17 ± 0.02 0.80 ± 0.13 1.07 ± 0.03 30.28
5 0.61 ± 0.14 6.13 ± 0.15 0.14 ± 0.02 0.20 ± 0.02 0.94 ± 0.10 1.10 ± 0.02 31.59

100 6 1 0.44 ± 0.06 0.71 ± 0.10 0.13 ± 0.04 0.08 ± 0.02 0.15 ± 0.04 0.75 ± 0.05 12.26
2 0.44 ± 0.10 1.60 ± 0.05 0.14 ± 0.02 0.13 ± 0.03 0.30 ± 0.05 0.85 ± 0.02 12.86
3 0.41 ± 0.05 2.74 ± 0.11 0.18 ± 0.04 0.18 ± 0.02 0.60 ± 0.02 0.90 ± 0.05 14.56
4 0.40 ± 0.10 3.73 ± 0.12 ND 0.23 ± 0.03 0.75 ± 0.05 0.96 ± 0.03 16.27
5 0.50 ± 0.15 4.85 ± 0.10 0.10 ± 0.02 0.20 ± 0.02 0.90 ± 0.10 1.01 ± 0.03 17.19

12 1 0.50 ± 0.13 1.20 ± 0.06 0.06 ± 0.03 0.10 ± 0.03 0.20 ± 0.12 0.87 ± 0.04 19.32
2 0.56 ± 0.13 3.01 ± 0.14 0.10 ± 0.03 0.18 ± 0.02 0.41 ± 0.08 0.94 ± 0.03 20.65
3 0.50 ± 0.18 4.44 ± 0.10 ND 0.24 ± 0.04 0.64 ± 0.07 1.02 ± 0.03 22.43
4 0.65 ± 0.10 5.76 ± 0.14 ND 0.28 ± 0.04 0.80 ± 0.10 1.06 ± 0.0.05 23.87
5 0.75 ± 0.10 7.21 ± 0.08 0.07 ± 0.02 0.34 ± 0.03 1.02 ± 0.12 1.09 ± 0.03 25.72

18 1 0.62 ± 0.05 1.69 ± 0.05 0.14 ± 0.03 0.19 ± 0.02 0.26± 0.03 1.05 ± 0.02 27.48
2 0.65 ± 0.13 3.84 ± 0.05 0.16 ± 0.03 0.25 ± 0.03 0.55 ± 0.06 1.08 ± 0.03 29.69
3 0.69 ± 0.17 5.70 ± 0.16 0.12 ± 0.02 0.27 ± 0.05 0.74 ± 0.05 1.10 ± 0.03 31.08
4 0.79 ± 0.14 7.80 ± 0.20 0.14 ± 0.02 0.30 ± 0.05 0.92 ± 0.09 1.10 ± 0.03 32.39
5 0.91 ± 0.21 9.20 ± 0.10 0.05 ± 0.02 0.31 ± 0.04 1.20 ± 0.05 1.10 ± 0.03 32.59

Note: ND-not detected. TS-total solids.

gel, paper additives, and biofuels (Persson et al., 2009; Chirat et al.,
2012; Hamzeh et al., 2013; Bai et al., 2012). Detailed experiments on
the recovery of silica and hemicelluloses from the AEL are being car-
ried out and will be described in a subsequent paper. The AEL after
silica and hemicelluloses removal would be sent to the chemical
recovery circuit of a typical kraft process to recover inorganic chem-
icals such as sodium hydroxide. The impact of the pre-treatments
on subsequent kraft pulping is discussed below.
3.4. Kraft pulping
Chips from three representative alkaline pre-treatment runs
with residual silica content less than 0.05% were selected for subse-
quent kraft pulping. The three pre-treatment runs were those using
18% NaOH at 100 ◦ C for 1 and 5 h and 18% NaOH at 80 ◦ C for 3 h. To
improve the efficiency when applied in a mill process, higher NaOH
charge and shorter reaction times were used for the pre-treatment
These conditions have the potential to extract higher levels of hemi-
celluloses and silica with less cellulose degradation (see previous
discussion in Sections 3.2 and 3.3).
Since increasing effective alkali (EA) charge has been consid-
ered to be more important than increasing H-factor in removing
lignin during the kraft pulping (Sixta, 2006), EA charge was cho-
sen as the variable while reaction temperature and time were kept
constant. In the kraft cooking process, four levels of effective alkali
(EA) charge were studied to investigate the effectiveness of alkaline
pre-extraction on the kraft pulping of bamboo. To compare the kraft
pulping process of extracted bamboo chips and original chips on a
uniform basis, the alkali charged to the treated chips was adjusted
according to the analysis of the residual alkali in the extract liquor.
Table 5 shows the effect of alkaline pre-extraction on the kraft
pulping of bamboo chips. It should be noted that the pulping yield
was expressed as the overall pulp yield (measured based on the
initial oven dry mass of bamboo chips). As shown in Table 5, at all
EA charges, kraft pulps from alkaline pre-treated chips had lower
kappa numbers (lower residual lignin content in the kraft pulp)
than the non pre-extracted bamboo chips, showing that the alkaline
pre-treatment had a positive effect on delignification during kraft
cooking. This might be due to the fact that the removal of hemicellu-
loses/lignin during alkaline pre-treatment process resulted in chips
having a more open structure thus improving the accessibility of the
cooking chemicals to lignin in chips and improving the rate of diffu-
sion of degraded lignin into the black liquor. For example, a kappa
number of 16.0 could be achieved by pulping extracted chips at
100 ◦ C for 1 h with 17% EA while 19% EA was needed when pulping
with control chips (without pre-treatment) under the same condi-
tions. Increasing the pre-treatment severity (longer time and higher
temperature) also decreased the kappa number of pulp obtained
under the same kraft cooking conditions (results of chips treated at
100 ◦ C for 1 and 5 h, respectively in Table 5). Moreover, lower kappa
numbers (lower lignin contents) translate into lower demand for
bleaching chemicals and, hence lower bleaching costs.
The total pulp yield of extracted chips was generally slightly
lower than that of the control under the same kraft cooking condi-
tions (Table 5). It should be noted that pulps from extracted chips
had lower kappa numbers (lower lignin content), which accounted
for 0.3–0.6% of the pulp yield. In addition, a lower rejects content
in the pulp could be obtained with alkaline pre-extracted (chips-
below 0.5%) compared to the 1.3–1.5% of the controls; this could be
related to the fact that extracted chips have a more open struc-
ture enabling better penetration of cooking chemicals resulting
in a more even cook. The screened pulp yield obtained from the
extracted chips was similar to that of the control or even higher.
Total pulp yield decreased with increasing EA charge for both the
pre-treated chips and control. Similar results have been obtained
72 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75

Table 5
Effect of alkaline pre-extraction and effective alkali charge on kraft pulping of bamboo.

Pre-extracted EA (%) Rejectsa (%) Total yielda (%) Kappa number Residual silica (%) Silica in BLa (%) CSF (ml) Fines (%)
bamboo chips in pulpa

Control 13 2.3 ± 0.2 55.1 ± 1.4 30.1 ± 0.5 0.19 ± 0.03 0.91 ± 0.03 549 ± 10 17.4
15 1.8 ± 0.4 53.9 ± 1.2 22.6 ± 0.2 0.16 ± 0.01 0.95 ± 0.04 538 ± 8 18.6
17 1.5 ± 0.5 53.6 ± 1.7 18.8 ± 0.6 0.14 ± 0.02 0.95 ± 0.03 544 ± 12 19.1
19 1.3 ± 0.3 53.1 ± 1.2 15.9 ± 0.5 0.13 ± 0.03 0.97 ± 0.04 531 ± 7 19.8

80 ◦ C 3h 13 0.5 ± 0.2 54.3 ± 1.8 27.2 ± 0.6 ≈0.01 ≈0.01 629 ± 12 14.2
15 0.4 ± 0.3 53.1 ± 1.2 20.7 ± 0.7 ≈0.01 ≈0.01 624 ± 9 14.4
17 0.2 ± 0.1 52.2 ± 1.5 16.5 ± 0.4 ND ≈0.04 608 ± 13 14.4
19 ≈0.1 51.0 ± 0.8 13.9 ± 0.2 ND ≈0.02 618 ± 11 14.7

100 ◦ C 1h 13 0.3 ± 0.1 52.3 ± 2.3 27.6 ± 1.2 ≈0.01 ≈0.01 635 ± 8 13.8
15 ≈0.1 52.7 ± 1.3 19.8 ± 0.9 ND 0.04 ± 0.02 624 ± 8 14.0
17 ≈0.1 52.1 ± 1.5 16.4 ± 0.3 ND ≈0.02 619 ± 12 14.4
19 ND 51.4 ± 1.2 12.9 ± 0.8 ND 0.04 ± 0.01 620 ± 11 14.6

100 ◦ C 5h 13 ≈0.1 52.2 ± 1.6 22.4 ± 1.0 ND ND 649 ± 5 13.1

15 ND 51.5 ± 1.9 16.1 ± 0.7 ND ND 640 ± 16 13.6
17 ND 50.9 ± 1.0 13.8 ± 0.6 ND ND 620 ± 9 14.0
19 ND 50.3 ± 1.0 11.1 ± 0.4 ND ND 612 ± 12 14.2
a
Calculations were based on original oven dried chip mass. ND-not detected. BL-black liquor.

by kraft pulping of alkaline pre-extracted aspen chips (Jun et al.,

2012).
The initial kraft pulp (brownstock), drainage resistance is an
important parameter as it strongly affects the downstream opera-
tions such as pulp washing. In this study, the drainage resistance
of the brownstock was determined as Canadian Standard Free-
ness (CSF). As shown in Table 5, the CSF of pre-extracted pulps
were in the range of 600–700 mL whereas the freeness of the
non-extracted pulps ranged from 520–560 mL. Additionally, the
measured amount of fines, determined as fibrous materials with
sizes between 0.07 and 0.2 mm, was lower in pre-extracted pulps
than in control pulps (Table 5); these results were in agreement
with studies on kraft pulping of hemicellulose extracted sugar
maple (Duarte et al., 2011). Therefore, the higher CSF values of
extracted pulps were in accordance with the decrease in the fines
content. Higher CSF means faster rates of water drainage during
brownstock washing, which improves the mill efficiency.
The most significant observation was the very low residual sil-
ica content in kraft pulp from pre-extracted chips. As can be seen in
Table 5, the residual silica content of the pulp from pre-extracted Fig. 1. Plot of pulp freeness (CSF) versus PFI mill revolution for pulps obtained from
kraft pulping of extracted and non-extracted chips with 19% EA.
chips was below 0.02% while it was 0.15–0.19% (based on original
o.d. chip mass) in the control. One reason for the high residual silica
content of the pulp from non-extracted chips might be that the sili-
cates dissolved during pulping adhere onto the fiber surface and are need more refining energy to attain the same level of freeness as
not removed during subsequent pulp washing. High silica contents the control. This agrees well with the generalized experience that
in kraft pulp make it unsuitable for use in high grade products such pulps with low content of hemicelluloses and fines are difficult to
as ashless filter paper or facial tissue. In addition to the challenges of beat to a target freeness due to the small degree of internal fibrilla-
silica in the kraft pulp, high silica content in black liquor also causes tion with increased refining (Walton et al., 2010). Similar refining
problems in the chemical recovery process such as scaling of evap- results were also obtained in kraft pulping with extracted and non-
orators, decrease in causticizing efficiency, and the generation of extracted chips with 15%, 17% and 19% EA (data not shown).
large amount of solid waste (calcium silicate mixed with calcium The strength properties of all pulps were determined at the
carbonate). Moreover, silica in the black liquor is difficult to remove CSF of 425 mL. Plots of tensile and tear indices against EA charge
because of high lignin content. Therefore, alkaline pre-treatment is of handsheets of pulps from pre-extracted chips and the control
a promising approach to solve the silica problems when pulping pulp are shown Figs. 2 and 3, respectively. Tensile strength index
bamboo chips. of pulps from alkaline pretreated bamboo chips initially increased
with increasing EA charge, thereafter it decreased. For the control
samples, the tensile index increased with increasing EA charge.
3.5. Pulp physical properties These results confirmed the result that the delignification rate of
pre-extracted chips was faster than the control. With the higher
It is important to assess the impact of the extraction process on removal of lignin from treated chips at lower EA charge, more
the physical properties of resulting pulps. As indicated in Fig. 1 the bonding could be formed among cellulosic fibres than in the case
initial freeness of the control pulp was much lower than the ini- of the control, resulting in the improvement of physical proper-
tial freeness of the pulps from chip pre-extracted with 19% EA. The ties of handsheets. However, with continually increasing the EA
rate of freeness drop with PFI refining was similar for all the pulps. charge, compared to the control pulps, the handsheet strength of
These results indicate that pulps from alkaline pre-extracted chips pulps from extracted bamboo chips decreased significantly. One
 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75
Fig. 2. Effect of pre-extraction and effective alkali charge on the tensile index of
pulp.
Fig. 3. Effect of pre-extraction and effective alkali charge on the tear index of pulp.
likely reason is the lower hemicellulose content in extracted pulps,
resulting in fewer bonding.
It can be seen in Fig. 2 that the tensile strength index of
pulps from chips extracted using milder pre-treatment conditions
(80 ◦ C for 3 h and 100 ◦ C for 1 h) decreased at EA charges higher
than 17%. This decrease began at 15% EA in the pulps from chips
extracted at high severity (100 ◦ C for 5 h). This is probably due to
the loss of different amounts of hemicelluloses during the alkaline
pre-extraction processes. With the increase in the intensity of alka-
line pre-extraction, more hemicelluloses were removed, resulting
in higher cellulose/hemicelluloses ratio, which will form larger
macrofibrils during handsheet making (Molin and Teder, 2002;
Walton et al., 2010), resulting in lower bonding. In addition, at the
highest tensile index of handsheets, hemicelluloses contents of the
pulps were 7.01%, 5.45%, 5.78% and 5.12% (based on original o.d.
chip mass) for non-treated chips and chips pre-treated under con-
ditions of 80 ◦ C for 3 h, 100 ◦ C for 1 h, and 100 ◦ C for 5 h, respectively.
Thus, it confirmed the assumption that hemicellulose content plays
an important role in the strength properties of paper.
Fig. 3 shows that the tear index of extracted pulp was bet-
ter than that of non-extracted pulp. The overall improvement of
tear strength with alkaline pre-extraction can be explained by the
73
removal of lignin and hemicelluloses making the resultant kraft
pulps to contain more cellulose per gram handsheet.
Results of the kraft pulping with extracted and non-extracted
chips show that the alkaline pre-extraction is suitable for produc-
tion of both papermaking fiber and dissolving pulps (high purity
cellulose). Moreover, the pre-extraction process removes hemicel-
luloses and silica from the black liquor cycle which will improve
the efficiency of chemical recovery. The hemicellulose and silica
removed during the process can potentially be converted into other
value-added products.
3.6. Proposed modification to kraft pulping process and mass
balance
Based on our findings, we propose a process for the integration
of low temperature alkaline pre-extraction of silica and hemicellu-
loses from bamboo chips into a commercial kraft pulping process as
illustrated in Fig. 4. In a typical kraft pulp mill, alkali is readily abun-
dant as kraft white liquor, so the integration of this pre-extraction
stage could be achieved without major capital investment or exten-
sive process changes. In the proposed process scheme, washed
bamboo chips are treated with alkali solution under atmospheric
conditions from which a liquor rich in silica and hemicelluloses
is produced. Silica and hemicellulose fractions are recovered from
this AEL as potential starting materials for value added products.
The treated AEL is mixed with the black liquor for the recovery
of inorganic chemicals such as NaOH. Pre-extracted chips are then
processed through kraft pulping or pre-hydrolysis kraft pulping to
produce high-grade kraft pulp or dissolving pulp.
Taking the 4 h pre-extraction at 100 ◦ C with 18% NaOH as an
example, the mass balance of the main components of bamboo
around the whole system from pre-treatment to kraft cooking can
be determined (Fig. 4). Mass balance of each fraction is expressed
in terms of dried material mass. With regards to the pre-treatment
stage, the sum of recovered organics (cellulose, hemicelluloses,
lignin) and inorganic (silica) in both biomass residual and AEL cor-
responded to 98.4% of those in the raw bamboo chips. The 1.6%
material loss is due to the degradation of lignin and/or hemicellu-
loses into unidentified products. The analysis of the AEL showed
that about 37% of hemicelluloses (mainly xylan) and 99% of silica
contained in raw bamboo chips were extracted, showing a good
revenue source for the mill and a novel way for solving the sil-
ica problems. Then pretreated bamboo chips (without washing)
were subjected to kraft cooking, performed at 15% EA charge and
25% sulfidity. Based on 100 g o.d. mass of chips entering the pre-
extraction-kraft pulping process, the mass of obtained pulp was
determined to be 51.6 g, in which masses of cellulose, hemicel-
luloses, and lignin were 43.8 g, 4.8 g, and 2.7 g, respectively. The
recovered masses of cellulose and hemicelluloes in the brownstock
corresponded to 95.6% and 36.4% of the two components in the pre-
treated chips, respectively, showing reasonable agreement with
previous studies (Pinto et al., 2005; Vu Mân et al., 2004). The losses
of cellulose and hemicelluloses during delignification might be due
to peeling reactions and alkaline degradation, respectively (Rocha
et al., 2012). For the material balance of lignin during kraft pulp-
ing, as shown, the total amount of precipitated lignin in the black
liquor and lignin in the final pulp was 19.9 g, which was equivalent
to 81.9% of the lignin in pretreated chips. The 18.1% loss of lignin
in raw chips during kraft cooking might be due to water washing
of the kraft pulp and incomplete lignin precipitation during black
liquor acidification. Finally, with regards to the main components
(cellulose, hemicelluloses and lignin), the overall recovery of the
proposed system from pre-extraction to kraft pulping showed a
good mass balance of 82.7%.
The advantage of our proposed approach is that the method
decouples silica from organics-rich black liquor enabling silica
74 Z. Yuan et al. / Industrial Crops and Products 91 (2016) 66–75
Fig. 4. Proposed process of kraft pulping with silica and hemicelluloses extraction unit with NaOH.
recovery without substantial loss of lignin and hemicelluloses. A
further study on the recovery of silica and hemicelluloses in the
liquid fraction will be discussed in a forthcoming paper.
4. Conclusions
Analysis of the distribution of chemical components in the
bamboo stem showed that the whole stem should be used for
commercial chips preparation. Alkaline pre-extraction of bamboo
chips prior to pulping processes was demonstrated to be an effec-
tive way to extract silica and hemicelluloes selectively without
degrading cellulose and lignin. Under the studied extraction con-
ditions, almost 100% of silica and up to 50% of hemicelluloses in
bamboo chips were extracted. Taking account into the considera-
tion for efficiently dissolution of silica and hemicelluloses removal
was more efficient at a pre-treatment temperature at 100 ◦ C com-
pared to 80 ◦ C. Pre-extraction of the chips improved delignification
during kraft pulping even at lower effective alkali charges. Pulp
from pre-extracted bamboo chips showed similar screened yield to
that of non-extracted chips while initial drainage resistance (CSF)
improved slightly. The tensile strength index of the pulp actually
benefited from the alkaline pre-treatment at low EA charges. The
tear strength index of the kraft pulp was improved by the alkaline
pre-extraction. Silica was not detected in the kraft pulp and black
liquor obtained with pre-extracted bamboo chips indicating that
the process provides a solution to silica problems encountered in
bamboo pulping.
To make the proposed process fit well into the integrated forest
biorefinery concept, investigations into the isolation, purification
and transformation of silica and hemicelluloses from the AEL into
valuable products are being carried out in our laboratory.
Acknowledgements
This work was funded by Lee & Man Paper Manufacturing Lim-
ited. The authors are grateful to Elaine Woo, British Columbia
Institute of Technology, and Professors Jack Saddler, Valdeir Arantes
and Phillip Evans, University of British Columbia, Vancouver, for
providing devices and technical support in this study.
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